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At least 487 records · Page 27

Microstructure Scale Lithium-Ion Battery Modeling: Part III. When and Where Lithium Plating Occurs and its Correlation with the Electrode Microstructure

Li-ion battery performance and degradation are closely related to the cell’s underlying electrode microstructure. Electrode microstructures are typically characterized with volume-averaged properties that neglect the impact of local heterogeneities. However, local heterogeneities create hot spots that can trigger degradation onset. Herein, a microstructure scale electrochemical model is used to investigate the impact of microstructure heterogeneity on lithium plating. The model predicts lithium plating is not uniform, even when considering a relatively small portion of the electrode (a cross-sectional area of 154×144 µm 2 ), preferring to plate on larger particles as compared to smaller particles. While local heterogeneities control where plating occurs, the model predicts that volume-averaged properties control when plating occurs. Additionally, the model predicts that the active material specific surface area has a linear relationship with the plating onset. However, the linear relationship between increased active material surface area and delayed plating response appears to be sensitive to the microstructure feature used to increase the active interface area. Here, a comparative case-study is explored where the specific surface area is increased by either reducing the active material particle diameter, adding open-porosity cracks, or increasing the active material surface roughness. The model predicts that increasing the specific surface area by reducing the active material particle diameter is the most effective strategy for delaying lithium plating. At 6C, reducing particle size is shown to be 3 and 20 times more effective than, respectively, adding open-porosity cracks and increasing surface roughness. A dual-layer electrode architecture combining gradations both for average properties and uniformities is eventually proposed to improve homogeneous material utilization and reduce degradation at high charge rates.

25 ENERGY STORAGE↗

Two-layer cathode architecture for high-energy density and high-power density solid state batteries

Solid state batteries with high-energy density and high-power density require the development of thick and energy dense cathodes. Structured cathode electrodes with a double-layer configuration were enabled using a freeze tape casting technique. A bottom dense layer was utilized to enhance the energy density whereas a top porous layer with vertically aligned walls was utilized to enhance the power density. The porous structure of the power layer was achieved by ice templating this layer on top of the densified energy layer of the cathode. This configuration was found to better utilize the active material of the cathodes and was optimized using numerical simulation and computer modeling. Cells with Li metal anode and LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) at approximately 5 and 20 mg/cm 2 were cycled at 70 °C at different C-rates. Poly(ethylene oxide) (PEO) with lithium bis-trifluoromethanesulfonimide (LiTFSI) was used for the catholyte and the solid-state electrolyte. The structured cathodes exhibited more than double capacity values as well as better Coulombic efficiency compared to non-structured (single-layer) thick cathodes. In conclusion, synchrotron X-ray tomography and scanning electron microscopy were used to characterize the microstructure of the cathodes.

25 ENERGY STORAGE↗

Interface Evolutionand Long-Term Performance of NegativeCarbon Fiber Structural Electrodes

Abstract Laminated structural batteries present a transformative solution to reducing weight constraints in electric vehicles. These structural batteries are based on a multifunctional material that incorporates an energy storage function within a carbon fiber-reinforced polymer. Despite the potential of this technology, the intricate morphology of fiber–matrix or electrode–electrolyte interfaces and the impact of long-term cycling at low current rates (C-rates) on these interfaces remain insufficiently understood. This study addresses these critical knowledge gaps by examining the influence of matrix composition on the long-term electrochemical performance of structural battery electrodes and exploring advanced techniques to investigate carbon fiber–matrix interfaces. Localized imaging and X-ray scattering techniques were used to characterize morphological changes at the electrode–electrolyte interfaces by analyzing negative structural electrodes. The findings revealed that the matrix composition influences long-term electrochemical behavior and fiber–matrix interface formation. While the intrinsic properties of carbon fibers largely remain unaffected by long-term cycling, cycling promotes debonding at fiber–matrix interfaces. Nonetheless, residual regions of adhesion persist, underscoring the potential for preserving multifunctionality even under prolonged cycling conditions. These insights advance the understanding of interface dynamics, which is critical for optimizing structural battery technologies.

