Basic Energy Research Articles

Новая энергосырьевая денежная единица для расчетов в международной торговле

The article elaborates in detail the project of creating a neutral international currency for settlements in international trade — ERMU (Energy and Raw Material Unit), the purchasing power of which does not depend on political and economic actions of any country, nor on the exchange rate of national currencies. ERMU isn’t bound to any national currency, its purchasing power is nominated in a strictly specified amount of basic export energy raw materials of world trade — gas, oil, coal, ferrous and non-ferrous metals, mineral fertilizers, wheat and gold. Switching of international trade to ERMU will allow us to avoid the dictatorship of dollar and euro and to break the unnatural order in international trade, established after the Second World War, under which all countries traded with each other for the national currency of one country — the US dollar. In addition, the introduction of the ERMU will render meaningless any arrests and confiscation by Western countries of the assets of countries and individuals objectionable to them.

Exploring the Impact of Temperature on Non-Aqueous Redox Flow Cells

Nonaqueous redox flow batteries (NAqRFBs) remain an intriguing storage concept, but further improvements in performance and durability are needed to determine viability. An understudied but potentially-enabling feature of NAqRFBs is the ability to operate over a wide range of temperatures, facilitated by the breadth of solvent, supporting salt, and active species whose physicochemical properties differ from aqueous electrolytes. Elevated temperatures can increase reaction kinetics and transport rates, which are anticipated to improve performance, but may also promote decomposition processes, which are expected to lower durability. Elevated temperatures also increase system complexity, requiring energy input through additional balance-of-plant equipment, consequently necessitating energy balance and heat infrastructure considerations. While there are promising initial reports on molecular stability and electrolyte properties at elevated temperatures,1,2 there remains a need to better understand how temperature impacts performance-defining processes within NAqRFBs.In this presentation, we will discuss how molecular stability, electrolyte properties, and cell performance change as a function of temperature using 10-[2-(2-methoxyethoxy)ethyl]-10H-phenothiazine (MEEPT) as a model redox material.3 With increasing temperature, we observe that, as expected, the kinetic and species transport properties of the electrolyte improve (i.e., electrochemical reversibility, ionic conductivity, viscosity, active species diffusion). We connect these ex-situ findings to cell performance using a symmetric flow cell to quantify resistive losses and cycling stability, observing a marked decrease in cell resistance albeit at the expense of active species stability above a certain temperature threshold. Finally, we assess variable temperature operation of a NAqRFB full cell with MEEPT and (bis(2-(2-methoxyethoxy)ethyl)viologen bis(bis(trifluoromethanesulfonyl)imide) (MEEV-TFSI2) as the positive and negative electrolyte materials, respectively, observing enhancements in power performance but constraints on operating lifetime. These findings highlight that while temperature increases may be used as a means of increasing cell performance, care must be taken not to compromise component durability. While the exact set of conditions that balance this tradeoff are likely to be chemistry-dependent, the methods that will be described in the presentation are suitable for assessing these conditions in a general fashion. Acknowledgements This work was partially supported as part of the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy. A.H.Q., N.J.M., and B.J.N. gratefully acknowledge the National Science Foundation Graduate Research Fellowship Program under Grant Number 1745302. Any opinion, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the NSF. A.H.Q acknowledges the Alfred P. Sloan Foundation’s Minority Ph.D. (MPHD) Program. The authors thank Dr. Aman Kaur of the Odom Research Group in the Department of Chemistry at the University of Kentucky for insightful discussions and for synthesis of MEEPT-BF4, MEEPT-TFSI, and MEEV-TFSI2 species used in this study. References (1) Odom, S. A.; et al. Meet. Abstr. 2021, MA2021-02 (1), 110.(2) Shkrob, I. A.; et al. Journal of Molecular Liquids 2021, 334, 116533.(3) Kaur, A. P.; et al. Chem. Mater. 2020, 32 (7), 3007–3017. Figure 1

