Moderate Charge Research Articles

Microenvironment regulation to synthesize sub-3 nm Pt-based high-entropy alloy nanoparticles enabling compressed lattice to boost electrocatalysis

Platinum (Pt) is inevitably employed to facilitate various electrocatalysis including hydrogen oxidation/evolution and oxygen reduction reactions (HOR/HER/ORR), the foundation for renewable energy conversion and storage. Pt-based high-entropy-alloy (HEA) catalysts have been recently presenting promises to improve intrinsic activity of unit mass Pt. However, their current synthesis methods always produce large particles—some can control small size but have to use complicated recipe and/or highly toxic and expensive chemicals. Alternatively, a facile microenvironment regulation strategy is herein proposed to tune solvent polarity and nanoparticle-support interactions within the precursors for carbon-thermal shock pyrolysis. We found that the decreased solvent polarity and enhanced particle-support affinity can jointly control the nanoparticle size ultimately to ∼2.68 nm with ∼10 wt% Pt loading. The compressed lattice fringe in such HEA particles leads to electron accumulation at Pt atoms and build a moderate charge density rearrangement, showing superior multifunctional HER/HOR/ORR activity to Pt/C in acidic media.

Hybrid Local and Charge-Transfer Material with Ultralong Room Temperature Phosphorescence for Efficient Organic Afterglow Light-Emitting Diodes.

Organic ultralong room temperature phosphorescence (OURTP) materials capable of combining various emission behaviors for diversified optoelectronic properties and applications have recently gained a vigorous development, but it remains a forbidden challenge in designing OURTP molecules with hybrid local and charge-transfer (HLCT) feature, possibly due to the elevated difficulties in simultaneously meeting the stringent requirements of both HLCT and OURTP emitters. Here, through introducing multiple heteroatoms into one-dimensional fused ring of coumarin with moderate charge transfer perturbation in donor-π-acceptor architecture, we demonstrate a HLCT-featured OURTP molecule showing both promoted fluorescence with a quantum yield of 77 % in solution and long-lived OURTP with a lifetime of 251 ms in conventional host material used in electroluminescent device. Thus, efficient OURTP organic light-emitting diodes (OLEDs) were fabricated, exhibiting bright electroluminescence with an exciton utilization efficiency of 85 % and yellow OURTP lasting over 2 s for afterglow. Impressively, the HLCT OURTP-OLEDs can be further optimized to reach an unprecedented total external quantum efficiency (EQE) of ~12 % and OURTP EQE up to 3.11 %, representing the highest performance among the reported OURTP-OLEDs. These impressive results highlight the significance to fuse HLCT and OURTP together in enriching OURTP materials and improving the afterglow OLED performances.

Effect of Lattice Misfit on the Stability of the Misfit Layer Compound (SnS)1+xNbS2

The prototype misfit layer compound (SnS)1.17NbS2 consists alternatingly of a metallic triatomic NbS2 layer, in which Nb atoms are sandwiched by S atoms, and an insulating SnS double layer featuring a NaCl-type structure. Here we investigate the effect of lattice misfit on the stability and chemical bonding in the misfit layer compound using a first-principles density functional theory approach. The calculations show that for the (SnS)1+xNbS2 approximants, the most stable one has x = 0.167, close to the experimental observations. Charge analysis finds a moderate charge transfer from SnS to NbS2. Sn or S vacancies in the SnS part affect the electronic properties and interlayer interactions. The obtained information here helps in understanding the mechanism of formation and stability of misfit layer compounds and ferecrystals and further contributes to the design of novel multilayer compounds and emerging van der Waals heterostructures.