Chemistry↗

Persistent and partially mobile oxygen vacancies in Li-rich layered oxides

Increasing the energy density of layered oxide battery electrodes is challenging as accessing high states of delithiation often triggers voltage degradation and oxygen release. Here we utilize transmission-based X-ray absorption spectromicroscopy and ptychography on mechanically cross-sectioned Li 1.18–x Ni 0.21 Mn 0.53 Co 0.08 O 2–δ electrodes to quantitatively profile the oxygen deficiency over cycling at the nanoscale. The oxygen deficiency penetrates into the bulk of individual primary particles (~200 nm) and is well-described by oxygen vacancy diffusion. Using an array of characterization techniques, we demonstrate that, surprisingly, bulk oxygen vacancies that persist within the native layered phase are indeed responsible for the observed spectroscopic changes. We additionally show that the arrangement of primary particles within secondary particles (~5 μm) causes considerable heterogeneity in the extent of oxygen release between primary particles. Finally, our work merges an ensemble of length-spanning characterization methods and informs promising approaches to mitigate the deleterious effects of oxygen release in lithium-ion battery electrodes.

25 ENERGY STORAGE↗

Enhancing Cycling Stability and Capacity Retention of NMC811 Cathodes by Reengineering Interfaces via Electrochemical Fluorination

High-capacity cathodes (LiNi 0.8 Mn 0.1 Co 0.1 O 2 ) that can boost the energy density of lithium-ion batteries are promising candidates for vehicle electrification. However, several factors specific to high energy density materials entailing electrode reactions inhibit their application. Fluorination has shown a promising ability to combat the detrimental electrochemical performances of cathode materials, however, it remains difficult to achieve the desired functionality. In this work, a novel electrochemical fluorination (ECF) that demonstrates a promising electrochemical performance enhancement via stabilization of the cathode–electrolyte-interphase (CEI) by forming conformal LiF is proposed. Besides LiF surface layer formation, ECF reduces the degree of fluorination-induced Ni/Li disordering and enhances the layered structural stability as probed by X-ray diffraction. Because of the robust CEI, ECF-NMC811 cathodes deliver 203.0 mAh g -1 first discharge capacity at the current rate of C/10, with ≈98% capacity retention up to 100 cycles. Similarly, it delivers ≈180 mAh g -1 capacity at a 1 C rate with 86.4% capacity retention up to 200 cycles with average coulombic efficiency of > 99.5%. Comprehensive characterization with a multitude of probes reveals that ECF enhances the cycling stability of the electrode without altering bulk structure and morphology.

25 ENERGY STORAGE↗

Flux Upcycling of Degraded Layered Cathodes to LiNi x Mn y Co z O 2 (NMCs) with Gradient Transition Metal Distribution

The rising demand for lithium-ion batteries (LIBs) has intensified the need for efficient recycling methods to address both supply chain constraints and environmental impacts. Direct upcycling, distinguished by its ability to achieve both the structural and compositional integrity of cathode materials, has gained prominence as a sustainable alternative to conventional pyrometallurgical and hydrometallurgical processes. However, the current direct upcycling methods are typically limited by incorporating Li and/or Ni, significantly constraining the adaptability across diverse LiNi x Mn y Co z O 2 (NMCs). Here, in this study, a versatile molten salt approach is reported that expands the scope of direct upcycling by enabling simultaneous incorporation of Li, Ni, and Mn. This methodology facilitates flexible conversion among diverse NMC compositions, including non-stoichiometric Co/Mn systems such as upcycling degraded LiCoO 2 (D-LCO), LiNi 1/3 Mn 1/3 Co 1/3 O 2 (D-NMC111), LiNi 0.8 Mn 0.1 Co 0.1 O 2 (D-NMC811) to surface Mn enriched NMC111, LiNi 0.5 Mn 0.3 Co 0.2 O 2 (NMC532), and NMC811, respectively. The gradient transition metal distribution in upcycled products, characterized by Mn-enriched outer layers and Co/Ni-enriched cores enhances the interfacial stability of NMC cathodes, addressing critical challenges in long-term performance and structural integrity. These results highlight the potential of flux methods for advancing the upcycling of spent cathodes and producing high-performance materials for next-generation LIBs applications.

lithium -ion batteries↗

Nanostructures for Electrical Energy Storage (NEES) (2020 Final Technical Report)

