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At least 1,099 records · Page 61

Examination of actinide chemistry at solid-water interfaces to support advanced actinide separations (Final Report)

In this work we have examined the thermodynamics of actinide interactions with solid interfaces in the presence and absence of multi-functional complexing ligands. The term “interactions” is a global term to capture many potential reactions including aqueous complexation, sorption/surface complexation, surface-mediated redox reactions, electrostatic attraction and repulsion, surface passivation, surface precipitation, and counter-ion competition. Each of these potential reactions may control actinide interactions with a solid surface. This work is helping to develop a more fundamental understanding of actinide bonding at solid:water interfaces and examine unique surface mediated oxidation/reduction reactions which are not expected based on the reduction potentials of aqueous species. We place a large emphasis on understanding both sorption and desorption processes as a means of understanding the sorption mechanisms. This work is directly aligned with the DOE BES Heavy Element Chemistry programs interests in understanding “the chemical and physical properties of these elements to determine solution, interfacial and solid-state bonding and reactivity”.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Development of Composite Photocatalyst Materials that are Highly Selective for Solar Hydrogen Production and their Evaluation in Z-Scheme Reactor Designs

The key technology gap preventing a vertically stacked dual-bed particle suspension reactor from achieving the DOE MYRD&D ultimate cost target for H 2 production remains the lack of materials in particle form factor that exhibit ≥10% solar-to-H 2 energy conversion (STH) efficiency as a suspension. Therefore, our project goals centered around strategies to increase the STH efficiency by enhancing photophysical properties of perovskite oxide particles including increased visible-light absorption, increased selectivity for electrocatalysis of the H 2 evolution reaction (HER) and the O 2 evolution reaction (OER) through development of ultrathin oxide coatings, correlating composition and structure to function, and improving understanding of multiscale transport and kinetic processes.

08 HYDROGEN↗

Multi-omic characterization of bifunctional peroxidase 4-coumarate 3-hydroxylase knockdown in Brachypodium distachyon provides insights into lignin modification-associated pleiotropic effects

A bifunctional peroxidase enzyme, 4-coumarate 3-hydroxylase (C3H/APX), provides a parallel route to the shikimate shunt pathway for the conversion of 4-coumarate to caffeate in the early steps of lignin biosynthesis. Knockdown of C3H/APX (C3H/APX-KD) expression has been shown to reduce the lignin content in Brachypodium distachyon . However, like many other lignin-modified plants, C3H/APX-KDs show unpredictable pleiotropic phenotypes, including stunted growth, delayed senescence, and reduced seed yield. A system-wide level understanding of altered biological processes in lignin-modified plants can help pinpoint the lignin-modification associated growth defects to benefit future studies aiming to negate the yield penalty. Here, a multi-omic approach was used to characterize molecular changes resulting from C3H/APX-KD associated lignin modification and negative growth phenotype in Brachypodium distachyon . Our findings demonstrate that C3H/APX knockdown in Brachypodium stems substantially alters the abundance of enzymes implicated in the phenylpropanoid biosynthetic pathway and disrupt cellular redox homeostasis. Moreover, it elicits plant defense responses associated with intracellular kinases and phytohormone-based signaling to facilitate growth-defense trade-offs. A deeper understanding along with potential targets to mitigate the pleiotropic phenotypes identified in this study could aid to increase the economic feasibility of lignocellulosic biofuel production.

36 MATERIALS SCIENCE↗

Kinetics Data of Iron(II), Manganese(II), Dissolved Organic Carbon and Nitrate from Batch Incubation Experiments Using Hyporheic Sediments from the East River Watershed, Colorado.

Hyporheic zones act as critical ecological links between terrestrial and aquatic systems where redox-sensitive metals of iron (Fe) and manganese (Mn) significantly impact nutrient cycling and water quality. In order to understand the production, release and speciation of Fe(II) and Mn(II) in groundwater, we conducted batch incubation experiments using sediment samples from a hyporheic zone of the East River floodplain in Colorado. The East River is part of the Watershed Function Scientific Focus Area (WFSFA) located in the Upper Colorado River Basin, United States. Collection and processing of the data is described in the Methods, along with details of data file contents. There are 6 data files provided in two formats: 1 zip-folder of .csv (open source) files, and 1 zip-folder of .xlsx (Excel) files. The data tables provided in the two formats are the exact same.

