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At least 1,063 records · Page 59

Challenges in Lithium Metal Anodes for Solid-State Batteries

In this Perspective, we highlight recent progress and challenges related to the integration of lithium metal anodes in solid-state batteries. While prior reports have suggested that solid electrolytes may be impermeable to lithium metal, this hypothesis has been disproven under a variety of electrolyte compositions and cycling conditions. Herein, we describe the mechanistic origins and importance of lithium filament growth and interphase formation in inorganic and organic solid electrolytes. Multimodal techniques that combine real and reciprocal space imaging and modeling will be necessary to fully understand nonequilibrium dynamics at these buried interfaces. Currently, most studies on lithium electrode kinetics at solid electrolyte interfaces are completed in symmetric Li–Li configurations. To fully understand the challenges and opportunities afforded by Li-metal anodes, full-cell experiments are necessary. Lastly, the impacts of operating conditions on solid-state batteries are largely unknown with respect to pressure, geometry, and break-in protocols. Given the rapid growth of this community and the diverse portfolio of solid electrolytes, we highlight the need for detailed reporting of experimental conditions and standardization of protocols across the community.

25 ENERGY STORAGE↗

Phase shift method to estimate solids circulation rate in circulating fluidized beds

While solids circulation rate is a critical design and control parameter in circulating fluidized bed (CFB) reactor systems, there are no available techniques to measure it directly at conditions of industrial interest. Cold flow tests have been conducted at NETL in an industrial scale CFB unit where the solids flow has been the topic of research in order to develop an independent method which could be applied to CFBs operating under the erosive and corrosive high temperatures and pressures of a coal fired boiler or gasifier. The dynamic responses of the CFB loop to modest modulated aeration flows in the return leg or standpipe were imposed to establish a periodic response in the unit without causing upset in the process performance. The resulting periodic behavior could then be analyzed with a dynamic model and the average solids circulation rate could be established. This method was applied to the CFB unit operated under a wide range of operating conditions including fast fluidization, core annular flow, dilute and dense transport, and dense suspension upflow. In addition, the system was operated in both low and high total solids inventories to explore the influence of inventory limiting cases on the estimated results. The technique was able to estimate the solids circulation rate for all transport circulating fluidized beds when operating above upper transport velocity, U{sub tr2}. For CFB operating in the fast fluidized bed regime (i.e., U{sub g}< U{sub tr2}), the phase shift technique was not successful. The riser pressure drop becomes independent of the solids circulation rate and the mass flow rate out of the riser does not show modulated behavior even when the riser pressure drop does.

42 ENGINEERING↗

Metal Structural Environment in Zn x Ni 1-x O Macroscale and Nanoscale Solid Solutions

The metal structural environments in macroscale and nanoscale Zn x Ni 1–x O solid solutions were examined using X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and X-ray photoelectron spectroscopy (XPS). XRD demonstrates that solid solutions form for both macroscale (bulk) and nanoscale crystallites, and that the lattice parameter increases linearly as the amount of zinc increases, an indication of a homogeneous solid solution. XAS for both the bulk material and the nanoparticles reveals that the zinc atoms are incorporated into the rocksalt lattice and do not form zinc oxide clusters. The X-ray absorption near edge spectroscopy (XANES) of the Zn k-edge region in the solid solution is similar to the Ni k-edge region of NiO, and not the Zn k-edge region of ZnO. XPS confirms that solid solutions are formed; Auger parameters for zinc are consistent with a different geometry than the tetrahedral coordination of wurtzite ZnO. Nanoscaled solid solutions show evidence of a lattice contraction relative to macroscale solutions of the same concentration. While the contraction persists across the entire concentration range, the nanoparticle lattice parameter approaches the bulk Zn x Ni 1–x O value as the concentration of zinc increases to predict ZnO rocksalt lattice parameters that are in agreement with observed ZnO data.