Nanostructures for Electrical Energy Storage (NEES, www.efrc.umd.edu) was an Energy Frontier Research Center supported by the DOE Office of Science, Basic Energy Sciences, from 8/1/2009 to 7/31/2020. Led by the University of Maryland, NEES enjoyed extensive collaborations with its funded partners, including two DOE Laboratories and six universities. The NEES vision has been to reveal a set of scientific insights and design principles that can underpin a next-generation electrical energy storage approach, building on advances in nanoscale science and technology to achieve simultaneous high power and high energy over extended charge/discharge cycling. The vision is motivated by the recognition that scaling into the nano regime opens the door to new physical phenomena and that the tools enlisted in nanoscale research provide major new opportunities for the synthesis not only of materials at molecular scale but for structures at nano scale and above. NEES has translated this vision into its research program based on two observations. First, while the behavior of ions and electrons in electrolytes and in electrode materials is crucial to electrical energy storage (or more appropriately electrochemical energy storage), it is the transport of ion and electron charge between different structural components of a storage device that ultimately determine its performance. With it well recognized that the choice of electrode materials typically constrain ion transport kinetics as well as maximum ion concentration, the search for better electrode materials has been a primary driver of battery research. At the same time the synthesis of electrodes is typically based on aggregation of particles with varying size, shape, and orientation in the electrode. Together with the presence of additional materials to impart electrical conductivity and cohesion to the composite electrode, change in electrode materials is necessarily accompanied by structural changes at the nano/micro scale that are difficult to categorize and manage. From the beginning, NEES’ vision has been to create and study simpler, highly controlled spatial arrangements of known materials as battery components (electrodes, current collectors, and electrolyte) and to understand how design and structure above the molecular scale determines the energy storage performance available from known materials. Second, advances in nanoscience dramatically expanded the portfolio of synthesis methods, structural motifs, and new phenomena available for research. Some of these gave rapid access to new building blocks at the deep nanoscale (e.g., carbon nanotubes grown by self-assembly, nanoscale arrays formed by electrochemical self-alignment, monolayer films controlled by self-limiting reaction). Such advances served as the enabler for the NEES vision to be pursued experimentally through study of 3D structures created and controlled at the nano, micro, and meso scales. Here, we use meso as in the BES MESO Report, implying not only intermediate or varying length scales, but very much the way behavior is influenced by other factors including aggregation of nanocomponents at different densities and spatial configurations, statistical variations in the aggregates, hierarchical architectures in which they can be assembled, or local 3D configurations that result from the architectures. Over its life cycle, NEES has pursued two overarching goals: (1) to understand the scientific fundamentals of electrochemical storage from the nanoscale to the mesoscale; and (2) to create and learn from innovative, controlled, heterogeneous nanostructures, where such nanostructures can enable the first goal and serve as models for future paradigms in energy storage. Specific goals have included: Synthesize heterogeneous nanostructures comprised of multiple materials arranged in controlled fashion and characterize their behavior; Demonstrate and elucidate design principles for achieving simultaneous high power and high energy; Develop materials processes which enable precision control of thin layers and 3D structures; Investigate the impact of artificial interphases on electrode stability during ion insertion/deinsertion; Create dense arrays of nanostructures to understand how the architecture of these assemblies, along with nanostructure design, influences energy storage behavior at the mesoscale; Identify and understand the consequences of nanoconfinement and local inhomogeneities in 3D mesoscale arrays; Develop and apply computational models to stimulate, guide and interpret experiments.

25 ENERGY STORAGE↗

Electrochemically-Induced Phase Transformations in Battery Storage Compounds (Final Technical Report)