54 ENVIRONMENTAL SCIENCES↗

Microscopic Investigation of H 2 Reduced CuO x /Cu(111) and ZnO/CuO x /Cu(111) Inverse Catalysts: STM, AP-XPS, and DFT Studies

Understanding the reduction mechanism of ZnO/CuO x interfaces by hydrogen is of great importance for advancing the performance of industrial catalysts for CO 2 hydrogenation to methanol. Here, the reduction of pristine and ZnO-modified CuO x /Cu(111) by H 2 was investigated using ambient pressure scanning tunnelling microscopy (AP-STM), ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and density functional theory (DFT). The morphological changes and reaction rates seen for the reduction of CuO x /Cu(111) and ZnO/CuO x /Cu(111) are very different. On CuO x /Cu(111), perfect "44" and "29" structures displayed a very low reactivity towards H 2 at room temperature. A long induction period associated with an autocatalytic process was observed to enable the reduction by the removal of chemisorbed non-lattice oxygen initially and lattice oxygen sequentially at the CuO x -Cu interface, which led to formation of oxygen deficient "5-7" hex and honeycomb structures. In the final stages of the reduction process, regions of residual oxygen species and metallic Cu were seen. The addition of ZnO particles to CuO x /Cu(111) opened new reaction channels. On the ZnO sites, the dissociation of H 2 was fast and H adatoms easily migrated to adjacent regions of copper oxide. This hydrogen spillover substantially enhanced the rate of oxygen removal, resulting in the rapid reduction of the copper oxide located in the periphery of the zinc oxide islands with no signs for the reduction of ZnO. The deposited ZnO completely modified the dynamics for H 2 dissociation and hydrogen migration, providing an excellent source for CO 2 hydrogenation processes on the inverse oxide/metal system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Manifesto on the Thermochemistry of Nanoscale Redox Reactions for Energy Conversion

Advancements in the use of nanoscale materials for energy conversions will rely on a clear understanding of reaction thermochemistry. While band edge and Fermi energies can be rigorous thermodynamic descriptors of bulk materials, we show here that their application to nanoscale systems is problematic. A change of one electron at a 1000 atom nanoparticle or a localized surface site on a catalyst/electrode causes significant nuclear reorganization of the system. Electron transfer is often coupled with solvent reorganization and/or with the transfer of ions, including ion intercalation, surface binding, and movement within the surrounding double layer. These effects can be significant (even for some bulk materials). However, Fermi and band energies, as typically used, do not include the energetics of nuclear reorganizations or cation coupling. A comprehensive approach to nanoscale charge transfer thermodynamics must explicitly consider these effects in order to have a more complete understanding and greater control of nanoscale redox reactivity.

30 DIRECT ENERGY CONVERSION↗

Multilevel Computational Studies Reveal the Importance of Axial Ligand for Oxygen Reduction Reaction on Fe–N–C Materials

The systematic improvement of Fe–N–C materials for fuel cell applications has proven challenging, due in part to an incomplete atomistic understanding of the oxygen reduction reaction (ORR) under electrochemical conditions. Herein, a multilevel computational approach, which combines ab initio molecular dynamics simulations and constant potential density functional theory calculations, is used to assess proton-coupled electron transfer (PCET) processes and adsorption thermodynamics of key ORR intermediates. These calculations indicate that the potential-limiting step for ORR on Fe–N–C materials is the formation of the Fe III –OOH intermediate. They also show that an active site model with a water molecule axially ligated to the iron center throughout the catalytic cycle produces results that are consistent with the experimental measurements. In particular, reliable prediction of the ORR onset potential and the Fe(III/II) redox potential associated with the conversion of Fe III –OH to Fe II and desorbed H 2 O requires an axial H 2 O co-adsorbed to the iron center. The observation of a five-coordinate rather than four-coordinate active site has significant implications for the thermodynamics and mechanism of ORR. Importantly, these findings highlight the importance of solvent–substrate interactions and surface charge effects for understanding the PCET reaction mechanisms and transition-metal redox couples under realistic electrochemical conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis, structure, and electrochemical properties of [LNi(R f )(C 4 F 8 )] - and [LNi(R f ) 3 ] - complexes