Peck, Matthea A.↗

Solid cancer incidence other than lung, liver and bone in Mayak workers: 1948–2004

Background: Cancer incidence in the Mayak Production Association (PA) cohort was analysed to investigate for the first time whether external gamma-ray and internal plutonium exposure are associated with raised incidence of solid cancers other than lung, liver and bone (other solid cancers). Methods: The cohort includes 22 366 workers of both sexes who were first employed between 1948 and 1982. A total of 1447 cases of other solid cancers were registered in the follow-up period until 2004. The Poisson regression was used to estimate the excess relative risk (ERR) per unit of cumulative exposure to plutonium and external gamma-ray. Results: A weak association was found between cumulative exposure to external gamma-ray and the incidence of other solid cancers (ERR/Gy = 0.07; 95% confidence intervals (CIs): 0.01–0.15), but this association lost its significance after adjusting for internal plutonium exposure. There was no indication of any association with plutonium exposure for other solid cancers. Among 16 individual cancer sites, there was a statistically significant association with external exposure for lip cancer (ERR/Gy = 1.74; 95% CI: 0.37; 6.71) and with plutonium exposure for pancreatic cancer (ERR/Gy = 1.58; 95% CI; 0.17; 4.77). Conclusion: This study of Mayak workers does not provide evidence of an increased risk of other solid cancers. The observed increase in the risk of cancer of the lip and pancreas should be treated with caution because of the limited amount of relevant data and because the observations may be simply due to chance.

60 APPLIED LIFE SCIENCES↗

Linking void and interphase evolution to electrochemistry in solid-state batteries using operando X-ray tomography

Despite progress in solid-state battery engineering, our understanding of the chemo-mechanical phenomena that govern electrochemical behavior and stability at solid-solid interfaces remains limited compared to solid-liquid interfaces. Here, we use operando synchrotron X-ray computed microtomography to investigate the evolution of lithium/solid-state electrolyte interfaces during battery cycling, revealing how the complex interplay among void formation, interphase growth, and volumetric changes determines cell behavior. Void formation during lithium stripping is directly visualized in symmetric cells, and the loss of contact that drives current constriction at the interface between lithium and the solid-state electrolyte (Li10SnP2S12) is quantified and found to be the primary cause of cell failure. The interphase is found to be redox-active upon charge, and global volume changes occur due to partial molar volume mismatches at either electrode. Finally, these results provide new insight into how chemo-mechanical phenomena can impact cell performance, which is necessary to understand for the development of solid-state batteries.

42 ENGINEERING↗

Polymorphism of garnet solid electrolytes and its implications for grain-level chemo-mechanics

Understanding and mitigating filament formation, short-circuit and solid electrolyte fracture is necessary for advanced all-solid-state batteries. Here, we employ a coupled far-field high-energy diffraction microscopy and tomography approach for assessing the chemo-mechanical behaviour for dense, polycrystalline garnet (Li 7 La 3 Zr 2 O 12 ) solid electrolytes with grain-level resolution. In situ monitoring of grain-level stress responses reveals that the failure mechanism is stochastic and affected by local microstructural heterogeneity. In this work, coupling high-energy X-ray diffraction and far-field high-energy diffraction microscopy measurements reveals the presence of phase heterogeneity that can alter local chemo-mechanics within the bulk solid electrolyte. These local regions are proposed to be regions with the presence of a cubic polymorph of LLZO, potentially arising from local dopant concentration variation. The coupled tomography and FF-HEDM experiments are combined with transport and mechanics modelling to illustrate the degradation of polycrystalline garnet solid electrolytes. The results showcase the pathways for processing high-performing solid-state batteries.

36 MATERIALS SCIENCE↗

Superionic conducting vacancy-rich β-Li 3 N electrolyte for stable cycling of all-solid-state lithium metal batteries