Cost‐Effective Layered Oxide – Olivine Blend Cathodes for High‐Rate Pulse Power Lithium‐Ion Batteries

AbstractSustainability and supply‐chain concerns require lithium‐ion batteries (LIBs) free from critical minerals, such as nickel and cobalt. While recent advances provide encouraging signs that cobalt can be removed, the question remains how much Ni can be removed from Co‐free layered oxide cathodes before sacrificing critical performance metrics. This study highlights the effect of reducing Ni by benchmarking several Co‐free cathodes with decreasing Ni content. Keeping the energy density the same by increasing the charge voltage, cathodes below 80% Ni content exhibit worsened capacity fade due to increasing oxygen release and electrolyte decomposition. Charge transfer and diffusion kinetics are also hindered with increasing Mn content and exacerbated by resistive surface phases formed at high voltages, rendering lower‐Ni, Co‐free cathodes less competitive than high‐Ni cathodes for high energy and power applications. It is demonstrated blending layered oxide with olivine as an effective alternative to deliver energy density and cycling stability comparable to lower‐Ni cathodes with moderate charging voltages. Blending with 30 wt% olivine LiMn0.5Fe0.5PO4 (LMFP) virtually eliminates the diffusion limitation of layered oxides at low state‐of‐charge, with enhanced pulse power characteristics rivaling the high‐Ni counterparts. Cathode blending can further reduce the overall Ni content and cost without the performance limitations of lower‐Ni, Co‐free cathodes.

Boosting electrocatalytic nitrate-to-ammonia of single Fe active sites via coordination engineering: From theory to experiments

Atomically dispersed iron–nitrogen-carbon (Fe–N4–C) catalysts show great promises for the electrocatalytic nitrate (NO3−) reduction to ammonia (NH3). Nevertheless, the microenvironmental engineering of the single Fe active sites for further optimizing the catalytic performance remains a challenge. Herein, we proposed to regulate the coordination environment of single Fe active sites to boost its intrinsic electrocatalytic activity for NO3− –to–NH3 conversion by the incorporation of new heteroatoms, including B, C, O, Si, P, and S. Our results revealed that most of the candidates possess low formation energies, showing great potential for experimental synthesis. Moreover, incorporating heteroatoms effectively modulates the charge redistribution and the d–band center of single Fe active sites, enabling the regulation of the binding strength of nitrogenous intermediates. As a result, the N and C coordinated Fe active site (Fe–N3C) exhibits superior catalytic performance for NO3− electroreduction with a relatively low limiting potential (–0.13 V) due to its optimal adsorption strength with nitrogenous intermediates induced by its moderate charge and d–band center. Importantly, our experimental measures confirmed such theoretical prediction: a maximum NH3 yield rate of 21.07 mg h−1 mgcat.−1 and 95.74 % Faradaic efficiency were achieved for NO3− electroreduction on Fe–N3C catalyst. These findings not only suggest a highly efficient catalyst for nitrate reduction but also provide insight into how to design and prepare electrocatalysts with enhanced catalytic performance.

Large and Small Polarons in Highly Efficient and Stable Organic‐Inorganic Lead Halide Perovskite Solar Cells: A Review

Polarons, which arise from the intricate interplay between excess electrons and/or holes and lattice vibrations (phonons), represent quasiparticles pivotal to the electronic behavior of materials. This review reaffirms the established classification of small and large polarons, emphasizing its relevance in the context of recent advances in understanding lead halide perovskites' behavior. The distinct characteristics of large and small polarons stem from the electron–phonon interaction range, which exerts a profound influence on materials’ characteristics and functionalities. Concurrently, lead halides have emerged with exceptional opto‐electronic properties, featuring prolonged carrier lifetimes, low recombination rates, high defect tolerance, and moderate charge carrier mobilities; these characteristics make them a compelling contender for integration of optoelectronic devices. In this review, the formation of both small and large polarons within the lattice of lead halide perovskites, elucidating their role in protecting photogenerated charge carriers from recombination processes, is discussed. As optoelectronic devices continue to advance, this review underscores the importance of unraveling polaron dynamics to pave the way for innovative strategies for enhancing the performance of next‐generation photovoltaic technologies. Future research should explore novel polaronic effects using advanced computational and experimental techniques, enhancing our understanding and unlocking new applications in materials science and device engineering.