The new anionic nickelate complexes [(MeCN)Ni(C 4 F 8 )(CF 3 )] -, [(MeCN)Ni(C 4 F 8 )(C 2 F 5 )] - , [(IMes)Ni(C 4 F 8 )(CF 3 )] - , [(IMes)Ni(CF 3 ) 3 ] - (IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene), and [(F-NHC)Ni(Rf) 3 ] - (F-NHC = 1,3-bis(2,4-F2Ph), 2,4,6-F 3 Ph- or 3,4,5-F 3 Ph)imidazol-2-ylidene; (R f = CF 3 or C 2 F 5 ) were synthesized and structurally characterized. The electrochemical properties of all new compounds were revealed by cyclic voltammetry studies and compared to the known CF 3 analogue [(MeCN)Ni(CF 3 ) 3 ] -. The IMes-coordinated complexes exhibited initial oxidation events that were well-separated from a second oxidation process in the cyclic voltammograms. The complexes containing F-substituted NHC ligands [(F-NHC)Ni(CF 3 ) 3 ] - are structurally quite similar to the IMes derivative and reveal also two separated oxidation waves in their cyclic voltammograms. The absolute potentials as well as the separation between the two waves vary with the substitution pattern, suggesting that the NHC ligand environment (NHC = N-heterocyclic carbene) is an interesting platform for the development of new redox-triggered reactions that release trifluoromethyl and perfluoroalkyl radicals upon oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Biogeochemical Processes Across Aquatic Interfaces

The aquatic interfaces exposing terrestrial soils to oxic-anoxic regime shifts represent biogeochemical “hotspots” that are extremely sensitive to climate and environmental change. However, processes and interaction across theses aquatic interfaces are poorly understood and underrepresented in current Earth system models. In this project, we aim to develop predictive understanding of the feedbacks between microbial systems and geochemical environments that determine emergent ecosystem behaviors and resilience in response to disturbances. We use experimental, mechanistic modeling and meta-analysis tools to elucidate interactions among soil, water, geomorphology and microbiology that regulate the molecular transformations and fluxes of carbon, nutrients, and redox-sensitive compounds across aquatic interfaces.

58 GEOSCIENCES↗

An Easily Prepared Monomeric Cobalt(II) Tetrapyrrole Complex That Efficiently Promotes the 4e – /4H + Peractivation of O 2 to Water

The selective 4e – /4H + reduction of dioxygen to water is an important reaction that takes place at the cathode of fuel cells. Monomeric aromatic tetrapyrroles (such as porphyrins, phthalocyanines, and corroles) coordinated to Co(II) or Co(III) have been considered as oxygen reduction catalysts due to their low cost and relative ease of synthesis. Furthermore, these systems have been repeatedly shown to be selective for O 2 reduction by the less desired 2e – /2H + pathway to yield hydrogen peroxide. Herein, we report the initial synthesis and study of a Co(II) tetrapyrrole complex based on a nonaromatic isocorrole scaffold that is competent for 4e – /4H + oxygen reduction reaction (ORR). This Co(II) 10,10-dimethyl isocorrole (Co[10-DMIC]) is obtained in just four simple steps and has excellent yield from a known dipyrromethane synthon. Evaluation of the steady state spectroscopic and redox properties of Co[10-DMIC] against those of Co porphyrin (cobalt 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin, [Co(TPFPP)]) and corrole (cobalt 5,10,15-tris(pentafluorophenyl)corrole triphenylphosphine, Co[TPFPC](PPh 3 )) homologues demonstrated that the spectroscopic and electrochemical properties of the isocorrole are distinct from those displayed by more traditional aromatic tetrapyrroles. Further, the investigation of the ORR activity of Co[10-DMIC] using a combination of electrochemical and chemical reduction studies revealed that this simple, unadorned monomeric Co(II) tetrapyrrole is ~85% selective for the 4e – /4H + reduction of O 2 to H 2 O over the more kinetically facile 2e – /2H + process that delivers H 2 O 2 . In contrast, the same ORR evaluations conducted for the Co porphyrin and corrole homologues demonstrated that these traditional aromatic systems catalyze the 2e – /2H + conversion of O 2 to H 2 O 2 with near complete selectivity. Despite being a simple, easily prepared, monomeric tetrapyrrole platform, Co[10-DMIC] supports an ORR catalysis that has historically only been achieved using elaborate porphyrinoid-based architectures that incorporate pendant proton-transfer groups or ditopic molecular clefts or that impose cofacially oriented O 2 binding sites. Accordingly, Co[10-DMIC] represents the first simple, unadorned, monomeric metalloisocorrole complex that can be easily prepared and shows a privileged performance for the 4e – /4H + peractivation of O 2 to water as compared to other simple cobalt containing tetrapyrroles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Efficiency and mechanisms of Sb(III/V) removal by Fe-modified biochars using X-ray absorption spectroscopy