The advancement of all-solid-state lithium metal batteries requires breakthroughs in solid-state electrolytes (SSEs) for the suppression of lithium dendrite growth at high current densities and high capacities (>3 mAh cm -2 ) and innovation of SSEs in terms of crystal structure, ionic conductivity and rigidness. Here we report a superionic conducting, highly lithium-compatible and air-stable vacancy-rich β-Li 3 N SSE. This vacancy-rich β-Li 3 N SSE shows a high ionic conductivity of 2.14 × 10 -3 S cm -1 at 25 °C and surpasses almost all the reported nitride-based SSEs. A Li- and N-vacancy-mediated fast lithium-ion migration mechanism is unravelled regarding vacancy-triggered reduced activation energy and increased mobile lithium-ion population. All-solid-state lithium symmetric cells using vacancy-rich β-Li 3 N achieve breakthroughs in high critical current densities up to 45 mA cm -2 and high capacities up to 7.5 mAh cm -2 , and ultra-stable lithium stripping and plating processes over 2,000 cycles. The high lithium compatibility mechanism of vacancy-rich β-Li 3 N is unveiled as intrinsic stability to lithium metal. In addition, β-Li 3 N possesses excellent air stability through the formation of protection surfaces. All-solid-state lithium metal batteries using the vacancy-rich β-Li 3 N as SSE interlayers and lithium cobalt oxide (LCO) and Ni-rich LiNi 0.83 Co 0.11 Mn 0.06 O 2 (NCM83) cathodes exhibit excellent battery performance. Extremely stable cycling performance is demonstrated with high capacity retentions of 82.05% with 95.2 mAh g -1 over 5,000 cycles at 1.0 C for LCO and 92.5% with 153.6 mAh g -1 over 3,500 cycles at 1.0 C for NCM83. Utilizing the vacancy-rich β-Li 3 N SSE and NCM83 cathodes, the all-solid-state lithium metal batteries successfully accomplished mild rapid charge and discharge rates up to 5.0 C, retaining 60.47% of the capacity. Notably, these batteries exhibited a high areal capacity, registering approximately 5.0 mAh cm -2 for the compact pellet-type cells and around 2.2 mAh cm -2 for the all-solid-state lithium metal pouch cells.

25 ENERGY STORAGE↗

Status and prospect of in situ and operando characterization of solid-state batteries

Electrification of the transportation sector relies on radical re-imagining of energy storage technologies to provide affordable, high energy density, durable and safe systems. Next generation energy storage systems will need to leverage high energy density anodes and high voltage cathodes to achieve the required performance metrics (longer vehicle range, long life, production costs, safety). Solid-state batteries (SSBs) are promising materials technology for achieving these metrics by enabling these electrode systems due to the underlying material properties of the solid electrolyte (viz. mechanical strength, electrochemical stability, ionic conductivity). Electro-chemo-mechanical degradation in SSBs detrimentally impact the Coulombic efficiencies, capacity retention, durability and safety in SSBs restricting their practical implementation. Solid|solid interfaces in SSBs are hot-spots of dynamics that contribute to the degradation of SSBs. Characterizing and understanding the processes at the solid|solid interfaces in SSBs is crucial towards designing of resilient, durable, high energy density SSBs. This work provides a comprehensive and critical summary of the SSB characterization with a focus on in situ and operando studies. Additionally, perspectives on experimental design, emerging characterization techniques and data analysis methods are provided. Furthermore, this work provides a thorough analysis of current status of SSB characterization as well as highlights important avenues for future work.

25 ENERGY STORAGE↗

Level crossing analysis of chemically induced dynamic nuclear polarization: Towards a common description of liquid-state and solid-state cases

Chemically Induced Dynamic Nuclear Polarization (CIDNP) is an efficient method of creating non-equilibrium polarization of nuclear spins by using chemical reactions, which have radical pairs as intermediates. The CIDNP effect originates from (i) electron spin-selective recombination of radical pairs and (ii) the dependence of the inter-system crossing rate in radical pairs on the state of magnetic nuclei. The CIDNP effect can be investigated by using Nuclear Magnetic Resonance (NMR) methods. The gain from CIDNP is then two-fold: it allows one to obtain considerable amplification of NMR signals; in addition, it provides a very useful tool for investigating elusive radicals and radical pairs. While the mechanisms of the CIDNP effect in liquids are well established and understood, detailed analysis of solid-state CIDNP mechanisms still remains challenging; likewise a common theoretical frame for the description of CIDNP in both solids and liquids is missing. Difficulties in understanding the spin dynamics that lead to the CIDNP effect in the solid-state case are caused by the anisotropy of spin interactions, which increase the complexity of spin evolution. In this work, we propose to analyze CIDNP in terms of level crossing phenomena, namely, to attribute features in the CIDNP magnetic field dependence to Level Crossings (LCs) and Level Anti-Crossings (LACs) in a radical pair. This approach allows one to describe liquid-state CIDNP; the same holds for the solid-state case where anisotropic interactions play a significant role in CIDNP formation. In solids, features arise predominantly from LACs, since in most cases anisotropic couplings result in perturbations, which turn LCs into LACs. We have interpreted the CIDNP mechanisms in terms of the LC/LAC concept. This consideration allows one to find analytical expressions for a wide magnetic field range, where several different mechanisms are operative; furthermore, the LAC description gives a way to determine CIDNP sign rules. Thus, LCs/LACs provide a consistent description of CIDNP in both liquids and solids with the prospect of exploiting it for the analysis of short-lived radicals and for optimizing the polarization level.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solid structure of Li 2 BeF 4 (FLiBe) from room temperature to melting studied by neutron and X-ray diffraction

