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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 613 records · Page 34
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Fluorine-Tuned Carbon-Based Nickel Single-Atom Catalysts for Scalable and Highly Efficient CO 2 Electrocatalytic Reduction

Electrocatalytic CO 2 reduction is garnering significant interest due to its potential applications in mitigating CO 2 and producing fuel. However, the scaling up of related catalysis is still hindered by several challenges, including the cost of the catalytic materials, low selectivity, small current densities to maintain desirable selectivity. In this study, Fluorine (F) atoms were introduced into an N-doped carbon-supported single nickel (Ni) atom catalyst via facile polymer-assisted pyrolysis. This method not only maintains the high atom utilization efficiency of Ni in a cost-effective and sustainable manner but also effectively manipulates the electronic structure of the active Ni-N 4 site through F doping. The catalyst has also been further optimized by controlling the F states, including convalent and semi-ionic states, by adjusting the fluorine sources involved. Consequently, this catalyst with unique structure exhibited comparable electrocatalytic performance for CO 2 -to-CO conversion, achieving a Faradaic efficiency (FE) of over 99% across a wide potential range and an exceptional CO evolution rate of 9.5 x 10 4 h -1 at -1.16 V vs reversible hydrogen electrode (RHE). It also delivered a practical current of 400 mA cm -2 while maintaining more than 95% CO FE. Experimental analysis combined with density functional theory (DFT) calculations have also shown that F-doping modifies the electron configuration at the central Ni-N 4 sites. In conclusion, this modification lowers the energy barrier for CO 2 activation, thereby facilitating the production of the crucial *COOH intermediate.

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

Chemo-Mechanical Instabilities in Lithium Cobalt Oxide at Higher State-Of-Charge in Li-Ion Batteries

Transition metal oxide cathodes are widely used in commercial Li-ion batteries. However, their practical charge capacity is limited due to severe chemo-mechanical instabilities at higher charge voltage, and state-of-charge condition. Here, in situ stress and strain measurements were synchronized to probe mechanical deformations in the lithium cobalt oxide (LCO) cathode via a multi-beam stress sensor and digital image correlation, respectively. In situ mechanical measurements revealed how Li removal from the electrode structure induces deformations on the LCO composite cathodes during cycling. The structure and morphology of the LCO cathodes were further investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies. Two distinct electrochemical and mechanical behaviors were identified when the LCO was charged up to 4.65 V. The LCO undergoes a compressive stress generation when charged up to 4.2 V and surface fractures on the LCO particles were detected by SEM. LCO cathode experienced significantly large contractions (negative strains) when charged up to 4.65 V, where intergranular crack formation and phase transformation were detected on the LCO particles via SEM and XRD, respectively. Overall, the study bridges complicated structural deformations with in situ analysis of mechanical degradations in LCO cathodes charged at higher voltages. The correlation is vital to understanding instability mechanisms in transition metal oxides at high voltages for alkali metal ion batteries.

higher state-of-charge↗
DOE OSTI2026

Towards a Unified Low-Cost Flow Plate, Flow-Field, PTL Solution for Proton Exchange Membrane Electrolyzers

Proton exchange membrane (PEM) water electrolysis is a highly efficient method for hydrogen production. Research cells typically consist of one proton exchange membrane, two catalyst layers, two porous transport layers, two flow-field plates, and two endplates. In commercial systems, the machined flow-field plates that are employed in research cells are typically replaced by stamped parts or open mesh material solutions to reduce manufacturing cost at scale. Nonetheless, the cell contains about 8 total interfaces: bipolar plate / flow plate material / porous transport medium / electrode / membrane / electrode / porous transport medium / flow plate material / bipolar plate. All these materials and interfaces need to be optimized for maximum performance and efficiency. Reducing the amount of interfaces by combining individual cell components directly benefits the fabrication cost (by reducing the parts count and the needs for surface coatings) and the electrochemical performance (by reducing ohmic losses). We have designed a novel PEM electrolysis cell with a piece of channeled titanium felt functioning as both the anode flow-field and the PTL, referred to as the channeled diffusion layer (CDL). The pores of the felt facilitate both in-plane and through-plane diffusion, ensuring maximum catalyst utilization while also minimizing mass transport loss. The titanium felt can be mass manufactured with existing stamping and forming methods and is therefore a promising candidate to reduce the capital cost of PEM electrolyzers whilst improving hydrogen production efficiency. Experiments conducted with 3mg IrOx/cm2 loading MEAs have shown a approximately 40% boost in peak current by implementing the CDL design. Low catalyst-loading MEAs are being tested in ongoing experiments and their results will be discussed and compared.