Compounds of interest for ion storage in advanced batteries frequently exhibit phase transformations as the working ion concentration varies. Under large electrochemical driving forces inherent to practical use, systems are often driven far from equilibrium. This program combines experiments and theory to understand the phase transition behavior of ion insertion compounds when electrochemically driven far from equilibrium. As model systems, we focus on alkaline metal phosphates AMPO4 (A = alkali; M = first row transition metal) of olivine structure, which are both technologically interesting and ideally suited for fundamental study due to the ability to systematically tune transformation strain, and along with it, the phase transformation pathway. Behavior in compositions having large transformation strains (~15 vol%) requiring plasticity for strain accommodation is emphasized. Experimental techniques include operando characterization of structure while simultaneously varying electrokinetic parameters, and high resolution microscopy of nanoscale and interfacial phenomena. Phase-field modeling is used to model the thermodynamics and kinetics of competing transformation pathways, extended to include the effects of plasticity, and integrated with porous electrode kinetic theory to treat multi-particle effects. Success in this project will lead to an ability to design ion storage compounds with predictable transformation pathways, electrochemical kinetics, capacity utilization, and durability. New technologically important compounds may also be discovered.

36 MATERIALS SCIENCE↗

Influence of Electrolyte Additives on Interfacial Stability of Manganese-Rich Lithium-Ion Battery Cathodes

Affordable, long-lasting energy storage has become critical to support increased electricity demand in recent years. Cobalt-free, lithium- and manganese-rich lithium nickel manganese oxide (LMR-NM) cathodes stand to reduce cost and supply-chain concerns associated with traditional cobalt-containing cathodes for lithium-ion batteries by leveraging more earth-abundant materials; however, they have shown issues with long-term cycling stability. Here, we investigate lithium difluoro(oxalate)borate (LiDFOB), tris(trimethylsilyl) phosphite (TMSPi), and vinylene carbonate (VC) electrolyte additives for their ability to improve cycling performance of LMR-NM (0.3 Li 2 MnO 3 + 0.7 LiMn 0.5 Ni 0.5 0 2 ) cells. Cryogenic scanning transmission electron microscopy (cryo-STEM) with electron energy loss spectroscopy enables the construction of a structure–function relationship between cathode electrolyte interphase (CEI) characteristics and the electrochemical performance of cells aged with these additives. We find the combination of 2 wt % TMSPi + 1 wt % LiDFOB performs better than any single additive, achieving a 28% improvement in specific capacity over the baseline electrolyte after long-term cycling. We attribute this to LiDFOB mitigating Mn ion dissolution, with cryo-STEM showing Mn stabilized up to the CEI surface, coupled with improved CEI structure and chemistry enabled by TMSPi, evidenced by a moderately thick (∼7–15 nm) CEI that appears to protect against further electrolyte reactions with the particle. These results, achieved through site-specific nanoscale characterization, directly reveal mechanisms through which electrolyte engineering can improve the performance of earth-abundant cathodes, enabling informed development of more affordable and reliable batteries to meet future energy storage needs.

25 ENERGY STORAGE↗

Phonon Dispersion Relation of Bulk Boron-Doped Graphitic Carbon

In this work, bulk turbostratic graphitic carbon of varying levels of disorder and chemical compositions has been synthesized by a direct synthesis method in the temperature range of 750–1100 °C, with a focus on boron incorporation within the graphitic lattice. The atomistic and electronic/vibrational structures were characterized by X-ray diffraction, energy-dispersive X-ray spectroscopy, Auger electron spectroscopy, X-ray absorption spectroscopy, and Raman spectroscopy. The phonon dispersion relation of graphitic carbon was found to be uniquely sensitive to substitutional boron doping, which perturbs the phonon structure while leaving the lattice structure unchanged. The dispersion relation of the D peak measured by Raman spectroscopy can be used to uniquely identify bulk graphitic materials containing a large content of ordered trigonal planar g-BC 3 units, which are of high interest in applications ranging from hydrogen storage to lithium-ion batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrogenated and Carbon-coated Na2Ti6O13 Nanowires as High-Rate Anode Materials for Lithium Ion Batteries

The main disadvantage for sodium titanate as an anode material for LIBs is its low electronic conductivity, resulting in poor rate capability. Several approaches have been taken in an attempt to improve the electronic conductivity of sodium/lithium titanate, such as electronic material coating/mixing, ionic doping, comminution, etc.; but as of yet there has been no uniform carbon coating reported on sodium titanate for LIBs. In this work, we detail a facile technique to create uniform thin carbon coating layers on Na2Ti6O13 nanowires (NTO-C). In addition, we also explored self-doped Ti3+ on carbon coated Na2Ti6O13 nanowires (H-NTO-C) in an effort to further improve its electronic conductivity. The detailed results of the synthesis, characterization, and electrochemical performance of the NTO-based materials (NTO, NTO-C and H-NTO-C) will be presented.