Li Morphology Evolution during Initial Cycling in a Gel Composite Electrolyte

Li metal anodes are the potential solution for high-energy batteries. One of the challenges of applying such a high-energy anode is Li dendrite growth, which results in short-circuit and thermal runaway. Current battery research focuses on developing solid electrolytes to serve as a physical barrier to prevent dendrite growth. However, the Li morphology change during plating and stripping, and the mechanisms of how Li dendrite grows and propagates into a complex composite solid electrolyte are poorly understood. Understanding and controlling Li morphology evolution, dendrite formation, and growth during cycling are crucial to developing dendrite suppression strategies for solid electrolytes and enabling high-energy lithium metal batteries.In this work, Li morphology evolution during initial cycling in a crosslinked PEO-based gel composite electrolyte full cell with NMC 811 cathode is monitored via post-mortem SEM. The results show that severe surface pitting occurs as early as the second stripping cycle. Pit formation and continuous dissolution is the main cause of Li surface roughening and dendrite growth mechanism in the model gel composite electrolyte. Comparing Li dendrite growth mechanisms in liquid, polymer, and solid electrolytes, the observed dendrite growth mechanism resembles that of the liquid electrolyte the most. This study suggests that strategies to improve the electrochemical reversibility of electrodeposited Li reported in liquid electrolytes to control Li morphology and prevent dendrite growth may be transferrable in a gel electrolyte.This work is sponsored by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory (ORNL), managed by UT-Battelle, LLC for the U.S. Department of Energy under Contract No. DE-AC05-00OR22725. Part of the measurements was performed at the Center for Nanophase Materials Sciences (CNMS), which is sponsored at Oak Ridge National Laboratory by the Scientific User Facilities Division, Office of Basic Energy Sciences.

Investigation of Surface Adsorption and Electrode Passivation during Electrochemical Oxidation of Redox-Active Organics

Redox-active organic molecules (ROMs) have gained interest as electroactive materials for redox flow batteries (RFBs). Electrochemical properties of ROMs, i.e., their solubility and redox potential, can be tuned through molecular engineering of the base molecule. Previously, we reported values of the apparent anodic charge transfer coefficient α (values approaching 1) associated with the electrochemical oxidation of a model ROM, 4-hydroxy-TEMPO.1 Also, we have proposed an adsorption-mediated mechanism to explain this unusual value of α, and have presented evidence to support the occurrence of adsorbed intermediates. Here, we extend this investigation to gain further insights using techniques of slow-scan voltammetry and electrode cycling, and apply them to other ROMs. We will discuss results of spectroscopic and micro-gravimetric studies, which provide further insights into the physicochemical properties of the adsorbed surface-passivating films. Ramifications of these to implementation of ROMs in flow batteries will be discussed too.[1] N. A. Shaheen, M. Ijjada, M. B. Vukmirovic, R. Akolkar. J. Electrochem. Soc., 167 (2020) 143505. Acknowledgements: Investigation of the model ROM was supported by Breakthrough Electrolytes for Energy Storage (BEES)—an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award #DE-SC0019409. Work completed at Argonne was supported by the Joint Center for Energy Storage Research (JCESR), a U.S. Department of Energy, Energy Innovation Hub, and by the U.S. Department of Energy, Office of Science, Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) program. The SCGSR program is administered by the Oak Ridge Institute for Science and Education (ORISE) for the DOE. ORISE is managed by ORAU under contract #DE‐SC0014664. All opinions expressed in this paper are the author’s and do not necessarily reflect the policies and views of DOE, ORAU, or ORISE.

Exposure Aging of Passive Films on Multi-Principal Element Alloys and Ramifications Towards Local Corrosion Resistance

Both highly engineered legacy and emerging alloys lack information on the precise attributes of protective passive films especially after long-time exposures when it really matters. Relevant field exposure periods are nearly infinite in time but both accelerated testing and high-fidelity experiments are often very short term in duration. Recent studies have explored passivation and protection of a number of different MPEAs connecting oxide chemistry to corrosion electrochemistry but most reports are after reality brief exposure periods.The goals of this work are to (a) review the nature of passive films (i.e., solid solution oxides, phase separated single element oxides, and/or complex oxides) and (b) determine the effect of exposure aging on the evolution of oxide features such as composition, structure, phase separation and physical attributes such as thickness in MPEAs; and to correlate these features with both protectiveness in the passive range and local corrosion resistance. Furthermore, we aim to understand what factors limit beneficial alloying element enrichment in the oxide, and further insights on potential third element effects.The focus of the current work extends from the solid solution Ni-22Cr, Ni-22Cr-6Mo, and Ni-22Cr-6Mo-3W family to a variety of emerging MPEAs containing “d-block” elements. AC and DC electrochemistry during potential sweeps and potential step passivation studies were conducted in 0.1 M NaCl pH 4 (HCl) as well as other solutions in the passive range. Exposure and high-fidelity characterizations were investigated over 10 s to 10 days at select potentials.Improvements in passive films protectiveness were correlated with the enrichment of certain elements and depletion of others. Mn oxides were found to be detrimental when formed over the long term in the outer layer of oxides on MPEAs. The most corrosion-resistant alloys possess passivating films that are efficacious not only just after formation, but that self-heal as well as improve over long exposure times as evident from impedance spectroscopy and metastable pitting resistance. Such alloys were observed to be the most resistant when interrogated for local corrosion compared to inferior alloys whose impedance response degraded over time as the passive film evolved. The latter alloys eventually arrived at conditions susceptible to local corrosion. Time-potential-transformation diagrams based on long-term exposures in Cl- followed by high fidelity characterization is suggested to be an approach to improve scientific understanding of long-term passive-protection features relevant to chloride exposures.This work was supported as part of the Center of Performance and Design of Nuclear Waste Forms and Containers, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-SC0016584; the Office of Naval Research under MURI ONR N00014-16-1-2280 and N00014-19-1-2420.

