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At least 289 records · Page 16

Nanoparticle Surface Passivation Strategies to Improve the Cycle and Calendar Lifetime of Silicon Anodes in Standard Carbonate Electrolytes

Silicon Lithium alloys (SiLix) as the anode active material in a Li-Ion battery configuration offer possible energy densities paralleled only by pure lithium metal. However, the extreme mechanical deformation of alloying and dealloying SiLix through charge/discharge cycles paired with the highly reactive interface of SiLix which generates an interfacial layer known as the solid-electrolyte-interphase are large barriers to industrial adoption of high-silicon-content negative electrodes. Moreover, these challenges are magnified when the thickness of the electrode is brought to relevant levels (>3 mg/cm2). Here, I describe our efforts to address these challenges by utilizing single-nanometer-scale silicon nanoparticles to reduce capacity fade related to mechanical failure. I also detail our efforts to modify the silicon surface through interfacial chemical engineering strategies to passivate the silicon surface. This development three different majority silicon electrodes (50-74 wt%) to achieve cycle capacity retention of greater than 73% through 1000 charge/discharge cycles against capacity-matched NMC-based cathodes and calendar lifetimes greater than one year. This research is a part of the multi-national lab Silicon Consortium Project.

anodes↗

Solvent-Free and Non-Sintered 500 Wh/kg All Solid-State Battery

Navitas teamed up with UMD and ORNL to establish a reliable scientific research team. The project addressed processing limitations of state-of-the-art solid electrolytes by extending solvent-free electrode fabrication technology to the scalable production of cathode/solid electrolyte laminates. The innovation started with a solid-state sulfide electrolyte (LiPS) with Cl stabilization able to meet the keystone conductivity challenge in a film of practical thickness (μ 50 µm). The electrolyte was based on a composite of PTFE, and stabilized LiPSCl. With optimization, the ionic conductivity reached 3.3 ×10 -3 S/cm. The solid electrolyte with as low as 0.4% binder allowed long term cycling (> 500 cycles) of Li/SSE/Li cell at > 4 mA/cm 2 with the utilization of Li > 80%. The Li and SSE interfaces were successfully protected with LiF-rich SEI layer. NCM811cathode active materials were coated with a thin layer of Al 2 O 3 (5 nm). The free standing cathode film was fabricated through dry-process with Al2O3-coated NCM811, LiPSCl, active carbon, and small amount PTFE. The all-solid-state batteries were laminated with free standing surface coated NCM811 cathode film, free standing LiPSCl SSE film, and surface protected Li anode together in a single lamination step, and demonstrated high specific capacity (> 200 mAh/g) with coulombic efficiency > 99.5%. The all-solid-state batteries through solvent-free and no-sintering process are promising for large format cell with 500 Wh/Kg specific energy density.

25 ENERGY STORAGE↗

Designing Li 4 Ti 5 O 12 /LiMn 2 O 4 Cells: Negative-to-Positive Ratio and Electrolyte

Li 4 Ti 5 O12/LiMn2O 4 (LTO/LMO) system is a promising candidate for behind-the-meter storage (BTMS) applications due to its critical-material-free chemistry exhibiting good safety and long lifetime. In this paper we design LTO/LMO cells to mitigate their major degradation mechanism, loss of Li inventory, and improve their long-term cyclability. First, LMO electrodes with different loadings (2.61, 3.29, and 4.26 mAh cm -2 ) are paired with an LTO electrode (3.35 mAh cm -2 ) to create varying negative-to-positive ratios (N/P>1, =1, and <1). Additionally, conventional ethylene carbonate (EC)/ethyl methyl carbonate (EMC) mixture electrolyte and safety enhanced EC-only electrolyte are examined. We show that storing additional Li inventory in the cathode (i.e., using a thicker electrode and having N/P<1) is a convenient method to enhance the capacity retention of LTO/LMO cells, but only if the electrode utilization is not limited by the Li + ion transport. For systems that suffer from limited transport properties, prelithiating the anode will be more effective since LTO (~165 mAh g -1 LTO ) can store the same amount of capacity using less material compared to LMO (~100 mAh g -1 LMO ). In this work, we demonstrate how the electrolyte properties and the electrode thickness of LTO/LMO cells can be designed to enhance their performance.