25 ENERGY STORAGE↗

Process Optimization of Carbon Electrode Materials Manufacturing by Experimental Study and Machine Learning Techniques

Electrospun carbon fibers from coal have been investigated as electrodes for batteries and supercapacitors. Despite the excellent properties of coal-derived carbon fibers (CCNF) for energy storage devices, there still lacks systematic understanding on how various process parameters affect final electrode performances, which poses challenges to scale from pilot to high volume manufacturing. The goals of this project are twofold. First, we focuse on process optimization for converting a new precursor from powder river basin (PRB) coal, referred to as coal-based polyurethane (CPU) to CCNF using electrospinning. Second, different machine learning techniques will be examined using experimental data from this work and open literature. Specifically, for CPU the following process parameters need to be characterized and optimized in order to produce CCNFs with desirable mechanical integrity and physiochemical properties: precursor composition and viscosity, operating voltage and distance, oxidation and carbonization temperature and duration. Consequently, physiochemical properties of the fibers were characterized to correlate these process parameters with desirable electrochemical performance. Given the complex nature of the fiber production process, ML models are assessed for their ability to capture the nonlinear relationship between process parameters and the electrochemical properties in applications including supercapacitors. As such, we applied various machine learning techniques, to determine which technique produces a model that best predicts device function.

Cincotta, Robert E.F.↗

Supporting NASA Science with High-Altitude Long-Endurance Aircraft

NASA Earth Science and Aeronautics researchers have been involved in development and use of High Altitude Long Endurance (HALE) unmanned aircraft systems (UAS) since the 1990's. The NASA Environmental Research Aircraft Sensor and Technology Program (ERAST) demonstrated the promise of HALE aircraft for providing observations while also proving the importance of triple-redundant avionics to improve system reliability for large unmanned aircraft. Early efforts to develop an operational HALE capability for earth observations languished for nearly two decades owing to insufficient solar panel efficiency, battery power density, and light-weight, yet strong, materials. During this time NASA researchers focused on using the Global Hawk to demonstrate the utility of providing diurnal measurements over severe storms (ie. HS3) and to track stratospheric water vapor transport (ATTREX). Recent significant commercial investments are now leading to the realization of a long-held goal of week- to month-long sustained observations and measurements from the stratosphere. In addition to a historical review of NASA use and interest in HALE aircraft, this paper will present current concepts for exploiting current and planned HALE aircraft capabilities including in situ characterization of atmospheric composition and dynamics as well as imagery collection. NASA researchers anticipate HALE will provide a useful means to test smallsat instruments and components. Observations from HALE-based instruments might also provide useful gap-filler observations to flagship satellite missions where the repeat time doesn't allow for measurements of quickly changing phenomenon. HALE will likely also provide measurements and communications relay to facilitate other aircraft in multi-aircraft campaigns. We will also report on progress towards a NASA-funded flight test planned for summer 2019 of a solar-electric vehicle designed to carry 7kg (15lbs) for 30 days at 20km altitude.

earth observations↗

Demonstrating Next Generation High-Altitude, Long Endurance Aircraft for Earth Science