Fe-modified biochars (FeBC) are effective antimony (Sb) removal materials; however, the removal mechanisms require further investigation. In this study, aqueous Sb(III) and Sb(V) removal by FeBC (300, 600, and 900 °C) was evaluated, with the adsorption mechanisms investigated using X-ray absorption spectroscopy (XAS). Screening results (based on removal efficiencies) using different types of FeBC indicated the 900 °C FeCl3- modified biochar (FeCl3BC900) achieved the best Sb(III/V) removal performance. The kinetics of the Sb(III/V) removal process were best fitted by a pseudo-second-order model. Additionally, the isothermal results were described by Langmuir and Redlich-Peterson models. Aqueous analysis and X-ray absorption near-edge structure data fitting indicated Sb(III) was oxidized to Sb(V) in the Sb(III)-spiked system, and the oxidation extent increased with increasing pyrolysis temperature. The oxidation process rapidly occurred in both the solution and biochar. No Sb(V) was reduced to Sb(III) in the Sb(V)-spiked system. The XAS results of the isothermal experiment indicated the oxidation capacity of FeCl3BC900 was limited for high initial Sb(III) concentrations. The SbFe1 and Sb-Fe2 bonding distances were 3.05–3.10 and 3.47–3.54 Å, respectively, indicating inner-sphere complexes were formed during the Sb(III/V) removal processes. The Sb(III/V) removal mechanisms included electrostatic adsorption, inner-sphere complexes, and coprecipitation. Oxidation was also involved in Sb(III) removal.

Antimony↗

Acceleration and Stabilization of Electron Transfer Products with Improved Quantum Yields upon Cation Binding to a Fused Bis-Zinc Porphyrin-Quinone Donor–Acceptor Conjugate

The role of metal ions in promoting electron transfer processes in biological coenzymes is of great significance not only to understand their mechanistic details but also due to their direct utilization in a number of chemical and biochemical processes. Here, we demonstrate an increased rate of forward electron transfer with improved reaction quantum yield, and an enhanced lifetime of electron transfer products upon cation binding to the acceptor entity in a donor-acceptor conjugate. Selective binding of cations such as Mg 2+ or Sc 3+ to the electron acceptor, quinone, in a fused, bis-zinc porphyrin-quinone donor-acceptor conjugate leads to facile reduction of the quinone making the electron transfer process thermodynamically highly feasible. Furthermore, the binding of metal ions to the electron transfer product, quinone anion, decelerates the reverse electron transfer process due to ion-pairing interactions, resulting in improving both the lifetime and quantum yields of the electron transfer products. Furthermore, systematic studies including spectral, electrochemical, computational, spectroelectrochemical, and transient absorption techniques, coupled with data analysis by Global Target Analysis (GloTarAn), are performed to demonstrate these novel findings that are relevant to further our understanding of electron transfer processes occurring in biological coenzymes and pertinent energy harvesting schemes.

