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At least 469 records · Page 26

Analytical modeling for redox flow battery design

Deeper market penetration of redox flow batteries requires optimization of the cell performance. Though important for optimization, detailed analytical solutions have not been developed for electrolyte flow, mass and charge transport, and reaction kinetics within redox flow batteries. To this end, here we present analytical solutions to active species concentration and over-potential based on advection-diffusion transport for ions and Bulter-Volmer model for interface reaction kinetics. The solutions were validated with results from a finite element model. These solutions were then applied to investigate the relationship between over-potential and state of charge, current density, reaction rate constant, flow velocity, diffusivity, total active species concentration, and electrode structure. Explicit formulas were identified for minimum activation over-potential and limiting current density as well as their dependence on electrolyte properties, operation conditions, and electrode structure. With our new mathematical formulas, this work provides a theoretical framework for flow battery design.

25 ENERGY STORAGE↗

Enhancing the performance of lithium oxygen batteries through combining redox mediating salts with a lithium protecting salt

Li–O 2 batteries have recently emerged to meet nowadays elevated electric energy demands. Redox mediators (RMs) for solution-inducing decomposition of discharge products are one approach to increase energy efficiency and reduce high overpotentials in these batteries. However, multiple obstacles hinder their usage such as redox shuttling, capacity fading, electrolyte degradation, etc. Herein, we present a new chemistry based on a combination of LiNO 3 , TEGDME and an ionic liquid that enables LiI (1 M) to lower the charge potential (3.5V) with a long cycle life of 270 cycles. 0.1 M LiI increases the cyclability up to 500 with a slightly increased charge potential (~4V) for a fixed capacity of 1000 mAh/g. Up to 100 cycles, this battery system retained ~95% Li 2 O 2 capacity with a ~0.8 V charge-discharge polarization gap. The addition of LiNO 3 to the electrolyte provides a protective solid electrolyte interface (SEI) on anode that works in synergy with the LiI RM. Moreover, we found that this electrolyte blend results in domain formation of ionic and neutral species enhancing the discharge and charge processes. Finally, DFT calculations provide a better understanding of the role of the anode SEI layer and the Li 2 O 2 decomposition promoted by the LiI during charge on the cathode.

25 ENERGY STORAGE↗

A two-dimensional analytical unit cell model for redox flow battery evaluation and optimization

Cell performance optimization is important for improving the overall system efficiency of a redox flow battery. To gain better insights into key controlling factors of system efficiency, this work first proposed a theoretical model for a unit flow battery cell by extending a two-dimensional analytic model to a full battery cell. Such a model is then used for cell performance optimization after validating it with experimental and numerical modeling data. With the model results, the activation, equilibrium, and pump energy losses are identified as the dominant sources of battery energy losses. Further, a guideline for reducing these sources is also proposed. Following the guideline, the mass transport coefficient is shown as a key control factor of the equilibrium energy loss and Coulombic efficiency (CE). Approaches are then proposed to improve CE and the overall system efficiency. The mass transport is also revealed as the mechanism of pump rate optimization where an optimal pump rate significantly reduces the equilibrium energy loss. With both low equilibrium and pump energy losses, an optimal electrode porosity or specific area design can further improve a battery's system efficiency based on an optimal porosity predicted by the present model. The model also demonstrates distinct behaviors and overestimation in the system efficiency when reduced to a zero-dimensional model with neglected mass transport resistance. With the new model, the guideline, and new insights, this work provides a reliable and efficient tool for the evaluation and optimization of redox flow battery design in practical applications.

25 ENERGY STORAGE↗

Correlating the phase evolution and anionic redox in Co-Free Ni-Rich layered oxide cathodes

Current trend of high-capacity Ni-rich layered cathode is to develop high-Ni and low-Co or Co-free oxides. The high Ni content layered oxides provide great advantages in capacity, cost and environmental benignity, similar to LiNiO 2 parent compound. But they also inherit drawbacks in structural and chemical instability at high voltages upon cycling. As such, elemental substitution plays a profound role in addressing these challenges. This work elucidates the roles of Al doping in cationic redox and anionic oxygen activity in LiAl x Ni 1-x O 2 using combined X-ray absorption spectroscopy (XAS), resonant inelastic X-ray scattering (RIXS) as well as operando differential electrochemical mass spectrometry (DEMS). Using synchrotron wide-angle X-ray scattering (WAXS), we extrapolate a general principle of phase transition and its coupling with lattice anionic oxygen redox. These findings shed light on the advancement of high-capacity, stable-cycling and safe-operating Ni-rich cathode materials for next generation Li-ion batteries.