This paper will address NASA activities to monitor and study Earth processes from long-duration unmanned aircraft systems (UAS). NASA is currently supporting both large and small UAS development and demonstration. In a follow-on to previous work, NASA Armstrong Flight Research Center is hosting test flights of a large AeroVironment solar-powered aircraft, while NASA Ames Research Center is supporting the demonstration of a light-weight solar powered aircraft by Swift Engineering. Both are designed for long duration, multi-day flight. NASA Earth Science and Aeronautics researchers have been involved in the development and use of High Altitude Long Endurance (HALE) UAS since the 1990's. The NASA Environmental Research Aircraft Sensor and Technology Program (ERAST) demonstrated the promise of HALE aircraft for providing observations while also proving the importance of triple-redundant avionics to improve system reliability for large unmanned aircraft. Early efforts to develop an operational HALE capability for earth observations languished for nearly two decades owing to insufficient solar panel efficiency, battery power density, and light-weight, yet strong, materials. During this time NASA researchers focused on using the Global Hawk to demonstrate the utility of providing diurnal measurements over severe storms (i.e. HS3) and to track stratospheric water vapor transport (ATTREX). Recent significant commercial investments are now leading to the realization of a long-held goal of week- to month-long sustained observations and measurements from the stratosphere. In addition to a historical review of NASA use and interest in HALE aircraft, this paper will present current concepts for exploiting current and planned HALE aircraft capabilities including in situ characterization of atmospheric composition and dynamics as well as imagery collection and internet connectivity. NASA researchers anticipate HALE will also provide a useful means to test smallsat instruments and components. Observations from HALE-based instruments might also provide useful gap-filler observations to flagship satellite missions where the repeat time doesn't allow for measurements of quickly changing phenomenon. HALE will likely also provide measurements and communications relay to facilitate other aircraft in multi-aircraft campaigns. We will also report on progress towards a NASA-supported flight tests solar electric vehicles planned for 2019. One is the Swift Engineering UAS designed to carry 7kg (15lbs) for 30 days at 20km altitude. The other is the AeroVironment Hawk 30, also designed for multi-day flight.

high-altitude↗

Neutron imaging the spatial progression of chemical oxidation of lithium-ion cathode material in a packed bed reactor

Emerging electrochemical systems relevant to energy applications including redox targeted flow batteries rely on chemical redox of solid electroactive materials using dissolved redox couples. One configuration to facilitate contact between the redox shuttles and solid material which is volume efficient is a packed bed reactor. While methods have been reported to assess the overall progression by analysis of the packed bed reactor effluent, herein analysis of the spatial progression of the chemical redox will be reported. Combination of neutron and x-ray tomography enabled assessing the pore and particle structure in the packed bed reactor and the spatial homogeneity of the reaction at different overall extents of conversion of the reactor bed. Finally, these characterization tools provide methods to probe the chemical redox processes occurring within the reactor environment.

25 ENERGY STORAGE↗

Phase Stability and Kinetics of Topotactic Dual Ca 2+ –Na + Ion Electrochemistry in NaSICON NaV 2 (PO 4 ) 3

Recent reports of reversible calcium plating and stripping have rekindled interest in the development of Ca-ion batteries (CIBs) as next-generation energy storage devices. This technology has the potential to overcome the limitations of conventional Li-ion batteries, but CIBs are plagued by a paucity of suitable cathode materials. To date, NaSICON-structured NaV 2 (PO 4 ) 3 has been demonstrated as a successful cathode candidate, exhibiting reversible (de)intercalation of 0.6 mol Ca 2+ along with stable cycling performance. However, a complex multiphase mixture forms on discharge so the Ca-ion charge storage mechanism in the NaSICON framework is poorly understood. Here in this work, we report on an investigation of the structure and/or Na + /Ca 2+ environment(s) of a variety of chemically prepared NaSICON Ca x Na y V 2 (PO 4 ) 3 phases which were characterized using synchrotron XRD, SEM-EDS, 23 Na NMR, and TEM. Highly calciated CaV 2 (PO 4 ) 3 , Ca 1.5 V 2 (PO 4 ) 3 , and CaNaV 2 (PO 4 ) 3 phases can be prepared at high temperature, but -unlike Ca 0.6 NaV 2 (PO 4 ) 3 -these materials are electrochemically inactive. To better understand the fundamental factors impacting successful Ca 2+ electrochemistry in this system, DFT was employed to examine the Ca x Na y V 2 (PO 4 ) 3 phase diagram and Ca 2+ diffusion mechanism. Theoretical insights show that phase separation into Na-rich and Ca-rich phases is a reason for the capacity limitation and demonstrate that Na + ions in the host materials assist the migration of neighboring Ca 2+ ions, enabling reversible electrochemistry in Ca x Na y V 2 (PO 4 ) 3 . This investigation of fundamental principles affecting reversible Ca 2+ (de)intercalation in Ca x Na y V 2 (PO 4 ) 3 allows for the development of design principles to enable the discovery of a variety of successful cathodes for CIBs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surface and Bulk Stabilization of Silicon Anodes with Mixed-Multivalent Additives: Ca(TFSI) 2 and Mg(TFSI) 2