Molten fluoride salts such as Li 2 BeF 4 (FLiBe) are used in molten salt reactors, fluoride-salt-cooled high-temperature reactors and fusion reactors as a fuel solvent, coolant and/or tritium breeding medium. In engineered systems that use molten salt, solid-state material will be present during melting and freezing scenarios, and therefore the temperature-dependent properties of the solid and solid/liquid phase transition merit investigation. To observe the behavior of the solid state of Li 2 BeF 4 from room temperature to melting, this work used neutron and X-ray diffraction to measure the changes in the lattice parameters and volume of the crystalline unit cell and compared the results with prior low-temperature data for solid Li 2 BeF 4 . From neutron diffraction data it is also possible to identify anisotropy: centimetre-scaled crystals align preferentially with the a axes parallel to the direction of freezing front propagation, and the c axes expand 54% more than the a axes. This work provides the lattice constants as a function of temperature, quantifies the thermal expansion, and determines the equation describing the change in density for solid Li 2 BeF 4 from room temperature to 459°C to be ρ solid (kg m −3 ) = 2182 (3) − 0.115 (2) T (°C) and the volume expansion upon melting to be less than 5%. This density changes depending on molecular weight and enrichment.

36 MATERIALS SCIENCE↗

Global harmonization of immediate‐release solid oral drug product bioequivalence recommendations and the impact on generic drug development

Immediate-release (IR) solid oral drug products constitute a significant portion of approved drug products and products under development. Bioequivalence (BE) assessment for these oral products is important for establishing therapeutic equivalence for generic products to their respective comparator products. In December 2022, the International Council for Harmonisation of Technical Requirements for Pharmaceuticals for Human Use (ICH) published the first new draft guideline on BE for IR solid oral dosage forms (M13A). To support the development of ICH M13A, we comprehensively reviewed the landscape of oral IR products approved by the U.S. Food and Drug Administration (FDA) and compared BE recommendations for these products in the current U.S. FDA and European Medicines Agency (EMA) BE guidances. We utilized databases including Drugs@FDA, Orange Book, and product-specific guidances (PSGs) published on the U.S. FDA and EMA websites to collect information. Oral IR products account for 46% of all FDA-approved new drug applications currently listed in Orange Book with 82.5% solids, 0.9% semi-solids, and 16.6% liquids. For all published U.S. FDA PSGs for solid oral IR products, in vivo BE studies with pharmacokinetic (PK) endpoints account for 88% of BE approaches recommended. Of these PK BE studies, 86.5% recommended fasting and fed BE studies, while only 15.9% EMA PSGs recommended both fasting and fed BE studies. This review helps clarify the scope of U.S. solid oral IR products impacted by the new ICH M13A draft guideline and demonstrates how recommendations in draft ICH M13A could significantly harmonize BE recommendations for IR oral products to facilitate global drug development.

60 APPLIED LIFE SCIENCES↗

SU-D-209-01: Can Fluoroscopic Air-Kerma Rates Be Reliably Measured with Solid-State Meters?