The types of metal M and crystal surface in the PtM (M = Co, Ni, Zn) IMCs catalysts to regulate catalytic performance of ethane direct dehydrogenation

PtM IMCs have improved catalytic performance of ethane dehydrogenation (EDH), however, identifying the functions of the types of metal M and crystal surface for the PtM IMCs catalysts in regulating EDH catalytic performance are still a challenge in experiment. This work fully investigated catalytic performance of EDH over three crystal surfaces (110), (111) and (200) of PtM IMCs (M = Co, Ni, Zn) by using density functional theory (DFT) calculations and kinetic Monte Carlo (kMC) simulations. The results show that the catalytic performance of EDH over PtM IMCs strongly depend on the types of metal M and crystal surfaces, the PtZn(111) catalyst is screened out as the most promising in EDH reaction with the optimal reaction temperature of 773.15 K. The geometrically isolated Pt site in the [PtM3] assembly of PtZn(111) could catalyze the CH cleavage, and C2H4* exhibits weak π-adsorption model at the individual Pt sites, promoting C2H4* desorption. Compared to (110) and (200) surfaces, the (111) surface with moderate Bader charge transfer showed the highest C2H4(g) production activity, and Zn atoms transferred more electrons to Pt atoms, which greatly weakened the charge transfer between C2H4* and the catalyst surface, favoring C2H4* desorption to inhibit C2H4* deep dehydrogenation. Moreover, the catalytic performance of PtZn(111) catalyst is superior to the industrially used PtSn catalyst. This work provides valuable structure clue for the design of high-performance catalyst in alkane direct dehydrogenation.

MoS2, WS2, and MoWS2 Flakes as Reversible Host Materials for Sodium-Ion and Potassium-Ion Batteries.

Transition-metal dichalcogenides (TMDs) and their alloys are vital for the development of sustainable and economical energy storage alternatives due to their large interlayer spacing and hosting ability for alkali-metal ions. Although the Li-ion chemically correlates with the Na-ion and K-ion, research on batteries with TMD anodes for K+ is still in its infancy. This research explores TMDs such as molybdenum disulfide (MoS2) and tungsten disulfide (WS2) and TMD alloys such as molybdenum tungsten disulfide (MoWS2) for both sodium-ion batteries (NIBs) and potassium-ion batteries (KIBs). The cyclic stability test analysis indicates that in the initial cycle, the MoS2 NIB demonstrates exceptional performance, with a peak charge capacity of 1056 mAh g-1, while retaining high Coulombic efficiency. However, the WS2 KIB underperforms, with the least charge capacity of 130 mAh g-1 in the first cycle and exceptionally low retention at a current density of 100 mA g-1. The MoWS2 TMD alloy exhibits a moderate charge capacity and cyclic efficiency for both NIBs and KIBs. This comparison study shows that decreasing sizes of alkali-metal ions and constituent elements in TMDs or TMD alloys leads to decreased resistance and slower degradation processes as indicated by cyclic voltammetry and electrochemical impedance spectroscopy after 10 cycles. Furthermore, the study of probable electrochemical intercalation and removal processes of Na-ions and K-ions demonstrates that large geometrically shaped TMD flakes are more responsive to intercalation for Na-ions than K-ions. These performance comparisons of different TMD materials for NIBs and KIBs may promote the future development of these batteries.

Nanoemulsions and nanocapsules as carriers for the development of intranasal mRNA vaccines

The global emergency of coronavirus disease 2019 (COVID-19) has spurred extensive worldwide efforts to develop vaccines for protection against severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). Our contribution to this global endeavor involved the development of a diverse library of nanocarriers, as alternatives to lipid nanoparticles (LNPs), including nanoemulsions (NEs) and nanocapsules (NCs), with the aim of protecting and delivering messenger ribonucleic acid (mRNA) for nasal vaccination purposes. A wide range of prototypes underwent rigorous screening through a series of in vitro and in vivo experiments, encompassing assessments of cellular transfection, cytotoxicity, and intramuscular administration of a model mRNA for protein translation. As a result, two promising candidates were identified for nasal administration. One of them was a NE incorporating a combination of an ionizable lipid (C12-200) and cationic lipid (DOTAP), both intended to condense mRNA, along with DOPE, which is known to facilitate endosomal escape. This NE exhibited a size of 120 nm and a highly positive surface charge (+ 50 mV). Another candidate was an NC formulation comprising the same components and endowed with a dextran sulfate shell. This formulation showed a size of 130 nm and a moderate negative surface charge (-16 mV). Upon intranasal administration of mRNA encoding for ovalbumin (mOVA) associated with optimized versions of the said NE and NCs, a robust antigen-specific CD8 + T cell response was observed. These findings underscore the potential of NEs and polymeric NCs in advancing mRNA vaccine development for combating infectious diseases.Graphical