Here, silicon is drawing attention as the upcoming anode material for the next generation of lithium-ion batteries due to its higher capacity compared to commercial graphite. However, silicon anions formed during lithiation are highly reactive with binder and electrolyte components creating an unstable SEI layer and limiting the calendar life of silicon anodes. The reactivity of lithium silicide and the formation of an unstable SEI layer is mitigated by utilizing the use of a mixture of Ca and Mg multivalent cations as an electrolyte additive for Si anodes to improve their calendar life. The effect of mixed salts on the bulk and surface of silicon anodes was studied by multiple structural characterization techniques. Ca and Mg ions in the electrolyte formed relatively thermodynamically stable quaternary Li-Ca-Mg-Si Zintl phases in an in-situ fashion and more stable and denser SEI layer on the Si particles. These in turn protect silicon particles against side reactions with electrolytes in a coin cell. The full cell with the mixed cation electrolyte demonstrates enhanced calendar life performance with lower measured current and current leakage than that of the baseline electrolyte due to reduced side reactions. Electron Microscopy, HRXRD, and solid-state NMR results showed that electrodes with mixed cations tended to have less cracking on the electrode surface compared to Si electrodes with Gen2 + FEC and the presence of mixed cations enhances cation migration and formation of quaternary Zintl phases stabilizing bulk and forming a more stable SEI.

25 ENERGY STORAGE↗

NASA Tech Briefs, June 2008

Topics covered include: Charge-Control Unit for Testing Lithium-Ion Cells; Measuring Positions of Objects Using Two or More Cameras; Lidar System for Airborne Measurement of Clouds and Aerosols; Radiation-Insensitive Inverse Majority Gates; Reduced-Order Kalman Filtering for Processing Relative Measurements; Spaceborne Processor Array; Instrumentation System Diagnoses a Thermocouple; Chromatic Modulator for a High-Resolution CCD or APS; Commercial Product Activation Using RFID; Cup Cylindrical Waveguide Antenna; Aerobraking Maneuver (ABM) Report Generator; ABM Drag_Pass Report Generator; Transformation of OODT CAS to Perform Larger Tasks; Visualization Component of Vehicle Health Decision Support System; Mars Reconnaissance Orbiter Uplink Analysis Tool; Problem Reporting System; G-Guidance Interface Design for Small Body Mission Simulation; DSN Scheduling Engine; Replacement Sequence of Events Generator; Force-Control Algorithm for Surface Sampling; Tool for Merging Proposals Into DSN Schedules; Micromachined Slits for Imaging Spectrometers; Fabricating Nanodots Using Lift-Off of a Nanopore Template; Making Complex Electrically Conductive Patterns on Cloth; Special Polymer/Carbon Composite Films for Detecting SO2; Nickel-Based Superalloy Resists Embrittlement by Hydrogen; Chemical Passivation of Li+-Conducting Solid Electrolytes; Organic/Inorganic Polymeric Composites for Heat-Transfer Reduction; Composite Cathodes for Dual-Rate Li-Ion Batteries; Improved Descent-Rate Limiting Mechanism; Alignment-Insensitive Lower-Cost Telescope Architecture; Micro-Resistojet for Small Satellites; Using Piezoelectric Devices to Transmit Power through Walls; Miniature Latching Valve; Apparatus for Sampling Surface Contamination; Novel Species of Non-Spore-Forming Bacteria; Chamber for Aerosol Deposition of Bioparticles; Hyperspectral Sun Photometer for Atmospheric Characterization and Vicarious Calibrations; Dynamic Stability and Gravitational Balancing of Multiple Extended Bodies; Simulation of Stochastic Processes by Coupled ODE-PDE; Cluster Inter-Spacecraft Communications; Genetic Algorithm Optimizes Q-LAW Control Parameters; Low-Impact Mating System for Docking Spacecraft; Non-Destructive Evaluation of Materials via Ultraviolet Spectroscopy; Gold-on-Polymer-Based Sensing Films for Detection of Organic and Inorganic Analytes in the Air; and Quantum-Inspired Maximizer.

Source record↗