25 ENERGY STORAGE↗

I – /I 3 – Redox-Assisted Synthesis and Properties of Low Dimensional, Mixed-Valent Gold Iodide Perovskite Derivatives

Here, we report a set of three new mixed-valent Au I Au III iodides: (ClPy) 3 [AuI 2 ] 2 [AuI 4 ] [1], (BrPy) 3 [AuI 2 ] 2 [AuI 4 ] [2], and (ClPy) 2 [AuI 2 ][AuI 4 ] [3], as well as three new monovalent Au III iodides: (XPy) 2 [AuI 4 ][I 3 ] (Py = 4-X-pyridinium X = Cl, Br, and I) [4–6]. Two of these mixed-valent compounds (1 and 2) incorporate both monovalent Au I ···Au I (aurophilic bonding) and mixed-valent Au I I···Au III I couples (Au–I halogen bonding), to the best of our knowledge an unprecedented structural feature. These same two mixed-valent compounds also exhibit a rare low-dimensional molecular architecture with respect to second sphere Au···I interactions, namely, 1D chains of Au···I interactions, extending along a single crystallographic axis. All compounds were synthesized with the assistance of the I – /I 3 – redox couple and tacit manipulation of the polyiodide content during synthesis. Air-free synthesis was used to influence the redox process of I – /I 3 – , resulting in better selection for mixed-valent products. Compounds 1–2 and 4–5 exhibit a characteristically narrow bandgap (1.04–1.25 eV), as measured via diffuse reflectance spectroscopy (DRS). Computational analyses were used to rationalize the specific assembly modes of [AuI 2 ] – and [AuI 4 ] – species, and they show that the Au I ···I interaction type is favored over the Au III ···I.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular Determination of Organic Adsorption Sites on Smectite during Fe Redox Processes Using ToF-SIMS Analysis

Turnover of soil organic carbon (SOC) is strongly affected by a balance between mineral protection and microbial degradation. However, the mechanisms controlling the heterogeneous and preferential adsorption of different types of SOC remain elusive, especially for humic substrates (HSs) and microbial carbon (MC), two hotly-debated forms of SOC prevalent in soils. In this work, the heterogeneous adsorption of HSs and MC on a clay mineral (nontronite NAu-2) during microbial-mediated Fe redox cycling was determined with the use of time-of-flight secondary ion mass spectrometry (ToF-SIMS). The results revealed that HSs pre-adsorbed on NAu-2 would partially inhibit the microbial Fe(III) reduction and structural modification of NAu-2, thus retarding the subsequent adsorption of MC. In contrast, NAu-2 without pre-coated HSs was adsorbed by a significant amount of MC from microbial polysaccharides as a result of Fe(III) reduction. This was attributed to the deposition of a thin Al-rich layer on clay surface, which provided active sites for MC adsorption. This study provides direct and detailed molecular evidence for the first time to explain the preferential adsorption of MC over HSs on the surface of clay minerals in the iron redox processes, which could be critical for the preservation of MC in soil. The results also indicate that ToF-SIMS is a unique tool for understanding complex organic-mineral-microbe interactions.