08 HYDROGEN↗
DOE OSTI2023

Kinetically versus thermodynamically controlled factors governing elementary pathways of GaP(111) surface oxidation

GaP and related III-V semiconductors have attracted interest as high-efficiency photoelectrochemical electrodes for solar water splitting. However, their efficacy is linked to the presence, identity, and integrity of native surface oxides, which are structurally and chemically complex and evolve during operation. Using ambient pressure X-ray photoelectron spectroscopy (APXPS) coupled with ab initio simulations, we track key chemical motifs expressed during evolution of GaP(111) surface oxides, their associated reaction kinetics, and their correlations with electronic properties. We identify two distinct thermal regimes corresponding to kinetically and thermodynamically controlled oxidation. Below 600 K, exposure to O2 generates kinetically facile Ga-O-Ga configurations, whereas higher temperatures cause activated oxygen to insert into Ga–P bonds as part of a thermodynamically driven transformation into a complex, heterogeneous 3D network of surface POx (1≤x ≤ 4) groups and Ga2O3 species, the latter of which eventually dominates upon depletion of surface phosphorus. Here our study highlights the critical competition between kinetic and thermodynamic factors during GaP oxidation, yielding insights for fabricating stable III-P-based photoelectrodes with precisely engineered surface properties.

08 HYDROGEN↗
DOE OSTI2025

Hydrotrope-enabled high concentration aqueous electrolytes for reversible and sustainable iron metal anodes

Iron metal-based energy storage devices hold great potential in stationary grid-scale sustainable energy due to the high theoretical specific capacity, ultralow cost, and abundance of iron. However, their practical deployment is limited by the poor reversibility of iron plating and stripping, as well as competitive hydrogen evolution. Here we introduce the concept of hydrotropy into iron electrolytes by developing an environmentally friendly and cost-effective high-concentration ferrous sulfate electrolyte using urea as a hydrotropic agent. The designed electrolyte increases the Coulombic efficiency of iron metal electrodes to approximately 96.5%, compared with ~84.6% for the dilute electrolyte. Molecular dynamics simulations and Raman spectroscopy illustrate that urea regulates the competitive coordination of anions and urea in the iron solvation sheath, while reconstructing the hydrogen-bond network in free water molecules. This reduces the activity of both solvated and free water, thereby alleviating hydrogen evolution. Moreover, the coordinated anions and urea molecules facilitate the in-situ formation of an organic-inorganic hybrid protective layer on the metallic iron, establishing a physical barrier against water and promoting homogeneous interfacial reactions. This work demonstrates an appealing opportunity to design cost-effective and high-performance electrolytes and propels the practical application of iron metal-based energy storage devices.

Feng, Guangxia [Stanford Univ., CA (United States)↗
DOE OSTI2020

Methanol tolerance of atomically dispersed single metal site catalysts: mechanistic understanding and high-performance direct methanol fuel cells

Proton-exchange membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs) are promising power sources from portable electronic devices to vehicles. The high-cost issue of these low-temperature fuel cells can be primarily addressed by using platinum-group metal (PGM)-free oxygen reduction reaction (ORR) catalysts, in particular atomically dispersed metal–nitrogen–carbon (M–N–C, M = Fe, Co, Mn). Furthermore, a significant advantage of M–N–C catalysts is their superior methanol tolerance over Pt, which can mitigate the methanol cross-over effect and offer great potential of using a higher concentration of methanol in DMFCs. In this work, we investigated the ORR catalytic properties of M–N–C catalysts in methanol-containing acidic electrolytes via experiments and density functional theory (DFT) calculations. FeN 4 sites demonstrated the highest methanol tolerance ability when compared to metal-free pyridinic N, CoN 4 , and MnN 4 active sites. The methanol adsorption on MN 4 sites is even strengthened when electrode potentials are applied during the ORR. The negative influence of methanol adsorption becomes significant for methanol concentrations higher than 2.0 M. However, the methanol adsorption does not affect the 4e - ORR pathway or chemically destroy the FeN 4 sites. The understanding of the methanol-induced ORR activity loss guides the design of promising M–N–C cathode catalyst in DMFCs. Accordingly, we developed a dual-metal site Fe/Co–N–C catalyst through a combined chemical-doping and adsorption strategy. Instead of generating a possible synergistic effect, the introduced Co atoms in the first doping step act as “scissors” for Zn removal in metal–organic frameworks (MOFs), which is crucial for modifying the porosity of the catalyst and providing more defects for stabilizing the active FeN 4 sites generated in the second adsorption step. The Fe/Co–N–C catalyst significantly improved the ORR catalytic activity and delivered remarkably enhanced peak power densities (i.e., 502 and 135 mW cm -2 ) under H 2 –air and methanol–air conditions, respectively, representing the best performance for both types of fuel cells. Notably, the fundamental understanding of methanol tolerance, along with the encouraging DMFC performance, will open an avenue for the potential application of atomically dispersed M–N–C catalysts in other direct alcohol or ammonia fuel cells.