Charge transfer↗

Biogenic sulfide control by nitrate and (per)chlorate – A monitoring and modeling investigation

Biosouring is commonly encountered during secondary oil recovery when seawater or another high sulfate water source is utilized for flooding; as a result, effective souring control is of great interest to the oil industry. Here we describe a laboratory study to evaluate the relative effectiveness of souring interventions through the injection of nitrate, chlorate and perchlorate, collectively (per)chlorate, solutions and whether in-situ galvanic potential measurements can be used for convenient and quantitative tracking of sulfide dynamics. Nitrate has typically been the chemical of choice for souring treatments, while the efficacy of (per)chlorate as a new candidate inhibitor has only been explored recently. (Per)chlorate is known to inhibit oil reservoir souring via mechanisms such as toxicity, bio-competitive exclusion and sulfur redox cycling. Two sets of experiments under different matrix and inoculation conditions were conducted to evaluate treatment efficiency under variable baseline physical and biogeochemical conditions. Our data demonstrated the sensitivity of the galvanic potential signals to sulfide concentrations where the sulfide-galvanic potential correlation is similar to the theoretical predictions based on the Nernst equation, demonstrating the feasibility of using galvanic potential as a quick and economical method for quantifying in situ sulfide concentrations for tracking reservoir souring processes and subsequent intervention effectiveness. Our results show that all three chemicals were effective at suppressing sulfidogenesis. A reactive transport model for perchlorate treatment was developed to simulate the reaction processes and explore the interactions between the underlying competing mechanisms of this inhibitor. A baseline simulation captured the temporal patterns of the effluent chemical species. Subsequent simulations in which individual inhibition mechanisms were systematically removed elucidated the relative role that each inhibition mechanism played at the different phases of the experiment. The simulation results complement the experimental findings. Our study supports the potential advantages of souring control with (per)chlorate treatments, and the application of galvanic signal as an economic, in-situ monitoring approach for tracking souring dynamics and treatment efficacy.

02 PETROLEUM↗

Enhancing the Visible-Light Absorption and Excited-State Properties of Cu(I) MLCT Excited States

A computationally inspired Cu(I) metal-to-ligand charge transfer (MLCT) chromophore, [Cu(sbmpep) 2 ] + (sbmpep = 2,9-di( sec -butyl)-3,8-dimethyl-4,7-di(phenylethynyl)-1,10-phenanthroline), was synthesized in seven total steps, prepared from either dichloro- or dibromophenanthroline precursors. Complete synthesis, structural characterization, and electrochemistry, in addition to static and dynamic photophysical properties of [Cu(sbmpep) 2 ] + , are observed on all relevant time scales. UV–Vis absorption spectroscopy revealed significant increases in oscillator strength along with a concomitant bathochromic shift in the MLCT absorption bands with respect to structurally related model complexes (ε = 16 500 M –1 cm –1 at 491 nm). Strong red photoluminescence (Φ = 2.7%, λ max = 687 nm) was determined from [Cu(sbmpep) 2 ] + , which featured an average excited-state lifetime of 1.4 μs in deaerated dichloromethane. Cyclic and differential pulse voltammetry revealed ~300 mV positive shifts in the measured one-electron reversible reduction and oxidation waves in relation to a Cu(I) model complex possessing identical structural elements without the π-conjugated 4,7-substituents. The excited-state redox potential of [Cu(sbmpep) 2 ] + was estimated to be -1.36 V, a notably powerful reductant for driving photoredox chemistry. The combination of conventional and ultrafast transient absorption and luminescence spectroscopy successfully map the excited-state dynamics of [Cu(sbmpep) 2 ] + from initial photoexcitation to the formation of the lowest-energy MLCT excited state and ultimately its relaxation to the ground state. This newly conceived molecule appears poised for photosensitization reactions involving energy and electron-transfer processes relevant to photochemical upconversion, photoredox catalysis, and solar fuels photochemistry.

14 SOLAR ENERGY↗

Non-equilibrium crystallization pathways of manganese oxides in aqueous solution

Aqueous precipitation of transition metal oxides normally proceeds through non-equilibrium phases, whose appearance cannot be anticipated from traditional phase diagrams. Without a precise understanding of which metastable phases form, or their lifetimes, targeted synthesis of specific metal oxides can become a trial-and-error process. In this work, we construct a theoretical framework to reveal the nanoscale and metastable energy landscapes of Pourbaix (E-pH) diagrams, providing quantitative insights into the size-dependent thermodynamics of metastable oxide nucleation and growth in water. By combining this framework with classical nucleation theory, we interrogate how solution conditions influence the multistage oxidation pathways of manganese oxides. We calculate that even within the same stability region of a Pourbaix diagram, subtle variations in pH and redox potential can redirect a non-equilibrium crystallization pathway through different metastable intermediates. Our theoretical framework offers a predictive platform to navigate through the thermodynamic and kinetic energy landscape towards the rational synthesis of target materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental Protocols for Studying Organic Non-aqueous Redox Flow Batteries