How Halide Sub-Lattice Affects Li Ion Transport in Antiperovskites

Li-based antiperovskites (LiAP, Li3-x OH x X, X = Cl, Br) are an emergent class of Li-ion conductors that are potential candidates for electrolytes in all-solid-state batteries. As a material class, pLiAP shows vast compositional design freedom; however, the resulting properties are susceptible to synthesis and processing methodologies. For example, proton incorporation and halide mixing stabilize the perovskite cubic phase near room temperature, and halides mixtures near the eutectic points drive the solid-state reaction temperature down, allowing for faster synthesis and processing conditions (< 1 h). The mixed halogen compositions, such as Li2OHCl0.37Br0.63, also show a 30-fold improvement in room temperature ionic conductivity of a single halide structure, 1.5 x 10-6 vs. 4.9 x 10-8 S cm-1 (Li2OHCl). Despite the growing interest in these materials, important questions remain about LiAPs on the structure-property correlation upon halide substitution and the correlations between the OH/halide dynamics and the Li-ion transport. We thus attempted to deconvolute how proton dynamics and halide substitution enhance or impede ionic conduction in pLiAP at compositions near the halide salts' eutectic points.We combined infrared spectroscopy and nuclear magnetic resonance (NMR) with first-principles density functional theory (DFT) calculations to deconvolute halide mixing effects from local proton dynamics on Li-ion transport. The NMR results and ab initio molecular dynamics suggest that Li+ transport is more strongly correlated with halide dynamics. While the hydroxide does stabilize the highly conductive cubic structure, it limits correlative ionic transport and thus lowers Li+ conductivity.Experiment design, data analysis, and manuscript preparation (RLS) were supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Science and Engineering. Synthesis (THB and JN) were supported by Asst. Secretary, Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (VTO) through the Advanced Battery Materials Research (BMR) Program. P. J. acknowledges partial support by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under Award DE-FG02-96ER45579. H. F. was supported from U.S. Department of Energy (Award No. DE-EE0008865). This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. The NMR characterization part of the work is supported by the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, and Basic Energy Sciences. The NMR work was performed at the W. R. Wiley Environmental Molecular Sciences Laboratory, a DOE User Facility sponsored by the Office of Biological and Environmental Research, located at Pacific Northwest National Laboratory. Figure 1

(Invited) Identification of Lithium Hydride and Nanocrystalline Lithium Fluoride in the SEI of Lithium Metal Anodes and the Stabilization of High Ni Layered Structure at Ultra-High Voltage through Cathode Electrolyte Interphase Engineering

Solid-electrolyte interphase (SEI) plays a pivotal role in the performance of lithium metal anode, which is promising for high energy batteries. Understanding SEI composition is important but very challenging. Here we report on the use of synchrotron-based X-ray diffraction and pair distribution function analysis to identify and differentiate the two elusive components, LiH and LiF, in the SEI of lithium metal anodes. LiH is identified as a component of SEI in high abundance, and the possibility of its misidentification as LiF in the literature is discussed. LiF in the SEI is found to have different structural features from LiF in bulk phase, including larger lattice parameter and smaller grain size (<3 nm). These characteristics favor Li+ transport, and explain why an ionic insulator, like LiF, has been found to be a favored component for SEI. PDF analysis of the SEI reveals key amorphous components related to solvent or anion decomposition.Nickel-rich layered cathode materials with high energy density are very promising for next generation batteries when coupled with lithium metal anode. However, the practical capacities accessible are far less than the theoretical value due to their structural instability during cycling, especially when charged at high voltages. Such challenge has been attributed to the concomitant electrolyte instability and cathode structural and morphological degradation. Therefore, various approaches have been developed through electrolyte engineering and bulk cathode material modifications. In this presentation, we will report a simple interphase engineering approach by using an ionic electrolyte additive, lithium difluorophosphate (LiDFP). Through theoretical calculation, we found that self-decomposition product PO2F of LiDFP additive is adsorbed strongly and uniformly on the Ni-rich cathode, which is further decomposed to Li3PO4 and LiF through the catalytic effect of transition metals. The new interphasial chemistry contributed from LiDFP stabilizes the bulk structure of Ni-rich cathode materials and prevents the performance degradation by suppressing the dissolution of transition metals and undesired structural changes. Even after 200 cycles with charge limit as high as 4.8 V, no rock-salt phase can be detected in LiNi0.76Co0.10Mn0.14O2 (NMC76), and the cell consisting of NMC76 cathode and lithium metal anode retains 97% of the initial capacity (235 mAh/g). Various advanced characterizations were used, on both atomic and electrode levels, to reveal the mechanism how a new interphase stabilizes the layer structures in bulk electrode. The dissolution of nickel was identified to be most serious at high voltage, rather than the widely believed manganese dissolution. The transition metal dissolution can be effectively suppressed by LiDFP additive. Furthermore, the cathode surface protected by LiDFP-derived interphase is shown to regulate a more uniform lithium distribution within the bulk cathode particles and effectively mitigate the strain and crack formation. Machine-learning assisted nano-tomography discovered that such interphase-bulk interaction is most effective for those small-sized, spherically-shaped particles.Acknowledgement:The work done at Brookhaven National Laboratory was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the U.S. DOE through the Advanced Battery Materials Research (BMR) Program, (Battery500 Consortium), and Applied Battery Research for Transportation (ABRT) program under contract No. DE-SC0012704. This work used the resources of the Center for Functional Nanomaterials, a U.S. DOE office of Science User Facility, at Brookhaven National Laboratory, and beamlines 5-ID, 7-BM, 23-ID-2, and 28-ID-2 of the National Synchrotron Light Source II, a US DOE Office of Science user facility operated for the DOE Office of Science by Brookhaven National Laboratory under contract no. DE-SC0012704. The work done at Pacific Northwest National Laboratory was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy through the Advanced Battery Materials Research (BMR) Program (Battery500 Consortium) under contract No. DE-AC02-05CH11231. The work at ARL was performed under JCESR, an Energy Research Hub funded by Basic Energy Science, US Department of Energy.