25 ENERGY STORAGE↗
DOE OSTI2025

Understanding the Beneficial Role of Transition-Metal Layer Na + Substitution on the Structure and Electrochemical Properties of the P2-Layered Cathode Na 2+ x Ni 2– x /2 TeO 6

Layered Na x MO 2 sodium oxide positive electrode materials have experienced renewed interest owing to the current commercial attention on sodium-ion batteries. Although there are many attractive qualities of these materials, they suffer from serious shortcomings owing to Na + ordering and transition-metal layer gliding that cause a plethora of voltage plateaus during cycling. The P2-layered Na 2+x Ni 2–x/2 TeO 6 (0 ≤ x ≤ 0.5) system provides a framework for investigating the effect of dual Na + substitution into the sodium layer and the transition-metal layer of the structure and its effects on the electrochemical properties of the materials. A careful investigation into the synthesis and properties of these materials reveals that the sodium content used during material preparation has a drastic effect on the composition and electrochemical profile of these materials. The sodium substitution disrupts ordering within the transition-metal layer, thereby disrupting Na + ordering in the adjacent sodium layers. Beyond a critical sodium concentration, the layer stacking shifts, and all voltage plateaus of the P2-Na 2 Ni 2 TeO 6 material are no longer observed at 4.4 V versus Na + /Na. These results also question the common belief that additional sodium precursor is required when preparing layered sodium oxide cathodes, providing new guidelines for material synthesis and characterization.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Excitonic Effects in X-ray Absorption Spectra of Fluoride Salts and Their Surfaces

Given their natural abundance and thermodynamic stability, fluoride salts may appear as evolving components of electrochemical interfaces in Li-ion batteries and emergent multivalent ion cells. This is due to the practice of employing electrolytes with fluorine-containing species (salt, solvent, or additives) that electrochemically decompose and deposit on the electrodes. Operando X-ray absorption spectroscopy (XAS) can probe the electrode–electrolyte interface with a single-digit nanometer depth resolution and offers a wealth of insights into the evolution and Coulombic efficiency or degradation of prototype cells, provided that the spectra can be reliably interpreted in terms of local oxidation state, atomic coordination, and electronic structure about the excited atoms. Here we explore fluorine K-edge XAS of mono- (Li, Na, and K) and di-valent (Mg, Ca, and Zn) fluoride salts from a theoretical standpoint and discover a surprising level of detailed electronic structure information about these materials despite the relatively predictable oxidation state and ionicity of the fluoride anion and the metal cation. Utilizing a recently developed many-body approach based on the ΔSCF method, we calculate the XAS using density functional theory and experimental spectral profiles are well reproduced despite some experimental discrepancies in energy alignment within the literature, which we can correct for in our simulations. We outline a general methodology to explain shifts in the main XAS peak energies in terms of a simple exciton model and explain line-shape differences resulting from the mixing of core-excited states with metal d character (for K and Ca specifically). Given ultimate applications to evolving interfaces, some understanding of the role of surfaces and their terminations in defining new spectral features is provided to indicate the sensitivity of such measurements to changes in interfacial chemistry.