Evaluating hydrogen embrittlement susceptibility of operated natural gas pipeline steel intended for hydrogen service

Green hydrogen produced by renewable energy sources is expected to play an important role as a decarbonized energy carrier. It can be transported cost-effectively over long distances by pipelines. Hydrogen transport through existing natural gas pipeline networks is supposed to be prospective. However, a possible degradation of gas pipeline steels as a result of their long-term operation should be taken into account in assessing the prospects of using the existing gas network for hydrogen transportation safely. In this study, hydrogen embrittlement susceptibility of low-carbon pipeline steel in the as-received state and after long-term operation is investigated. The influence of long-term operation on the microstructure, mechanical properties, and fracture mechanism of steel is assessed, considering the direction of cutting the specimens relative to the pipe axis. The electrolytic hydrogen pre-charging process with different intensities is used to analyze the influence of absorbed hydrogen on the mechanical behaviour of steel by tensile tests of uncharged and hydrogen-charged specimens. The as-delivered steel is not prone to hydrogen embrittlement after moderate hydrogen charging, while the operated one is sensitive to it. Metallographic and fractographic analyses revealed a crucial role of non-metallic inclusions in the hydrogen embrittlement of steel, which depended on its technical state and hydrogen charging conditions. Moderate hydrogen charging led to intergranular embrittlement of steel, while intensive − to transgranular embrittlement, indicating different mechanisms of transport of hydrogen absorbed by the metal.

Nature of C-C coupling and strategy of tuning the catalytic activity of Cu-N-C catalysts for electro-reduction of CO2 to ethanol

With high atomic utilization and remarkable catalytic activity, Cu-N-C type catalysts display great potential for electro-catalysis in CO2 reduction. However, the relationship between the active moiety and catalytic activity of generating high-value C2 products is still unclear, and the explicit screening criteria is scarcity. Herein, based on the first-principle simulation, the structure-performance relationship on Cu-N-C type catalysts has been investigated by modulating the CO2 reduction process as the number of Cu atom (Cu1, Cu2, Cu3) and the ligand environment (B, C, N, O, P, S) changed. We find the adsorption strength of intermediate *CO strongly affect the possibility of C-C coupling, which can be determined by Bader charge on Cu atom, mainly depending on the number of loaded atomic Cu on Cu-N-C catalysts. Furthermore, the Bader charge can be refined by adjusting the coordination atom of Cu, thus optimizing catalytic activity for the CO2 to ethanol. The moderate Bader charge value, between +0.35 and +0.45, enables the catalyst to behave as a potentially excellent activity with low limiting potential for generating ethanol. More importantly, an intrinsic descriptor, composed of the radius, electronegativity, and number of valence electrons of coordination atoms (φ=∑χ∑r*∑np), was established to characterize the catalytic activity of Cu-N(X)-C catalysts for producing ethanol. Two excellent catalysts, Cu3-N2O2 (-0.51 V) and Cu3-N3S (-0.64 V), are screened out for the CO2RR to generate ethanol. This work discloses theoretical basis for catalytic selectivity of C2 products on Cu-N-C catalysts and provides a regulating and screening principle for high performance catalysts to ethanol.