(Invited) Effects of Halide Anion Type and Alkyl Chain Length on Hydrogen Bonding in Eutectic Solvent System

Deep eutectic solvent (DES), formed by the intermolecular hydrogen bonding between its components of an H–bond acceptor (HBA) and an H–bond donor (HBD), has been extensively studied in the area of material synthesis, catalysis, electrochemistry, etc. The properties of DES including melting point, color, density, viscosity, conductivity, etc. are closely related to the H-bond network. Establishing an understanding of the H-bond structure offers an opportunity to fine-tune these properties.Hence, in this study, we systematically investigated the effects of halide anion type and alkyl chain length on the hydrogen bond network of a series of eutectic solvent systems and attempted to establish an unambiguous H-bond correlation with the conductivity. We varied the halide anion from Cl− to I− (Cl−, Br−, I−) and the alkyl chain length from methyl to butyl (n c = 1, 2, 4), and performed FTIR and conductivity measurements. Results show that the OH stretching peak exhibits a blue shift with the halide anion varies in the order of Cl−, Br−, I− when compared with the neat ethylene glycol (Figure 1a), indicating an increase in H-bond strength. A similar trend can be found with the increasing alkyl chain length as well. A stronger H-bond network inhibits the mobility of these halide anions in the eutectic system, as a result, the conductivity will decrease as shown in Figure 1b. Further probing the H-bond network with ultrafast spectroscopy is currently underway. Figure 1. (a) FTIR spectrum of neat EG and TBAX:EG(1:10) sample, X= Cl−, Br−,I−. (b) Trend between the OH stretching peak shift (vs. neat EG) and conductivity of these investigated samples.AcknowledgememtsThis work was supported as part of the Breakthrough Electrolytes for Energy Storage (BEES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-SC0019409 Figure 1

Repassivation Temperature of One-Dimensional Artificial Pits in Stainless Steel

A new framework has been developed in recent works to describe pit growth stability 1-8, based on which many critical scientific issues in localized corrosion were addressed, such as the rate-controlling step in pit growth, the salt film growth and self-regulating mechanism, and the kinetics and the activation energy of metal dissolution in the local pit environment. Although many new insights were generated, there are still some phenomena that are not well understood, such as the pit repassivation temperature (T rp). According to the new framework, T rp is predicted to decrease with the increase of applied potential (E app). However, T rp sometimes exhibits an unexpected dependence on E app that contradicts with the prediction, and the underlying mechanism is not clear.In this study, T rp of one-dimensional artificial pits made from 316L stainless steel was investigated in 3.5 wt.% NaCl by downward temperature scanning. For a given pit depth, T rp exhibits an unexpected “S” dependence on applied potential, which has never been reported previously. Further analysis shows that this relationship is derived from repassivation underneath the salt film, which is different from repassivation that occurs when the pit surface concentration decreases below a critical value. This indicates that there is a reversal of the effect of the salt film on pit growth stability. The systematic study shows that such a reversal depends on temperature, E app, and pit depth. Acknowledgments: This work was supported as part of the Center for Performance and Design of Nuclear Waste Forms and Containers, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-SC0016584.References G. S. Frankel, T. Li, and J. R. Scully, Journal of the Electrochemical Society, 164 (4), C180-C181 (2017).T. Li, J. R. Scully, and G. S. Frankel, Journal of The Electrochemical Society, 165 (9), C484-C491 (2018).T. Li, J. R. Scully, and G. S. Frankel, Journal of The Electrochemical Society, 165 (11), C762-C770 (2018).T. Li, J. R. Scully, and G. S. Frankel, Journal of The Electrochemical Society, 166 (6), C115-C124 (2019).T. Li, J. R. Scully, and G. S. Frankel, Journal of The Electrochemical Society, 166 (11), C3341-C3354 (2019).T. Li, J. Wu, and G. S. Frankel, Corrosion Science, 182 109277 (2021).T. Li, J. Wu, X. Guo, A. M. Panindre, and G. S. Frankel, Corrosion Science, 193 109901 (2021).T. Li, D. E. Perea, D. K. Schreiber, M. G. Wirth, G. J. Orren, and G. S. Frankel, Corrosion Science, 174 108812 (2020).