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

A mechanistic study of mesoporous TiO 2 nanoparticle negative electrode materials with varying crystallinity for lithium ion batteries

Nanoscale oxide-based negative electrodes are of great interest for lithium ion batteries due to their high energy density, power density and enhanced safety. In this work, we conducted a case study on mesoporous TiO 2 nanoparticle negative electrodes with uniform size and varying crystallinity in order to investigate the trend in the electrochemical properties of oxide-based nanoscale negative electrodes with varying crystallinity. Furthermore, mesoporous solid spherical TiO 2 nanoparticles with a uniform particle size and varying crystallinity, i.e. , amorphous TiO 2 (A-TiO 2 ), partially crystalline TiO 2 (PC-TiO 2 ) and fully crystalline TiO 2 (FC-TiO 2 ) nanoparticles were studied. At low current rate (quasi steady-state), the specific capacity of the samples drops with the decrease of crystallinity. Ex situ synchrotron pair distribution function analysis reveals that the 1D zigzag Li ion diffusion pathway becomes expanded with the increase of crystallinity, which promotes ion mobility and charge storage. At high current rates (away from equilibrium states), however, the A-TiO 2 sample demonstrates slightly larger capacity than the FC-TiO 2 sample, both of which show larger capacities than that of the PC-TiO 2 sample. Both A-TiO 2 and FC-TiO 2 samples exhibit higher capacitive contribution to the charge storage and larger Li + diffusivity than those of the PC-TiO 2 sample, which explains their better rate capability. Moreover, the larger Li + diffusivity of the A-TiO 2 sample leads to the slightly larger specific capacity than the FC-TiO 2 sample at the highest current rate.

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

In-Situ FTIR Detection of Transition Metal (TM)-Ion Dissolution From Cathodes in Li-Ion Batteries

Transition metal (TM) ions, commonly Ni and Mn, play a crucial role in Li-ion battery cathodes as the reaction centers for rapid redox reactions. A major challenge with TM-based cathodes is capacity degradation, particularly at higher operating voltages. This degradation is closely linked to the dissolution of TMs from the cathode materials and their subsequent deposition on the anode. This process not only modifies the surface structure of the cathode but, more significantly, alters the SEI composition on the anode [1-2]. The dissolution of TMs cations into a liquid electrolyte from cathode materials, such as Mn-ion dissolution from Mn-rich cathode (LMR), is detrimental to the cycling performance of Li-ion batteries [3-4]. Much attention has been paid to this issue but there remains a lack of characterization techniques which can detect the TM-ion dissolution from the cathode during electrochemical measurements. In our study, we use in-situ ATR-FTIR as an effective technique to probe the TM-ion dissolution from the cathode. We have first demonstrated the detrimental effects of TM ions on the electrochemical performance of Li-ion batteries by adding a small amount of TM salt (50 mM Mn(PF6)) to the electrolyte of a Li-ion coin cell with LFP and graphite electrode. We observed a rapid capacity fade after the first delithiation cycle. To investigate TM ion dissolution, we established a baseline IR spectrum for various TM solvation states (such as Mn and Ni) by measuring concentration-dependent IR spectra. This baseline spectrum helps us detect TM ion dissolution during battery cycling. In this work, we discuss in detail the effect of TM ions on the electrochemical performance of Li-ion batteries and the detection of TM ions during battery cycling using in-situ FTIR spectroscopy. We will compare TM dissolution between coated and uncoated cathodes to examine the effect of cathode coatings to mitigate degradation due to TM dissolution and cross-over from cathode to anode. References: (1) Zhan, C.; Wu, T.; Lu, J.; Amine, K. Dissolution, migration, anddeposition of transition metal ions in Li-ion batteries exemplified byMn-based cathodes - a critical review. Energy Environ. Sci. 2018, 11,243-257. (2) Jung, R.; Linsenmann, F.; Thomas, R.; Wandt, J.; Solchenbach,S.; Maglia, F.; Stinner, C.; Tromp, M.; Gasteiger, H. A. Nickel,Manganese, and Cobalt Dissolution from Ni-Rich NMC and TheirEffects on NMC622-Graphite Cells. J. Electrochem. Soc. 2019, 166,A378-A389. (3) Zhao, L.; Chenard, E.; Capraz, O. O.; Sottos, N. R.; White, S.R. Direct Detection of Manganese Ions in Organic Electrolyte by UV-Vis Spectroscopy. J. Electrochem. Soc. 2018, 165, A345-A348 (4) Zhang, Y.; Hu, A.; Xia, D.; Hwang, S.; Sainio, S.; Nordlund, D.;Michel, F. M.; Moore, R. B.; Li, L.; Lin, F. Operando characterization and regulation of metal dissolution and redeposition dynamics nearbattery electrode surface. Nat. Nanotechnol. 2023, 18, 790.