54 ENVIRONMENTAL SCIENCES↗

Spectroscopic and Theoretical Studies of Ruthenium Complexes with a Noninnocent N 2 S 2 Ligand in Different Redox States

Herein we report an electronic structure investigation of neutral and oxidized Ru complexes containing a redox noninnocent N 2 S 2 ligand derived from o-phenylenediamide (L1). UV–vis spectroelectrochemistry (SEC) studies were conducted on the square pyramidal complex [Ru I I(L1)(PPh 3 )] (1) and the six-coordinate complexes [Ru I I(μ-BH 3 )(L1)(PPh 3 )] (2) – which has BH 3 bound in a metal–ligand cooperative (MLC) fashion across Ru and L1 – and [Ru II (L1)(PPh 3 )(MeCN)] (3). The SEC results yielded spectra assigned to singly and doubly oxidized 1 and 3, revealing electronic structure changes as a function of oxidation state and in response to the presence and absence of bound MeCN. By contrast, the SEC results of 2 showed that it rapidly loses MLC-bound BH 3 upon oxidation. The SEC results for 1 and 3 were compared to single-crystal XRD data and UV–vis, EPR, and P K-edge, S K-edge, and Ru L 3 -edge X-ray absorption spectroscopy (XAS) data collected on isolated samples of chemically oxidized 3. The data revealed that the first two oxidations are primarily localized on the ligand, which was supported by DFT and TDDFT calculations. DFT calculations for the doubly oxidized species revealed a singlet ground state with a singlet–triplet gap of 8.9 kcal/mol. CASPT2 calculations corroborated the DFT calculations and further revealed that the singlet ground state is multiconfigurational with 21% radical character. Collectively, the results establish redox formalisms and the underlying electronic structure of Ru complexes containing a noninnocent tetradentate ligand in different oxidation states.

electronic structure↗

Experimental and Multiscale Modeling Insights for Radiation-Driven Neptunium Redox Processes at Elevated Temperatures

Studies of the radiation-driven reactions of actinide elements at elevated temperatures are extremely limited, but important given that radiation heating of used nuclear fuel can affect the radiolytically promoted actinide redox processes occurring in hydroprocessing environments. Under these conditions, the high concentration of nitric acid present makes the reaction of actinides, such as neptunium, with nitric acid radiolysis products significant. Therefore, here we present derivation of the rate coefficients for the reaction of pentavalent neptunium with the nitrate radical at elevated temperature, resulting in Eyring and Arrhenius parameters for this important reaction. Here, we also revisit our previously published multiscale model predictions for radiation-induced neptunium redox chemistry and present an iteration which successfully operates over a wider range of nitric acid concentrations, 0.1–6.0 M.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Theoretical Investigation of the Hydrogenation of Cyclohexene Catalyzed by Supported Single-Atom Sites on Redox Noninnocent LiMn 2 O 4 and Li 2 Mn 2 O 4 Surfaces

Here, the tuning of catalyst activity via stereoelectronic modulation of the active-site structure remains a grand challenge in heterogeneous catalysis. In homogeneous catalysis, the redox noninnocent ligands can be introduced to organometallic fragments to donate electrons to the metal center and fine-tune the catalytic activity. Analogously, lithium-ion battery materials, such as lithium manganese oxide (LMO), lithium titanium oxides (LTO), etc., can serve as redox noninnocent catalyst support to modulate the electronic structures of the active site via lithiation, hence tuning the catalytic activity of supported active sites. Experimentally, the Ni single-atom site was supported on LiMn 2 O 4 via oxidative grafting and exhibited no catalytic activity toward the hydrogenation of cyclohexene. After introducing additional Li into the catalyst support forming Li 2 Mn 2 O 4 , the Ni single-atom site becomes active, with the catalytic rates increasing as a function of the lithiation for Li/Mn ratios >0.9. In this paper, density functional theory (DFT) calculations are performed to study the Ni site structure via X-ray absorption near edge structure (XANES) simulations and investigate the electronic properties of Ni single-atom site before and after the addition of intercalated lithium in the LMO spinel structure. Furthermore, the study of the reaction mechanism is also carried out to understand the thermodynamically and kinetically favored pathways. XANES simulation suggests that the Ni single-atom site is likely to stay in the Li channel of the spinel support structure and form an octahedral structure. After Li intercalation, the Ni site becomes less positively charged, indicating the partial reduction of the Ni site. The simulated reaction energy profile over the LiMn 2 O 4 support exhibits high-energy barriers (1.07 eV) for the hydrogenation of cyclohexene; however, the Li 2 Mn 2 O 4 support is able to better stabilize low-coordinated ion sites and improve ion mobility, leading to lower overall energy barriers (0.64 eV). The reduced and low-coordinated ion site, thus, can better stabilize the reaction intermediates and promote hydrogenation reaction. Similarly, other transition metal ions (Fe, Co, and Cu) are also considered over the LiMn 2 O 4 and Li 2 Mn 2 O 4 catalyst supports for hydrogenation reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solar Thermochemical Redox Cycling Using Ga- and Al-Doped LSM Perovskites for Renewable Hydrogen Production