(Invited) Transient Absorption and Compressive Sensing for Understanding Dynamics in Photocatalytic Nanoparticles and Energy Conversion Materials

Transient absorption (TA) is a well-known tool for understanding the dynamical response of materials following the absorption of a photon. TA allows the dynamics of photoinduced energy flow and energy conversion to be monitored, along with other competing dissipative processes. With current technologies, TA can provide dynamical information over the ultraviolet, visible, near-infrared, mid-infrared, and terahertz spectral ranges, which allows the study of a concomitant range of photoinduced processes of relevance to photocatalysis. However, since TA usually involves very small changes in absorption, the approach can be quite time consuming and, as a result, signal averaging for hours is not uncommon. In addition to time limitations, long signal averages are challenging for many materials, including photocatalytic systems, because many materials degrade under long periods of laser illumination. Longer experiments also place greater demands on the stability of lasers, usually leading to the need for environmental controls, which adds cost and complexity to TA spectroscopies. Thus, there are several important reasons to increase the speed of TA as long as accuracy and sensitivity can be maintained.In this talk, I present recent efforts to dramatically decrease the time needed to perform TA through compressive sensing, whereby a smaller number of data points are randomly collected over the chosed dynamical range of the TA experiment.[1] The general principle works well when the transformation of the optical signal to another domain has a low density of TA features. Studies and applications to colloidal plasmonic nanoparticles, such as nanostructures made of refractory materials, and energy conversion materials are shown. I also present imaging efforts using femtosecond optical pulses in scattering environments where conventional imaging is difficult.[2] By utilizing enhanced second harmonic generation from high peak-power ultrashort pulses, combined with compressive sensing approaches, successful reconstruction of optical images can be undertaken.Work performed at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, was supported by the U.S. DOE, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. This material is based on work supported by Laboratory Directed Research and Development (LDRD) funding from Argonne National Laboratory, provided by the Director, Office of Science, of the U.S. Department of Energy under Contract No. DE-AC02-06CH11357. References Adhikari, S., Cortes, C. L., Wen X., Panuganti, S., Gosztola, D. J., Schaller, R. D., Wiederrecht, G. P., Gray, S. K., “Accelerating ultrafast spectroscopy with compressive sensing,” Phys. Rev. Appl., Vol. 15, 024032, 2021.Wen, X., Adhikari, S., Cortes, C. L., Gosztola, D. J., Gray, S. K., Wiederrecht, G. P., “Ghost imaging second harmonic generation microscopy,” Appl. Phys. Lett., Vol. 116, 191101, 2020.

Driving Force behind the Amorphization in the Crystalline Cathode Structures during Alkali Metal Ion Intercalation for Electrochemical Energy Storage

Development of cathode structures suitable for Na-ion and K-ion batteries is still one of the major challenges on the way to the design of next-generation alkali metal-ion batteries. Although Li, Na and K belong to the same alkali metal group with a single charge in their cation form, intercalation of Na+ and K+ ions in electrodes is difficult since ionic radii of Na+ (0.98 Å) and K+ (1.38 Å) are larger than that of Li+ (0.69Å). Intercalation of alkali metal ions results in volumetric expansions in the electrode structure. Even modest expansions in brittle cathodes can cause particle fracturing in a larger crystalline-size scale. Intercalation of larger ions can cause structural collapse and amorphization induced by continuous accumulation of strains and distortions. However, the lack of understanding behind the amorphization mechanisms in the crystalline electrodes upon ion intercalation materials hinders the development of electrode structures suitable for these large ions.In the first part of the talk, we will first report the utilization of in situ digital image correlation and in-operando X-ray diffraction (XRD) techniques to probe dynamic changes in the amorphous phase of iron phosphate during potassium intercalation1. A new experimental approach allows to monitor dynamic physical and structural changes in the amorphous phase of the electrodes. This method offers new insights to study mechanics of ion intercalation in the amorphous nanostructures.In the second part of the talk, we will discuss the electrochemical and mechanical response of the iron phosphate cathodes upon Li, Na and K ion intercalation. Strain evolution during Li and Na intercalation results in more linear dependence on the state of charge / discharge. However, strains generated in the electrode shows nonlinear behavior during insertion / extraction of K ions. Strain rate calculations showed that K ion intercalation results in a progressive increase in the strain rate, whereas Li and Na intercalation induce nearly constant strain rates2. Our results shows that strain rates are critical factor for the amorphization of the crystalline structure, rather than the absolute value of electrochemical strains. These observations provide a fundamental insight into the impact of alkali ions on the redox chemistry and associated chemomechanical deformations.Acknowledgement: This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences (Award number DE-SC0021251).