25 ENERGY STORAGE↗
DOE OSTI2022

Core-Shell Heterostructures as Functional Materials for Solid Oxide Fuel Cell (SOFC) Electrodes

The principal objective of this project was to synthesize core-shell heterostructures for solid oxide fuel cell cathodes using a molten salt solvent. In doing so, the main goals were split into a) to elucidate and understand the influence of molten salt chemistries to expeditiously synthesize perovskite type oxides for solid oxide fuel cells, b) provide a chemical framework for future molten salt syntheses of energy relevant ceramic materials, c) demonstrate and investigate the required parameters for the optimal core-shell synthesis and yield of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 (LSCF) – La 0.8 Sr 0.2 MnO 3 (shell), and d) demonstrate improved cathode performance of core-shell LSCF-LSM compared to an LSCF cathode on symmetric cells. The results clearly show that a) the influence of the molten salt cation outweighs the anion in regards to product stoichiometry, b) molten salts should be tailored to balance cationic and anionic acidity for high product yield, c) high yield of core-shell nanoparticles can be achieved by optimal mass ratio between core to shell, dwell time in the salt, size ratio between core to shell, and mass ratio between overall powder to salt, and d) the core-shell LSCF-LSM cathodes have lower polarization resistances than LSCF at higher temperatures. More work is required to optimize core-shell cathode performance at lower temperatures. However, this work thus provided justification for using the molten salt synthesis for SOFC cathodes and provided insights into future material modifications for improved performance.

08 HYDROGEN↗
DOE OSTI2023

Study on the Carbon Nanostructures for Nanosized Si Electrodes

Silicon (Si) has been considered as a next-generation anode material due to natural abundance, low operating potential (<0.5 V vs. Li/Li+), and high theoretical specific capacity of 4200 mAh g-1.[1] However, the electrochemical alloying reaction of Si involves large volume changes of 400% during lithiation and delithiation, causing cracking and pulverization of Si.[1] In addition, solid electrolyte interface (SEI) of Si anode experiences constant changes due to unstable SEI reactivity.[2] Considerable efforts have been made to design nanostructured Si materials to address the issues because nanostructuring can relieve the mechanical strain.[3] However, when compared to micrometer-sized active materials having sufficient electrolyte pathway through interparticle space, the nanoparticle (NP)-based electrodes tend to be densely packed. As mass loading is higher and electrode is thicker, ion transport issue can become more severe in the densely packed electrodes.[4] In this work, we will present studies on engineered porosity impacts performance in Si NP electrodes by altering carbon nanostructures. We explore the extreme limit of effectively non-porous electrodes using quasi-spherical, Si NPs, which result in densely packed electrodes when slurry is prepared with conventional carbon black. We engineer porosity using carbon nanostructures including multi-walled carbon nanotubes and carbon nanorods in place of conventional carbon black to create pore structure in Si NP-based electrodes. These experiments provide a correlation between mass loading, porosity and silicon utilization in Si NP-based electrodes. References: [1] C. K. Chan, H. Peng, G. Liu, K. Mcllwrath, X. F. Zhang, R. A. Huggins, Y. Cui, "High-performance lithium battery anodes using silicon nanowires", Nat. Nanotechnol., 2008, 3, 31, [2] J. D. McBrayer, M.-T. F. Rodrigues, M. C. Schulze, D. P. Abraham, C. A. Apblett, I. Bloom, G. M. Carroll, A. M. Coclasure, C. Fang, K. L. Harrison, G. Liu, S. D. Minteer, N. R. Neale, G. M. Veith, C. S. Johnson, J. T. Vaughey, A. K. Burrel, B. Cunningham, "Calendar aging of silicon-containing batteries", Nat. Energy, 2021, 6, 1164, [3] H. Wu, G. Zheng, N. Liu, T. J. Carney, Y. Yang, Y. Cui, "Engineering Empty space between Si Nanoparticles for Lithium-Ion Battery Anodes", Nano Lett., 2012, 12, 904, [4] X. Zhang, Z. Ju, Y. Zhu, K. J. Takeuchi, E. S. Takeuchi, A. C. Marschilok, G. Yu, "Multiscale Understanding and Architecture Design of High Energy/Power Lithium-Ion Battery Electrodes", Adv. Energy Mater., 2021, 11, 2000808

carbon nanostructure↗
DOE OSTI2022

Performance and Economic Analysis of Organosolv Softwood and Herbaceous Lignins to Activated Carbons as Electrode Materials in Supercapacitors