Solar thermochemical hydrogen production using redox-active metal oxides is a promising pathway for the production of green hydrogen and synthetic fuel precursors. Herein, the perovskite material (La 0.6 Sr 0.4 ) 0.95 Mn 0.8 Ga 0.2 O 3–δ (LSMG6482) is identified as a promising metal oxide for thermochemical water splitting. LSMG6482, along with more-established water splitters ceria and (La 0.6 Sr 0.4 ) 0.95 Mn x Al 1–x O 3–δ (LSMA) perovskites, is experimentally characterized via thermogravimetric (TGA) analysis and high-temperature water splitting in a reactor simulating solar concentrating conditions. TGA analysis demonstrated that LSMG6482 has high and stable oxygen exchange capacity under controlled pO 2 redox cycling, demonstrated by large changes in oxygen nonstoichiometry (δ) relative to ceria. Water splitting experiments using laser heating (T red = 1400 °C, T ox = 1200 °C) resulted in H 2 yields of 165.1 μmol g –1 for the candidate LSMG6482 composition, exceeding that of all benchmark materials tested. Under high conversion oxidation conditions, where H 2 is cointroduced with H 2 O (150 ≤ nH 2 O/nH 2 ≤ 500), H 2 yields were greatest for LSMG6482 and LSMA6482, up to four times that of ceria at the highest nH 2 O/nH 2 conditions. Crystallographic analysis showed that over the course of experimentation, there is some secondary phase growth for all perovskite compositions, except for LSMA6482, but there was no observable degradation in H 2 yields.

08 HYDROGEN↗

Automation-Accelerated Electrolyte Design Mitigates Solubility Competition between Redox-Active Molecules and Supporting Salts

In nonaqueous redox-flow batteries (NRFBs), redox-active organic molecules (ROMs) and supporting salts compete for solvation sites, limiting achievable energy density. We combine automated high-throughput experimentation (HTE) with camera-based saturation monitoring and quantitative NMR to measure paired (ROM, salt) solubilities across single and mixed organic solvents. Using 2,1,3-benzothiadiazole (BTZ) with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as a model system, we find that a binary m-xylene/acetonitrile mixture dissolves ≈3 M of both BTZ and LiTFSI─surpassing the previously reported 2 M ceiling for neat acetonitrile─by leveraging complementary solvation (MX is BTZ-philic and salt-phobic; ACN stabilizes LiTFSI). A random-forest model (RMSE ≈ 0.24) trained on solvent descriptors highlights log P and salt concentration as dominant predictors and predicts MX/ACN ≈0.3/0.7 (v/v) to be near-optimal. These formulations retain practical viscosity and ∼5 mS·cm –1 conductivity at high loading. In conclusion, the workflow provides a reproducible, data-centric route to NRFB electrolyte design and motivates an open, standardized dual-solute solubility resource for accelerated electrolyte discovery.

Electrolytes↗

Probing Depth-Dependent Transition-Metal Redox of Lithium Nickel, Manganese, and Cobalt Oxides in Li-Ion Batteries

Layered lithium nickel, manganese, and cobalt oxides (NMC) are among the most promising commercial positive electrodes in the past decades. Understanding the detailed surface and bulk redox processes of Ni-rich NMC can provide useful insights into material design options to boost reversible capacity and cycle life. Both hard X-ray absorption (XAS) of metal K-edges and soft XAS of metal L-edges collected from charged LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) and LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) showed that the charge capacity up to removing ~0.7 Li/f.u. was accompanied with Ni oxidation in bulk and near the surface (up to 100 nm). Of significance to note is that nickel oxidation is primarily responsible for the charge capacity of NMC622 and 811 up to similar lithium removal (~0.7 Li/f.u.) albeit charged to different potentials, beyond which was followed by Ni reduction near the surface (up to 100 nm) due to oxygen release and electrolyte parasitic reactions. Overall, this observation points toward several new strategies to enhance reversible redox capacities of Ni-rich and/or Co-free electrodes for high-energy Li-ion batteries.