Probing Local Ion Insertion through Strain-Current Correlation

Among different electrochemical energy storage devices, the ones that store a higher amount of energy (e.g., batteries) often undergo larger ion insertion-induced structural transformation and volume change, which results in lower rate performance. The ones that store a lower amount of energy (e.g., supercapacitors) usually show gradual structural change and smaller volume change. There is a strong correlation between electrochemistry and mechanical properties. Understanding the electro-chemo-mechanical coupling and controlling the ion insertion-induced strain is crucial for achieving high power and high energy storage devices. In-situ atomic force microscopy (AFM) is well suited to tackle this task as it allows tracking local volume changes and other mechanical responses sub-nanometer spatial resolution under the conditions close to the device operationIn this work, we monitored electrode volume change via in-situ AFM and demonstrated the electro-chemo-mechanical coupling behaviors during proton insertion into WO3 materials. The concept of mechanical cyclic voltammetry (mCV) curves was developed, and the relationship between electrochemical current and strain was investigated with simplified models. The results revealed multiple ion-intercalation processes with different mechanical responses are involved during electrode cycling. Local heterogeneity was investigated via mCV mapping, confirming that the charging mechanisms varied across the electrode. These local variations could be further correlated to local morphology, crystal orientations, or chemical compositions. We further demonstrate that the mCV approach is applicable to a variety of energy storage materials (e.g., birnessite and MXene) with the increasing complexity of current-deformation relationships.The work was supported by the Fluid Interface Reactions, Structures, and Transport (FIRST), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Measurements were performed at the Center for Nanophase Materials Sciences (CNMS), which is sponsored at Oak Ridge National Laboratory by the Scientific User Facilities Division, Office of Basic Energy Sciences.

Automating Correlative Electron Microscopy for Heavy Duty Fuel Cell Development

The efficiency and durability of proton exchange membrane fuel cells has come to the forefront of research and development efforts as sustainable transportation applications shift from passenger to heavy duty vehicles. Complementary research expertise and advanced instrumentation are required to accelerate materials discovery and degradation mitigation of fuel cell components, with significant attention on catalysts, ionomers and membranes. The scanning transmission electron microscope (STEM) is among the key characterization techniques for accelerating materials and device development, providing key insights into atomic scale structure. Automating STEM data acquisition and analysis enables large data sets with improved statistical relevance and throughput will expand the impact of this method in the rapid materials and accelerated stress test development.We will show how the latest instrument developments in automation and high speed detectors enable new insights into catalyst structure and electrode layer degradation. This includes correlative, multimodal STEM techniques, such as aberration-corrected imaging, secondary electron detection, energy dispersive X-ray spectroscopy, cryogenic microscopy and 4D-STEM, to build a more comprehensive view of the effect of particle size and composition on surface strain and durability. These results will be correlated with information obtained from X-ray scattering techniques and fuel cell performance testing to understand the type and degree of degradation occurring during accelerated stress tests under development for heavy duty applications. The prospect of automated electron tomography coupled with identical location (IL)-STEM to provide detailed three-dimensional information on catalyst-support interactions will also be discussed.This material is based on work performed by the Million Mile Fuel Cell Truck (M2FCT) Consortium, technology managers Greg Kleen and Dimitrios Papageorgopoulus, which is supported by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office. Electron microscopy research was supported by the Center for Nanophase Materials Sciences (CNMS), which is a US Department of Energy, Office of Science User Facility at Oak Ridge National Laboratory. The X-ray scattering experiments were performed at beamline 9-ID-C at the Advanced Photon Source (APS) at Argonne National Laboratory (ANL). Use of the APS, an Office of Science user facility operated by ANL, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AS02-06CH11357

Fully Exposed Metal Clusters: Fabrication and Application in Alkane Dehydrogenation