In this work, yellow pine (YP, softwood) and switchgrass (SG, grass) lignins were extracted as a coproduct of an organosolv γ-valerolactone (GVL) biorefinery that also produces biofuels and furfural. The extracted lignins were converted to carbon precursors for synthesizing porous activated carbon electrodes for high energy-density supercapacitors. This research details the impact of lignin composition on the derived porous structures and electrochemical properties of activated carbons. Lignin precursors with various syringyl (S) to guaiacyl (G) contents were characterized using 31 P nuclear magnetic resonance (NMR) and two-dimensional 1 H‒ 13 C NMR. A two-step activation process, using steam and carbon dioxide as the activating agents, enabled the formation of porous carbons structures with high surface area. The capacitive behavior of supercapacitors was systematically characterized by cyclic voltammetry, charge-discharge cycling, and electrochemical impedance spectroscopy. The specific capacitance of YP and SG capacitors reached 367 and 221 F g −1 , respectively. Both types of capacitors demonstrated remarkably stable capacitance (capacitance retention >90%) along with excellent Coulombic efficiency (>99%) over 10,000 cycles. Compared to SG electrode, the better electrochemical performance achieved with YP electrodes was mainly due to shorter diffusion path, improved ionic mobility, and increased active surface area. The inexpensive lignin-based porous electrodes synthesized in this work can be used for various electrochemical devices for improved performance, decreased cost, and enhanced durability. This work also demonstrates that the selection of feedstock and appropriate processing conditions can tailor the structure of carbon composites for targeted applications. Techno-economic analysis indicates that YP and SG activated carbons can be produced at a minimum selling price of $8,493 and $6,670 per ton, respectively, which is competitive with the commercially available supercapacitor-grade activated carbons.

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

Perovskite Grown in Gallium Nitride Nanowire Matrix for Stable and High‐Efficiency X‐Ray Detection

High-quality quasi-2D perovskites in a GaN nano-wire matrix are grown to build a 3D hetero-structure for high-performance X-ray sensing. In the 3D hetero-structure, GaN nano-wire matrix serves as an n-type charge collector that can rapidly extract carriers through the bulk film of the perovskite layer. Together with a p-type top electrode, a p–i–n diode with the 3D hetero-structure is built, that exhibits a rectified current–voltage characteristic. After analyzing the interface energy alignment, it is found that the fermi levels of the perovskite and GaN are aligned in the dark, and a quasi-fermi level splits upon illumination, introducing a built-in electrical field at the interface. As a result, strong photo-induced current is observed from the diode without an external field. Finally, the 3D diode for X-ray detection demonstration is used, revealing a sensitivity of 308.9 µC Gy air -1 cm -2 at an exceptionally low applied field of 0.125 V µm -1 . The X-ray-induced signal from the 3D diode is stable after 155 cycles of X-ray irradiation under a constant electric field. This demonstration informs a new 3D architecture for high-performance X-ray sensing, and it shows that GaN is a robust n-type interface for perovskite optoelectronic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Spontaneous sodium ion storage behaviors of reduced graphene oxide anodes exceeding 100% Coulombic efficiency by modulated ion solvation

Rechargeable batteries are essential energy storage devices that power portable devices and electrical vehicles throughout the world. In general, it is thought that the electrochemical performance of rechargeable batteries is mostly determined by the electrodes within them and that the electrolyte plays a relatively passive role. However, ion transport and storage can be greatly influenced by the electrolyte solution structure, specifically, ion solvation within the bulk and ion desolvation across the electrode/electrolyte interfaces. Herein, we studied the role of the electrolyte as an active component of electrochemical energy storage devices. We found that with an appropriate electrolyte formulation, ion storage in disordered carbonaceous anode materials can occur spontaneously without externally supplied electrical energy. Reduced graphene oxide (RGO) in an ether-based electrolyte demonstrates ‘spontaneous' ion storage behaviors of adsorbing and inserting the solvated ions utilizing facilitated permeability and wettability of RGO, which results in Coulombic efficiency of ~145% due to additional charging capacity of ~180 mAh g -1 during electrochemical processes. The unexpected spontaneous ion storage behavior was extensively investigated using a combination of electrochemical analyses and diagnostics, advanced characterizations, and computational simulation. In conclusion, we believe the spontaneous ion storage behavior offers a new way to further improve the energy efficiency of practical rechargeable batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Recent progress and future prospects of atomic layer deposition to prepare/modify solid-state electrolytes and interfaces between electrodes for next-generation lithium batteries