Purpose: Ionization chambers remain the standard for calibration of air-kerma rate measuring devices. Despite their strong energy-dependent response, solid state radiation detectors are increasingly used, primarily due to their efficiency in making standardized measurements. To test the reliability of these devices in measuring air-kerma rates, we compared ion chambers measurements with solid-state measurements for various mobile fluoroscopes operated at different beam qualities and air-kerma rates. Methods: Six mobile fluoroscopes (GE OEC models 9800 and 9900) were used to generate test beams. Using various field sizes and dose rate controls, copper attenuators and a lead attenuator were placed at the image receptor in varying combinations to generate a range of air-kerma rates. Air-kerma rates at 30 centimeters from the image receptors were measured using two 6-cm{sup 3} ion chambers with electrometers (Radcal, models 1015 and 9015) and two with solid state detectors (Unfors Xi and Raysafe X2). No error messages occurred during measurements. However, about two months later, one solid-state device stopped working and was replaced by the manufacturer. Two out of six mobile fluoroscopic units were retested with the replacement unit. Results: Generally, solid state and ionization chambers agreed favorably well, with two exceptions. Before replacement of the detector, the Xi meter when set in the “RF High” mode deviated from ion chamber readings by factors of 2 and 10 with no message indicating error in measurement. When set in the “RF Low” mode, readings were within −4% to +3%. The replacement Xi detector displayed messages alerting the user when settings were not compatible with air-kerma rates. Conclusion: Air-kerma rates can be measured favorably well using solid-state devices, but users must be aware of the possibility that readings can be grossly in error with no discernible indication for the deviation.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Efficient Reformulation of Solid Phase Diffusion in Electrochemical-Mechanical Coupled Models for Lithium-Ion Batteries: Effect of Intercalation Induced Stresses

Lithium-ion batteries are typically modeled using porous electrode theory coupled with various transport and reaction mechanisms with an appropriate discretization or approximation for the solid phase diffusion within the electrode particle. One of the major difficulties in simulating Li-ion battery models is the need for simulating solid-phase diffusion in the second radial dimension r within the particle. It increases the complexity of the model as well as the computation time/cost to a great extent. This is Particularly true for the inclusion of pressure induced diffusion inside particles experiencing volume change. A computationally efficient representation for solid-phase diffusion is discussed in this paper. The operating condition has a significant effect on the validity, accuracy, and efficiency of various approximations for the solid-phase transport governed by pressure induced diffusion. This paper introduces efficient methods for solid phase reformulation - (1) parabolic profile approach and (2) a mixed order finite difference method for approximating/representing solid-phase concentration variations within the active materials of porous electrodes for macroscopic models for lithium-ion batteries. (C) 2013 The Electrochemical Society. All rights reserved.

De, S↗

Pulse Jet Mixing Tests With Noncohesive Solids (Revised)

This report summarizes results from pulse jet mixing (PJM) tests with noncohesive solids in Newtonian liquid. The tests were conducted during FY 2007 and 2008 to support the design of mixing systems for the Hanford Waste Treatment and Immobilization Plant (WTP). Tests were conducted at three geometric scales using noncohesive simulants, and the test data were used to develop models predicting two measures of mixing performance for full-scale WTP vessels. The models predict the cloud height (the height to which solids will be lifted by the PJM action) and the critical suspension velocity (the minimum velocity needed to ensure all solids are suspended off the floor, though not fully mixed). From the cloud height, the concentration of solids at the pump inlet can be estimated. The predicted critical suspension velocity for lifting all solids is not precisely the same as the mixing requirement for 'disturbing' a sufficient volume of solids, but the values will be similar and closely related. These predictive models were successfully benchmarked against larger scale tests and compared well with results from computational fluid dynamics simulations. The application of the models to assess mixing in WTP vessels is illustrated in examples for 13 distinct designs and selected operational conditions. The values selected for these examples are not final; thus, the estimates of performance should not be interpreted as final conclusions of design adequacy or inadequacy. However, this work does reveal that several vessels may require adjustments to design, operating features, or waste feed properties to ensure confidence in operation. The models described in this report will prove to be valuable engineering tools to evaluate options as designs are finalized for the WTP. Revision 1 refines data sets used for model development and summarizes models developed since the completion of Revision 0.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Final Technical Report: Using Solid Particles as Heat Transfer Fluid for use in Concentrating Solar Power (CSP) Plants