25 ENERGY STORAGE↗

Tuning Bulk Redox and Altering Interfacial Reactivity in Highly Fluorinated Cation-Disordered Rocksalt Cathodes

Lithium-excess, cation-disordered rocksalt (DRX) materials have been subject to intense scrutiny and development in recent years as potential cathode materials for Li-ion batteries. Despite their compositional flexibility and high initial capacity, they suffer from poorly understood parasitic degradation reactions at the cathode-electrolyte interface. These interfacial degradation reactions deteriorate both the DRX material and electrolyte, ultimately leading to capacity fade and voltage hysteresis during cycling. In this work, differential electrochemical mass spectrometry (DEMS) and titration mass spectrometry are combined to quantify the extent of bulk redox and surface degradation reactions for a set of Mn 2+/4+ -based DRX oxyfluorides during initial cycling with a high-voltage charging cutoff (4.8 V vs Li/Li + ). Increasing the fluorine content from 7.5 to 33.75% is shown to diminish oxygen redox and suppresses high-voltage O 2 evolution from the DRX surface. Additionally, electrolyte degradation processes resulting in the formation of both gaseous species and electrolyte-soluble protic species are observed. Subsequently, DEMS is paired with a fluoride-scavenging additive to demonstrate that increasing fluorine content leads to increased dissolution of fluorine from the DRX material into the electrolyte. Finally, a suite of ex situ spectroscopy techniques (X-ray photoelectron spectroscopy, inductively coupled plasma optical emission spectroscopy, and solid-state nuclear magnetic resonance spectroscopy) are employed to study the change in DRX composition during charging, revealing the dissolution of manganese and fluorine from the DRX material at high voltages. Here this work provides insight into the degradation processes occurring at the DRX-electrolyte interface and points toward potential routes of interfacial stabilization.

25 ENERGY STORAGE↗

Coupled Experimental–Theoretical Characterization of a Carbon Electrode in Vanadium Redox Flow Batteries using X-ray Absorption Spectroscopy

Vanadium redox flow batteries (VRFBs) have emerged as promising solutions for stationary grid energy storage due to their high efficiency, scalability, safety, near room-temperature operation conditions, and the ability to independently size power and energy capacities. The performance of VRFBs heavily relies on the redox couple reactions of V 2+ /V 3+ and VO 2+ /VO 2 + on carbon electrodes. Therefore, a thorough understanding of the surface functionality of carbon electrodes and their propensity for degradation during electrochemical cycles is crucial for designing VRFBs with extended lifespans. In this study, we present a coupled experimental–theoretical approach based on carbon K edge X-ray absorption spectroscopy (XAS) to characterize carbon electrodes prepared under different conditions and identify relevant functional groups that contribute to unique spectroscopic features. Atomic models were created to represent functional groups, such as hydroxyl, carboxyl, methyl, and aldehyde, bonded to carbon atoms in either sp 2 or sp 3 environments. The interactions between functionalized carbon and various solvated vanadium complexes were modeled using density functional theory. A library of carbon K-edge XAS spectra was generated for distinct carbon atoms in different functional groups, both before and after interacting with solvated vanadium complexes. Here we demonstrate how these simulated spectra can be used to deconvolve ex situ experimental spectra measured from carbon electrodes and to track changes in the electrode composition following immersion in different electrolytes or extended cycling within a functional VRFB. By doing so, we identify the active species present on the carbon electrodes, which play a crucial role in determining their electrochemical performance.