Lithium ion batteries (LIBs) are encouraging electrochemical devices with remarkable properties including a high energy/power density, fast charging capability, and low self-discharge rate. Further increase in energy density as well as safe usage is needed for next-generation LIBs in electric transportation vehicles. Solid-state electrolytes (SSEs) are very promising for high-performance LIBs since they enable improved safety along with increased energy density compared to flammable liquid organic electrolytes. However, utilizing SSEs with a Li metal anode is very challenging due to the possibility of undesired side reactions and the formation of an unstable solid-electrolyte interphase. Therefore, it is critical to enhance the stability of SSEs against the Li anode. One feasible approach is to form a thin and conductive interlayer between the Li anode and solid-state electrolyte. Atomic layer deposition (ALD) is a unique technique for conformal coating of complex 3D structures with finely controlled film thickness (at the atomic scale). ALD coating on the surface of SSEs can be adopted for engineering solid-electrolyte interfaces with desired attributes and improved stability. In this review paper, we have discussed recent progress in implementing the ALD technique for depositing thin layers on various SSE configurations including lithium phosphorus oxynitride (LiPON), garnets, oxides, perovskites, sulphides, Li 3 BO 3 –Li 2 CO 3 (LBCO), and sodium super ionic conductors (NASICON). We have also highlighted the major areas for future research and development in the field. We believe that this review will be very helpful for directing future research on implementing ALD for synthesizing stable and high-performance SSEs with an engineered solid-electrolyte interface for next-generation electrochemical devices (e.g., Li-ion batteries, supercapacitors, and flow batteries).

36 MATERIALS SCIENCE↗
DOE OSTI2022

Fluorination Enables Simultaneous Improvements of a Dialkoxybenzene-Based Redoxmer for Nonaqueous Redox Flow Batteries

Redoxmers or redox-active organic materials, arc one critical component for nonaqueous redox flow batteries (RFBs), which hold high promise in enabling the time domain of the grid. While tuning redox potentials of redoxmers is a very effective way to enhance energy densities of NRFBs, those improvements often accompany accelerated kinetics of the charged species, undermining stability and cycling performance. In this paper, a strategy for designing redoxmers with simultaneous improvements in redox potential and stability is proposed. Specifically, the redoxmer 1,4-di-tert-butyl-2,5-bis(2,2,2-trifluoroethoxy)benzene (ANL-C46) is developed by incorporating fluorinated substitutions into the dialkoxybenzene-based platform. Compared to the non-fluorinated analogue, ANL-C46 demonstrates not only an increased (similar to 0.41 V) redox potential but also much enhanced stability (1.6 times) and cyclability (4 times) evidenced by electron paramagnetic resonance kinetic study, H-cell and flow cell cycling. In fact, the cycling performance of ANL-C46 is among the best of high potential (>1.0 V vs Ag/Ag + ) redoxmers ever reported. Density functional theory calculations suggest that while the introduced fluorine substitutions elevate the redox potentials, they also help to depress the decomposition reactions of the charged redoxmers, affording excellent stability. The findings represent an interesting strategy for simultaneously improving energy density and stability, which could further prompt the development of high-performance redoxmers.

25 ENERGY STORAGE↗
DOE OSTI2025

Evaluation of IrO 2 catalysts doped with Ti and Nb at industrially relevant electrolyzer conditions: A comprehensive study

A series of commercial Oxygen Evolution Reaction (OER) IrO 2 -based materials doped with acid-stable titanium and niobium species were comprehensively characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction analysis (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) with energy dispersive spectroscopy (EDS), and X-ray Scattering. Electrocatalysts were integrated into Membrane Electrode Assembly (MEA) using a fabrication method developed under the US DOE H2NEW consortium. An electrolysis performance in a commercial setup as well as a laboratory screening system was performed at conditions relevant to industrial application. According to the comprehensive characterizations, the studied materials are closer to doped iridium oxides rather than core–shell structures. In an electrolysis cell, the IrO 2 /TiO x catalyst slightly outperforms the IrO 2 /NbO x based on the activity. It was demonstrated that the operation of electrolysis cells at elevated temperatures and the implementation of thinner Nafion-type membranes allows for substantially increased performance, which is consistent with the literature report. Finally, this work provides valuable baselines including characterization and performance for guiding future research in this direction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