Ultrasonic assessment of aging in lithium metal pouch cells

Lithium metal anodes are prone to non-uniform lithium plating that can lead to dendrite formation, internal short circuits, and catastrophic ignition. This type of structural defect is not captured by battery management systems, prompting the need to advance nondestructive evaluation (NDE) techniques that are suitable for periodic monitoring of the internal structure. An ultrasonic inspection technique is evaluated here as a means of identifying flaws and irregular lithium plating that can be a precursor to dendrite formation and, ultimately, battery failure.Lithium metal pouch cell batteries were aged through electrochemical cycling at a range of moderate constant-current charging and discharging rates. They were inspected intermittently using a tailored local ultrasonic resonance spectroscopy (LURS) approach that measures the local through-thickness resonances of the battery as an indicator of the underlying structure. LURS results showed clear structural resonances in cells in the range of 3–7 MHz, which shifted significantly to lower frequencies as batteries aged. In addition to point measurements, scanning LURS measurements were implemented to map resonance frequencies over the electrode surface. These resonance maps revealed spatial variations in structure that developed during aging and showed better contrast to structural variation than achieved using conventional amplitude-based c-scans of the specimens.NDE results from pouch cell measurements were compared to a destructive physical analysis of the electrode structures using scanning electron microscopy (SEM). The SEM results showed differences in the end-of-life lithium anode structure at different charge rates. The results of this study show the capability of LURS as a means for identifying changes in battery structures during aging and establish resonance trends that may be applied in future work for prognostic modeling of batteries in service.

Efficient Alkene Hydroformylation by Co-C Symmetry-Breaking Sites.

Alkene hydroformylation is one of the largest industrial reactions on an industrial scale; however, the development of nonnoble heterogeneous catalysts is usually limited by their low activities and stabilities. Herein, we constructed a 1% Co2C/SiO2 catalyst featuring Co-Cvacancy-Co-C symmetry-breaking sites, which generated a polar surface exhibiting a moderate charge density gradient at the localized Co atoms. Comparatively, this catalyst exhibited notable enhancements in the adsorption and activation of the reactants, as well as in the polarity between intermediates. Significantly, the spatial distance between the adsorption sites of intermediates was reduced, thereby effectively decreasing the energy barrier of reaction processes. As the density of the symmetry-breaking sites increased, the turnover number for propene hydroformylation soared to 18 363, exceeding the activity of heterogeneous Co-based catalysts reported thus far by 1 or 2 orders of magnitude, and the catalyst exhibited high stability during the reaction. This study provides a methodology for constructing atomically active sites, which holds great potential for the design and development of highly efficient catalysts.

CFD-DEM study on transport and retention behaviors of nZVI-clay colloids in porous media

Transportation process of nano scale zero valent iron (nZVI) in clay-rich soils is complicated and crucial for in-situ remediation of contaminated sites. A coupled computational fluid dynamic and discrete element method (CFD-DEM) was used to investigate the interplays of repulsive and attractive forces and the injection velocity of this process. The screened Coulomb’s law was used to represent the electrostatic interaction, and surface energy density was introduced to represent the effects of the van der Waals interaction. A phase diagram was constructed to describe the interplay between injection velocity and repulsive force (in terms of charge of colloids). Under the boundary and initial conditions in this study, clogging formed at low repulsive force (colloidal charge = −1 ×10-15 C), where increment of injection velocity (from 0.002 m/s to 0.02 m/s) cannot prevent clogging, as in the case of bare nZVI transportation with limited mobility; On the other hand, excessive repulsive force (charge = −4 ×10-14 C) is detrimental to nZVI-clay transportation due to repulsion from the concentrated colloids in pore throats, a phenomenon as in the overuse of stabilizers and was defined as the “membrane repulsion effect” in this study. At moderate charge (−1 ×10-14 C), injection velocity increment induced clogging due to aggregates formed at the windward of cylinder and accumulated at the pore throats.