Alkanes are the foremost basic energy sources and represent an important basic chemical material for industrial applications. Highly efficient activation of C–H bonds can convert abundant alkanes into value-added products, such as alkenes and their corresponding polymers. Therefore, C–H bond activation of alkanes has attracted widespread attention in heterogeneous catalysis. Fully exposed cluster catalysts (FECCs), as a bridge linking metal single atoms (SAs) and nanoparticles (NPs), have been widely studied for many catalytic reactions, especially for alkane dehydrogenation. On FECCs, the highly exposed active sites with multiple metal atoms can promote adsorption of alkanes and intermediates, thus enabling facile C–H activation. Moreover, the electron-rich surface can facilitate the desorption of products to suppress overdehydrogenation and coke formation. Therefore, FECCs have exhibited remarkable catalytic performance in alkane dehydrogenation, compared with SAs and NPs. In this Review, we highlight the developments on FECCs, including the structure design and their unique catalytic performance in dehydrogenation of alkanes. The synthetic methods to fabricate FECCs are discussed for alkane dehydrogenation. Subsequently, recent progresses on understanding the relationship between catalytic performance and geometric/electronic structure of FECCs are summarized, to provide the insights into the nature of structure dependence and metal dependence in alkane dehydrogenation. The strategies to stabilize FECCs for alkane dehydrogenation, including support confining and bimetallic system construction, are systematically reviewed to provide a useful guidance for the catalyst design. Lastly, major prospects in FECCs are illustrated from the viewpoint of alkane dehydrogenation.

Combined neutron scattering and resonant ultrasound spectroscopy for lattice dynamics studies

Resonant ultrasound spectroscopy (RUS) and inelastic neutron scattering afford insight into solid state structures and excitations at vastly different frequency and length scales. We will discuss the combined use of these techniques to understand phase transitions in functional and structural materials. Structural complexity, such as chirality or incommensuration leads to emerging features in both techniques and modifies energy transport channels. Novel developments in techniques at the Oak Ridge neutron sources, that now enable in situ ultrasound spectrocopy in the neutron beam, and the RUSCal analysis software that now supports all Bravais classes and implements Monte-Carlo methods, will be discussed in example materials. [Work supported by the Deparment of Energy Office of Basic Energy Science and by Laboratory Directed Research at Oak Ridge National Laboratory. My thanks go to J. Torres, V. Fanelli, Y. Shinohara, E. Cakmak, C. Hua, A. Flores-Bettancourt, M. Ruis-Rodriguez for the collaboration and A. Zevalkink, D. Mandrus, V. Keppens, E. Lara-Curzio, and T. Watkins for fruitful discussions.]

Interactions Environmental Processes and Development of Human Organisms Activities Via Mechanisms of Mental Activity from the Point of Views of Biophysics, Biochemistry and Thermodynamics

The article studies development of human organism in condition interactions with environment activity. There were described the role of solar processes in forming both non-living substances and living organisms through, from the one hand, germination living substances and also processes germination prokaryotic organisms and, from the second hand, germination living substances and also processes germination prokaryotic organisms which peculiarities were presented. Further there were elucidated dependence eukaryotic lives on Environmental influences of Solar system via creating mechanism maintenance stability an open thermodynamic system of an eukaryotic organisms according to famous Prigogine theorem. Thus there were described in details mechanisms maintenance stability an open non equilibrium non linear thermodynamic system of human organism in which Basic Internal Energy (Ebas) as builded bonds into molecule and atoms, bonds among compound processes of open thermodynamic biologic system, as inherited energy of genomic processes, bonds processes development of open thermodynamic system of an organism form Basic Internal Energy of Molecular Bonds (EbasMolBonds), Basic Internal Energy of Trophic Processes (EbasTroPr) and Basic Internal Energy of Mental-Soul Processes (EbasMenPr). At last it was described mechanisms operations of different receptors between an organism and Environment as well as neurons cellular mechanisms with environmental interactions causing development and maintenance stability Basic Internal Energy of Mental-Soul Processes (EbasMenPr), of Trophic Processes (EbasTroPr) of Molecular Bonds (EbasMolBonds) that form mental peculiarity of an organism

Decoupling China’s mining carbon emissions from economic development: Analysis of influencing factors

Mining provides basic materials and energy for human life and supports economic and social prosperity and development. The decoupling of mining carbon emissions from economic development is an important way of achieving China’s carbon peaking and carbon neutrality goals. This study uses the Tapio decoupling model to measure the relationship between China’s economic development and carbon emissions from 2001 to 2018. It analyzes the overall industry as well as its subdivisions and identifies the factors driving carbon emissions with help from the improved Kaya identity and LMDI decomposition models. The results show that, except for the unstable situation in the oil and natural gas mining industry, the other mining divisions have attained strong decoupling and have become stable, showing a continuous positive trend. On the whole, the mining product smelting and processing industry has achieved a major transformation, moving from negative decoupling to weak decoupling, but there are great differences between different sub-sectors. The overall consumption of China’s mining products, and the incremental carbon emissions have continued to decline, while economic development has shifted from inefficient expansion to high-quality economic development, although without reaching the ideal state. The economic factor and energy intensity effects are the key factors in increasing and restraining carbon emissions, respectively, and their influence should not be ignored. This study aims to provide a decision-making basis for China’s mining industry, that it might carry out carbon emission reduction planning, and promote the clean and efficient construction of the industry and the green and high-quality development of the economy.