In today’s industrial economy, energy consumption has never been higher. Over the last 15 years the US alone has consumed an average of nearly 100 quadrillion BTUs per year [21]. A need for clean and renewable energy sources has become quite apparent. The SunShot Initiative is an ambitious effort taken on by the United States Department of Energy that targets the development of solar energy that is cost-competitive with other methods for generating electricity. Specifically, this work is concerned with the development of concentrating solar power plants (CSPs) with granular media as the heat transfer fluid (HTF) from the solar receiver. Unfortunately, the prediction of heat transfer in multiphase flows is not well understood. For this reason, our aim is to fundamentally advance the understanding of multiphase heat transfer, particularly in gas-solid flows, while providing quantitative input for the design of a near black body receiver (NBB) that uses solid grains (like sand) as the HTF. Over the course of this three-year project, a wide variety of contributions have been made to advance the state-of-the art description for non-radiative heat transfer in dense, gas-solid systems. Comparisons between a state-of-the-art continuum heat transfer model and discrete element method (DEM) simulations have been drawn. The results of these comparisons brought to light the limitations of the continuum model due to inherent assumptions in its derivation. A new continuum model was then developed for heat transfer at a solid boundary by rigorously accounting for the most dominant non-radiative heat transfer mechanism (particle-fluid-wall conduction). The new model is shown to be in excellent agreement with DEM data and captures the dependence of heat transfer on particle size, a dependency that previous continuum models were not capable of. DEM and the new continuum model were then employed to model heat transfer in a variety of receiver geometries. The results provided crucial feedback on the efficiency and feasibility of various designs. Namely, a prototype design consisting of an array of heated hexagonal tubes was later supplanted by a vertical conduit with internal baffles. Due to low solids heat transfer on the bottom faces of the hexagonal tubes in the prototype, the predicted wall temperature gradients exceeded the design limitations. By contrast, the vertical conduit can be constructed to continually force particle-wall contacts, and thus, result in more desirable solids heat transfer and wall temperature gradients. Finally, a new heat flux boundary condition was developed for DEM simulations to assess the aforementioned wall temperature gradients. The new boundary condition advances current state-of-the-art techniques by allowing the heat fluxes to each phase to vary with space and time while the total flux remains constant. Simulations with the new boundary condition show that the total boundary heat flux is in good agreement with the imposed total boundary heat flux. While the methods we have utilized here are primarily numerical and fundamental by nature, they offer some key advantages of: (i) being robust and valid over a large range of conditions, (ii) able to quickly explore large parameter spaces, and (iii) aid in the construction of experiments. We have ultimately leveraged our computational capabilities to provide feedback on the design of a CSP which possesses great potential to become a cost effective source of clean and renewable electricity. Overall, ensuring that future energy demands are met in a responsible and efficient manner has far reaching impacts that span both ecologic and economic concerns. Regarding logistics, the project was successfully re-negotiated after the go/no-decisions of Years 1 and 2. All milestones were successfully completed.

14 SOLAR ENERGY↗

Dendrite Growth Morphology Modeling in Liquid and Solid Electrolytes

The main goal of this project is to develop a multi-scale modeling approach that connects micron-scale phase-field models and atomic-scale density functional theory (DFT)-based simulations via parameter- and relationship-passing in order to predict Li-metal dendrite morphology evolution, in both liquid and solid electrolytes. The key hypothesis of the DFT-informed phase-field multiscale modeling approach is that it can capture the electrochemical-mechanical driving forces and incorporate the roles of nano-meter-thin solid electrolyte interphase (SEI) in liquid electrolytes as well as of the microstructures of micro-meter-thick solid electrolytes (SEs) for all-solid-state batteries. In this project, we have formulated and implemented phase-field models to incorporate the electrochemical driving forces in liquid electrolytes and then incorporate mechanical driving forces to simulate dendrite growth in solid electrolytes with resolved microstructures. We have implemented two treatments for the SEI: an explicit model to include the microstructure of the SE or SEI in the phase field model and an implicit model to simulate the impact of nano-meter thick SEI in liquid electrolytes by varying the electrode/electrolyte interfacial properties. The key interfacial properties, including the electronic and ionic transport properties, the charge transfer reaction kinetics, and mechanical properties, were computed by DFT-based calculations. At the DFT-based model, one key advancement is to directly predict the charge transfer reaction kinetics at a complex Li/SEI/electrolyte interface by linking DFT with density functional tight binding (DFTB) calculations. As the main accomplishments, we have demonstrated two successful predictions in both solid electrolyte and liquid electrolyte based on this multiscale approach. The predicted intergranular Li dendrite growth in LLZO revealed the importance of trapped electrons at internal interfaces in the microstructure of LLZO. The predicted electroplating morphology of mossy Li and faceted Mg agreed well with experiments. The insights provided by the multiscale model and the model enabled electrolyte and SEI design will accelerate the development of Li-metal electrode for high energy density batteries, that meet DOE’s target on cell density (>350 Wh/kg) and cost below $100/kWhuse for EV applications.