Microstructure and tribological behavior in ta-C films prepared by laser-induced filtered cathodic vacuum arc technique: Effect of charge voltage

As an important power supply parameter, charge voltage has a significant influence on the properties of deposited films. In this work, the ta-C films were fabricated by the laser-induced filtered cathodic vacuum arc technique (LI-FCVA). The effect of charge voltage on microstructure, mechanical and tribological properties of ta-C films was investigated. Although macro-particles with various sizes were clearly visible on surfaces of films, the surface roughness was declined with increase of charge voltage. The sp3-C bond ratio in films was closely dependent on the charge voltage. At 160 V charge voltage, the sp3-C bond ratio was 54.1 %, then reaching to 61.2 % at the charge voltage of 190 V. With further increasing to 250 V, the sp3-C ratio slowly down to 57.1 %. This is ascribed to the change in energy for incident carbon ions which governed by the charge voltage. The highest hardness value, 54.5 ± 2.1 GPa, was obtained at the 190 V charge voltage, which was due to the high sp3-C content and relatively high residual stress. Similarly, the film deposited at 190 V possessed both low coefficient of friction (COF) and wear rate under various load, indicating that the excellent tribological performance of film could be achieved at 190 V. In addition, the COFs for all films decreased with an increase of load. The present work revealed that the moderate charge voltage value is beneficial for the enhanced wear property of film.

Condensation of the N-terminal domain of human topoisomerase 1 is driven by electrostatic interactions and tuned by its charge distribution

Liquid-liquid phase separation (LLPS) is pivotal in forming biomolecular condensates, which are crucial in several biological processes. Intrinsically disordered regions (IDRs) are typically responsible for driving LLPS due to their multivalency and high content of charged residues that enable the establishment of electrostatic interactions.In our study, we examined the role of charge distribution in the condensation of the disordered N-terminal domain of human topoisomerase I (hNTD). hNTD is densely charged with oppositely charged residues evenly distributed along the sequence. Its LLPS behavior was compared with that of charge permutants exhibiting varying degrees of charge segregation.At low salt concentrations, hNTD undergoes LLPS. However, LLPS is inhibited by high concentrations of salt and RNA, disrupting electrostatic interactions. Our findings show that, in hNTD, moderate charge segregation promotes the formation of liquid condensates that are sensitive to salt and RNA, whereas marked charge segregation results in the formation of aberrant condensates.Although our study is based on a limited set of protein variants, it supports the applicability of the “stickers-and-spacers” model to biomolecular condensates involving highly charged IDRs. These results may help generate reliable models of the overall LLPS behavior of supercharged polypeptides.

Structure and Dynamics of Hybrid Colloid-Polyelectrolyte Coacervates: Insights from Molecular Simulations.

Electrostatic interactions in polymeric systems are responsible for a wide range of liquid-liquid phase transitions that are of importance for biology and materials science. Such transitions are referred to as complex coacervation, and recent studies have sought to understand the underlying physics and chemistry. Most theoretical and simulation efforts to date have focused on oppositely charged linear polyelectrolytes, which adopt nearly ideal-coil conformations in the condensed phase. However, when one of the coacervate components is a globular protein, a better model of complexation should replace one of the species with a spherical charged particle or colloid. In this work, we perform coarse-grained simulations of colloid-polyelectrolyte coacervation using a spherical model for the colloid. Simulation results indicate that the electroneutral cell of the resulting (hybrid) coacervates consists of a polyelectrolyte layer adsorbed on the colloid. Power laws for the structure and the density of the condensed phase, which are extracted from simulations, are found to be consistent with the adsorption-based scaling theory of hybrid coacervation. The coacervates remain amorphous (disordered) at a moderate colloid charge, Q, while an intra-coacervate colloidal crystal is formed above a certain threshold, at Q > Q*. In the disordered coacervate, if Q is sufficiently low, colloids diffuse as neutral nonsticky nanoparticles in the semidilute polymer solution. For higher Q, adsorption is strong and colloids become effectively sticky. Our findings are relevant for the coacervation of polyelectrolytes with proteins, spherical micelles of ionic surfactants, and solid organic or inorganic nanoparticles.