Techno-Economic Optimization Study of Interconnected Heat and Power Multi-Microgrids with a Novel Nature-Inspired Evolutionary Method

The world is once again facing massive energy- and environmental challenges, caused by global warming. This time, the situation is complicated by the increase in energy demand after the pandemic years, and the dramatic lack of basic energy supply. The purely “green” energy is still not ready to substitute the fossil energy, but this year the fossil supplies are heavily questioned. Consequently, engineering must take flexible, adaptive, unexpected directions. For example, even the natural gas power plants are currently considered “green” by the European Union Taxonomy, joining the “green” hydrogen. Through a tight integration of highly intermittent renewable, or other distributed energy resources, the microgrid is the technology of choice to guarantee the expected impacts, making clean energy affordable. The focus of this work lies in the techno-economic optimization analysis of Combined Heat and Power (CHP) Multi-Micro Grids (MMG), a novel distribution system architecture comprising two interconnected hybrid microgrids. High computational resources are needed to investigate the CHP-MMG. To this aim, a novel nature-inspired two-layer optimization-simulation algorithm is discussed. The proposed algorithm is used to execute a techno-economic analysis and find the best settings while the energy balance is achieved at minimum operational costs and highest revenues. At a lower level, inside the algorithm, a Sequential Least Squares Programming (SLSQP) method ensures that the stochastic generation and consumption of energy deriving from CHP-MMG trial settings are balanced at each time-step. At the upper level, a novel multi-objective self-adaptive evolutionary algorithm is discussed. This upper level is searching for the best design, sizing, siting, and setting, which guarantees the highest internal rate of return (IRR) and the lowest Levelized Cost of Energy (LCOE). The Artificial Immune Evolutionary (AIE) algorithm imitates how the immune system fights harmful viruses that enter the body. The optimization method is used for sensitivity analysis of hydrogen costs in off-grid and on-grid highly perturbed contexts. It has been observed that the best CHP-MMG settings are those that promote a tight thermal and electrical energy balance between interconnected microgrids. The results demonstrate that such mechanism of energy swarm can keep the LCOE lower than 15 c€/kWh and IRR of over 55%.

Comparison of damping performance of an aluminum bridge via material damping, support damping and external damping methods

Damping property is the basic energy dissipation mechanism that widely exists in almost all kinds of structures or components. This paper presents an experimental study on three different measures including rubber sheet pavements, rubber bearings and external passive damper to increase the damping of a lightly damped aluminum bridge. These methods are conventional treatments in engineering practice, and they aim to take effect through the aspects of material damping, support damping and external damping, respectively. The performance of these methods in damping increment is compared, and the possible damping mechanism of each measure is discussed. The external damper is found to be most effective in damping increment, followed by rubber bearings. The method of rubber sheet pavement is inefficient in damping increment owing to the huge difference in elastic modulus between aluminium and rubber. The rubber sheet keeps in tiny strain state during structural vibration and fails to generate effective internal friction between particles, and thus contributes little to the overall material damping. This indicates that the damping material method can take effect only if the damping layer has not only remarkable loss factor but also comparable elastic modulus with the target structure. In addition, the external damper generally follows the linear viscous damping law. The external damper having liquid viscosity of 3.05 Pa·s can increase the system damping to 1.5 %, which is almost one order greater than the performance of rubber sheet pavement and rubber bearing methods. Moreover, the external damping method is found to be sensitive to the installation location of the damper. The greater the modal displacement, the larger the system damping is. Furthermore, the system damping is not sensitive to structural frequency, whereas it slightly increases with the structural strain in small strain levels.

Molecular structure characterization analysis and molecular model construction of anthracite.

Coal is the largest non-renewable energy as well as an important basic energy and industrial raw material. Thus, correctly understanding the molecular structure characteristics of coal has important theoretical value for realizing carbon neutralization. In this work, we clarified the molecular structure characteristics of anthracite, where the organic matter in anthracite was characterized and analyzed by industrial/elemental analysis, FTIR, XPS, XRD and solid 13C NMR. The ratio of bridge carbon to the perimeter carbon of anthracite was 0.38, and the degree of condensation in the aromatic structure was high. Nitrogen in coal primarily exists in the form of pyridine and pyrrole. Based on the information on functional group composition, the carbon skeleton structure, and surface element composition, a molecular structure model of Yangquan anthracite could be constructed, where the molecular formula was C208H162O12N4. This study may serve as a reference for researchers in this field to consult and refer to the construction ideas and methods of molecular structure models of different coal samples.