We report that Redox flow batteries (RFBs) are promising devices for grid-scale energy storage due to the decoupling of power and energy, which can be independently scaled by the electrode area and storage tank size, respectively. To date, only aqueous RFBs, such as the vanadium RFB, have been implemented commercially. Nevertheless, the limited energy densities and high-cost materials may preclude their wider market penetration. Organic non-aqueous redox-flow batteries (O-NRFBs), which utilize redox-active organic molecules (ROMs), have been offered as an attractive alternative. Many possible advantages include the use of earth-abundant elements (C, H, N, O, S, F), wherein the ROMs can be prepared from low-cost and sustainable materials. Additionally, a large variety of electroactive moieties are accessible as building blocks, providing a synthetic platform to tune the properties of ROMs through rational design. As a consequence, the development of novel ROMs has attracted researchers with diverse backgrounds, prompting remarkable innovations in the past decade. However, consistency in experimental protocols (e.g., electrochemical methods, cycling stability, experimental conditions) has not coincided with this uptick in research, leading to sometimes ambiguous and incomparable results. This is further convoluted by the complexity innate to battery development, such as cell design, detection, and characterization of reactions and active components. The O-NRFB application imposes stringent requirements on the physical or/and chemical processes involved in electrochemical cycling. Yet such considerations are often overlooked. Further, while quantum mechanical calculations provide a convenient tool for evaluating and selecting ROM candidates, this simulation is not always performed. Thus, in this Energy Focus, we detail a means to standardize experimental protocols for studies of O-NRFBs and suggest practices to facilitate fundamental understanding and development of ROMs.

25 ENERGY STORAGE↗

Advanced strategies for the development of porous carbon as a Li host/current collector for lithium metal batteries

Lithium metal is considered a promising anode material for high-energy-density rechargeable batteries because of its high specific theoretical capacity (3860 mAh g -1 , low mass density (0.534 g cm -3 ), and low electrochemical redox potential (-3.04 V vs. the standard hydrogen electrode). However, the high reactivity of Li with the electrolyte leads to the formation of an unstable solid electrolyte interphase (SEI) and continuous side reactions. Also, the non-uniform lithium-ion flux and infinite volume expansion of Li metal cause the growth of Li dendrites. These pose significant safety challenges and cause rapid capacity fading of the lithium metal batteries (LiMBs). To resolve these issues, a low-cost, easily processed, lightweight, high-performance carbon-based porous matrix is considered promising to host Li metal deposition. The three-dimensional (3D) porous nano/microstructured carbon provides sufficient space for Li accommodation during Li plating, buffers the volume changes during Li plating/stripping, and lowers the effective current density contributing to dendrite-free Li deposition. Besides, the outstanding electrochemical and mechanical stability, flexibility and the high electronic conductivity enable the nano/microstructured carbon to serve as both Li host and current collector. The development of 3D carbon/Li composite by mechanical roll-press techniques not only eliminates the complex and risky procedure of making carbon/Li composite based on Li plating or molten Li infusion but also stabilizes the capacity at higher Li plating/stripping rates. Recently, there is an advancement in the lithiophilic decorations of 3D structure to introduce sufficient nucleation sites and the development of artificial SEI on top of the 3D matrix to suppress Li dendrite formation. Such 3D structural modifications create a uniform electric field, lower the Li nucleation overpotential, provide strong mechanical and chemical stability, and stabilize the interface thereby inhibiting the degradation of lithium and the electrolyte. Here we summarize the research progress on porous carbon/Li composites in terms of materials type, structure, fabrication technique, their electrochemical battery performance, and identify the critical challenges that need to be addressed for high-energy-density practical LiMBs.

25 ENERGY STORAGE↗