(Invited) Operando Observation of Fast Charging in Li-Ion Cells

Fast charging (<15 min) of lithium-ion batteries (LIBs) for electrical vehicles (EVs) is widely seen as the key factor that will greatly stimulate the EV markets, and its realization is mainly hindered by the sluggish diffusion of Li+. To have a mechanistic understanding of Li+ diffusion within LIBs, in this study, structural evolutions of electrodes for a Ni-rich LiNi0.6Mn0.2Co0.2O2 (NMC622) || graphite cylindrical cell with high areal loading (2.78 mAh cm−2) are developed for operando neutron powder diffraction study at different charging rates. Via sequential Rietveld refinements, changes in structures of NMC622 and Li x C6 are obtained during moderate and fast charging (from 0.27 C to 4.4 C). NMC622 exhibits the same structural evolution regardless of C-rates. For phase transitions of Li x C6, the stage I (LiC6) phase emerges earlier during the stepwise intercalation at a lower state of charge when charging rate is increased. It is also found that the stage II (LiC12) → stage I (LiC6) transition is the rate-limiting step during fast charging. The LiC12 → LiC6 transition mechanism is further analyzed using the Johnson–Mehl–Avrami–Kolmogorov model. It is concluded as a diffusion-controlled, 1D phase transition with decreasing nucleation kinetics under increasing charging rates.

Operando X-Ray Analyses of NMC811/Li Batteries: Progress Towards Understanding Capacity Fading Mechanisms at High Voltage and Fast Charge

LiNi0.8Mn0.1Co0.1O2 (NMC811) is a commercially successful Li-ion battery cathode due to its high energy density and cyclability. Utilizing this system under fast charge and high potential charge conditions is of great interest as this will help facilitate widespread electric vehicle adoption; however, these aggressive charging conditions lead to enhanced capacity fade. To design next-generation NMC811 batteries with longer life and higher capacity the origins of the capacity fade must be understood. Operando X-ray characterization techniques are critical for this endeavor as they allow the acquisition of information about the evolution of structure, oxidation state, and coordination environment as the material (de)lithiates in a functional battery. Charging to high potential (4.7 V) leads to greater delivered initial capacity but much more significant fading; while fast charging (4C) leads to slightly reduced capacity but with similar fading. Operando XRD and SEM results indicated that secondary particle fracture from increased structural distortions at >4.3 V was a contributor to capacity fade. On the other hand, fast charging led to a slight reduction in structural distortions consistent with the reduced capacity fade. Operando hard XAS revealed significant Ni and Co redox during cycling as well as a Jahn-Teller distortion at the discharged state (Ni3+). Greater bulk redox was observed when charged to 4.7 V while less bulk redox was observed at 4C, consistent with the different delivered capacities. Soft XAS analyses revealed significant surface reconstruction after cycling to 4.7 V. Overall, charging to 4.7 V leads to more structural distortions and particle fracture, as well as surface reconstruction that lead to increased capacity fading. Fast charge does not induce additional structural distortion or surface reconstruction as compared to the slower, moderate charging potential cycling suggesting that the phenomena at the anode may be more critical under fast charge.

Comparative analyses of MIL-88B(Fe) and MIL-100(Fe) metal organic frameworks as active anode materials for Li ion batteries

Two Fe based metal organic framework (MOF) nanorod structures, MIL-88B(Fe) and MIL-100(Fe), were synthesized and their performance as working electrodes for Li ion half-cell batteries was evaluated under identical testing conditions. It was found that MIL-88B(Fe) provides a charge / discharge capacity of 468 mAh/g at the current density of 100 mA/g, which is over 3 times higher as compared to that of MIL-100(Fe) under the same conditions. Nevertheless, after an impressive charge / discharge capacity in the first few cycles, a slow capacity degradation was noticed in the case of the MIL-88B(Fe) material. Energy dispersive spectroscopy (EDS) and Fourier transform infrared (FTIR) spectroscopy results suggest that capacity degradation may be due to strained metal coordination in the MIL-88B(Fe) network. In contrast, despite moderate charge / discharge capacity such issues are identified to be minimal in the case of MIL-100(Fe). Electrochemical impedance spectroscopy (EIS) analyses suggest that ohmic and polarization resistance are smaller for MIL-88B(Fe) as compared to MIL-100(Fe) (both cycle 1 and 100). This makes MIL-88B(Fe) an attractive anode over MIL-100(Fe) for Li ion batteries, but stability issues remain a concern with MIL-88(B)Fe.