25 ENERGY STORAGE↗

Lithium-Ion Battery Materials as Tunable, “Redox Non-Innocent” Catalyst Supports

The development of general strategies for the electronic tuning of a catalyst’s active site is an ongoing challenge in heterogeneous catalysis. To this end, herein, we describe the application of Li-ion battery cathode and anode materials as redox non-innocent catalyst supports that can be continuously modulated as a function of lithium intercalation. A zero-valent nickel complex was oxidatively grafted onto the surface of lithium manganese oxide (Li x Mn 2 O 4 ) to yield isolated Ni2+ occupying the vacant interstitial octahedral site in the Li diffusion channel on the surface and subsurface of the spinel structure (Ni/Li x Mn 2 O 4 ). Additionally, the activity of Ni/Li x Mn 2 O 4 for olefin hydrogenation, as a representative probe reaction, was found to increase monotonically as a function of support reductive lithiation. Simulation of Ni/Li x Mn 2 O 4 reveals the dramatic impact of surface redox states on the viability of the homolytic oxidative addition mechanism for H 2 activation. Catalyst control through support lithiation was extended to an organotantalum complex on Li x TiO 2 , demonstrating the generality of this phenomenon.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Kinetic and X-ray Absorption Spectroscopic Analysis of Catalytic Redox Cycles over Highly Uniform Polymetal Oxo Clusters

Metal–organic framework materials (MOFs) offer an opportunity for investigating catalytic properties of polymetal oxo clusters that are highly well defined and uniform in nature, in contrast to other classes of catalysts that may exhibit a propensity toward active site heterogeneity. We report herein a kinetic and X-ray absorption spectroscopy (XAS) analysis of the two-electron oxidation of CO over divalent metal sites in MIL-100(M = Fe, Cr) (MIL = Materials of Institut Lavoisier) materials carrying μ 3 -oxo bridged trimers, and connect observations about the kinetic relevance of redox steps to density functional theory (DFT) predictions published previously. The high degree of uniformity evident from in situ titration measurements leads to a congruence in mechanistic inferences made from steady-state catalytic, transient stoichiometric, isotopic exchange, and isotopic tracer data that all point to a sequential mechanism comprised of separate oxidation and reduction half-cycle steps conjoined by an active oxygen intermediate. In situ XAS data reinforce mechanistic conclusions derived from kinetic analysis, and suggest that the active oxygen intermediate may be more appropriately characterized as an iron-oxyl (Fe 3+ –O – ) rather than an iron-oxo (Fe 4+ =O 2– ) species. The Cr analogue of MIL-100 exhibits contrasting rate features that can be rationalized using an identical sequence of steps as MIL-100(Fe), but with a highly dissimilar set of kinetic parameters that can also be validated using transient stoichiometric experiments. The larger coverages of active oxygen intermediates on MIL-100(Cr) are consistent with predictions from prior DFT studies that suggest more stable and less reactive active oxygen species for metals with lower d-electron counts, and point to metal identity as a lever for precisely controlling the kinetic relevance of oxidation and reduction half-cycles in catalytic redox sequences over polymetal oxo clusters. Importantly, the results presented point to the utility of developing broadly applicable structure–catalytic property relationships over MOF nodes specifically, and highly uniform catalysts more generally.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surface Redox Pseudocapacitance of Partially Oxidized Titanium Carbide MXene in Water-in-Salt Electrolyte

Achieving pseudocapacitive intercalation in MXenes with neutral aqueous electrolytes and driving reversible redox reactions is scientifically appealing and practically useful. Here, we report that the partial oxidation of MXene intensifies pseudocapacitive Li + intercalation into Ti 3 C 2 T x MXene from neutral water-in-salt electrolytes. An in situ X-ray absorption near-edge structure analysis shows that the Ti oxidation state changes during the Li+ intercalation, indicating the presence of a surface redox reaction. The Ti oxidation/reduction is further confirmed by an in situ extended X-ray absorption fine structure analysis, which shows a reversible contraction/expansion of the Ti–C interatomic distance. The intensified Li + pseudocapacitive intercalation can be explained by the higher oxidation state of Ti at the open circuit potential. Furthermore, this work demonstrates the possibility of tuning the pseudocapacitive intercalation by adjusting the initial oxidation state of the transition metal on the MXene and offers a facile way to enhance the pseudocapacitance of various MXenes.

36 MATERIALS SCIENCE↗