25 ENERGY STORAGE↗

First-principles Modeling and Design of Solid-State Interfaces for the Protection and Use of Lithium Metal Anodes

Li-ion batteries are one of the most advanced energy storage technologies in use today. Li-ion batteries are used in a multitude of applications ranging from consumer electronics, medical devices, sensors and grid storage. However, improving the capacity and energy density delivered by current Li-ion technology requires advanced materials research into novel chemical systems. In this project we have focused particularly in the use of solid-state electrolytes with lithium metal electrodes. Research into all solid-state batteries (ASSB) with Li metal electrodes has significantly expanded in recent years, however most studies reported experimental findings, which left substantial room for theoretical and modeling work as a tool to understand and determine design principles allowing reliable and safe use of ASSBs with Li metal. Among the remaining obstacles preventing reliable use of ASSBs with a Li metal electrode, the stability of the interface between the solid electrolyte and Li metal, and the propagation/dendrite formation of Li metal and resulting mechanical degradation of the electrolyte are key phenomenon that are yet to be fully understood. In the current project we have addressed these two coupled phenomena using first principles calculations and mesoscale continuum modeling. We have obtained chemical and electrochemical stability windows for several solid electrolyte materials. Additionally, from mathematical and numerical modeling of Li protrusion and dendrite initiation during plating and stripping we have determined design criteria in terms of chemical, electrochemical, and mechanical properties and operating conditions for which stable deposition can occur. We also considered the effects of mixed electronic-ionic conduction in solid electrolytes, which has more recently been suggested as another important mechanism involved in ASSB failure. Throughout our work we have successfully addressed important questions necessary for the use of ASSB’s. We have determined guiding principles for materials properties and operating conditions necessary to operate ASSB’s. And have proposed novel solid electrolyte materials with predicted chemical stability an ionic conductivity. Although this represents significant progress in our understanding, open questions remain in order to fully develop reliable and safely operate ASSBs with Li metal. Future work, building on this project will require further experimental, theoretical and simulation efforts to address remaining questions.

25 ENERGY STORAGE↗

Development of 3D Printing Techniques for Solid-State Lithium Batteries: Energy Storage Internship (Final Report)

The goal of this internship was to develop a solid polymer electrolyte with a suitable ionic conductivity and mechanical properties and integrate it with 3D printed cathode for solid state lithium batteries. While liquid electrolytes will have much higher conductivities and therefore higher power densities than solid electrolytes, batteries with such electrolytes suffer from extreme dendritic growth, short-circuiting, and general failure. Typically, batteries prevent this by including a solid yet porous separator somewhere between the anode and cathode to suppress dendritic growth. Solid polymer electrolyte acts as the conductive medium between electrodes as well as the separator that prevents failure from short-circuiting. The specific system explored is a vinyl ethylene carbonate (VEC) and polyethylene glycol diacrylate (PEGDA) mixed polymer solution using both 2,2’-azobis(2-methylpropionitrile) (AIBN) and Irgacure 819, respectively as thermal and photo- initiators. Electrochemical and rheological techniques were used to determine the optimal polymer solution and curing conditions. Through this research, multiple new pathways of exploration have been determined to create a usable solid polymer electrolyte through a combination of varying cure intensities and initiator concentrations.

25 ENERGY STORAGE↗