25 ENERGY STORAGE↗

Dynamic Boundary Layer Simulation of Pulsed CO 2 Electrolysis on a Copper Catalyst

Pulsed electrolysis has been demonstrated to improve the faradaic efficiency (FE) to C 2+ products during the electrochemical reduction of CO 2 over a Cu catalyst, but the nature of this enhancement is poorly understood. Herein, we developed a time-dependent continuum model of pulsed CO 2 electrolysis on Cu in 0.1 M CsHCO 3 that faithfully represents the experimentally observed effects of pulsed electrolysis. This work shows that pulsing results in dynamic changes in the pH and CO 2 concentration near the Cu surface, which lead to an enhanced C 2+ FE as a consequence of repeatedly accessing a transient state of heightened pH and CO 2 concentration at high cathodic overpotential. Using these insights, a variety of pulse shapes were explored to establish operating conditions that maximize the rate of C 2+ product formation and minimize the rates of H 2 and C 1 product formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

MEMS Micropropulsion Activities at JPL

A status of MEMS-based micropropulsion activities conducted at JPL will be given. These activities include work conducted on the so called Vaporizing Liquid Micro-Thruster (VLM) which recently underwent proof-of-concept testing, demonstrating the ability to vaporize water propellant at 2 W and 2 V. Micro-ion engine technologies, such m field emitter arrays and micro-grids are being studied. Focus in the field emitter area is on arrays able to survive in thruster plumes and micro-ion engine plasmas to serve as neutralizers aW engine cathodes. Integrated, batch-fabricated Ion repeller grid structures are being studied as well as different emitter tip materials are being investigated to meet these goals. A micro-isolation valve is being studied to isolate microspacecraft feed system during long interplanetary cruises, avoiding leakage and prolonging lifetime and reliability of such systems. This concept relies on the melting of a thin silicon barrier. Burst pressure values as high as 2,900 psig were obtained for these valves and power requirements to melt barriers ranging between 10 - 50 microns in thickness, as determined through thermal finite element calculations, varied between 10 - 30 W to be applied over a duration of merely 0.5 ms.

Mueller, Juergen↗

Design Principles to Govern Electrode Fabrication for the Lithium Trivanadate Cathode

A full depth of discharge mathematical model for the lithium trivanadate cathode, considering lithiation of the layered α-phase, phase change, and lithiation of the rock-salt like β-phase at lower potentials, is developed. The coupled electrode-scale and crystal-scale model is fit to electrochemical data, and additionally validated with operando EDXRD. There is good agreement between the simulated and measured spatial variation of the volume fraction of the β-phase. This mathematical model is used to guide electrode fabrication, accounting for both ionic and electronic transport effects. Values of three design parameters—electrode thickness, porosity, and volume fraction of conductor—are identified, and the sensitivity of the energy density to these design parameters is quantified. The model is also used to investigate electrode design to create electrodes that deliver the maximum achievable energy density under the constraint that the α to β-phase transition is avoided, since phase change has been demonstrated to reduce cycle life. The energy density sacrificed to avoid phase change decreases at higher discharge rates, but the target values for electrode fabrication remain the same as those when optimizing the electrode for the full depth of discharge.

25 ENERGY STORAGE↗

(La 0.8 Sr 0.2 ) 0.98 MnO 3-δ -Zr 0.92 Y 0.16 O 2-δ :PrOx for oxygen electrode supported solid oxide cells

(La 0.8 Sr 0.2 ) 0.98 MnO 3-δ (LSM)- Zr 0.92 Y 0.16 O 2-δ (YSZ) has been widely studied as the cathode for solid oxide fuel cells (SOFCs), but its low activity has been a cell performance limiting factor. Herein, LSM-YSZ:PrO x composite is developed as an active electrocatalyst for both oxygen reduction and evolution reactions. A single step PrO x infiltration into LSM-YSZ lowers the polarization resistance (Rp) 10–20 times depending on the test temperature. Distribution of relaxation times (DRT) calculation reveals that adding PrO x affects surface exchange between adsorbed/desorbed oxygen and lattice oxygen, and oxygen dissociative adsorption/desorption. A symmetrical cell with a thin YSZ electrolyte sandwiched between thick LSM-YSZ:PrO x electrode-supports is developed and its oxygen generation performance and stability are evaluated under various current densities and temperatures. Finally, reversible solid oxide cell (ReSOC) performance is also reported for LSM-YSZ:PrO x supported cells with the oxide fuel electrode Sr 0.95 (Ti 0.3 Fe 0.63 Ni 0.07 )O 3-δ (STFN).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding of Low‐Porosity Sulfur Electrode for High‐Energy Lithium–Sulfur Batteries

Abstract The lithium–sulfur (Li–S) battery is a promising technology for large‐scale energy storage and vehicle electrification due to its high theoretical energy density and low cost. Reducing the sulfur cathode porosity has been identified recently as a viable strategy for improving the cell practical energy density and minimizing pore‐filling electrolytes to extend cell life at lean electrolyte conditions. Direct use of a low‐porosity cathode for Li–S battery results in poor electrode wetting, nonuniform electrode reactions, and thus early cell failure. To understand and mitigate the barriers associated with the use of low‐porosity electrodes, multiscale modeling is performed to predict electrode wetting, electrolyte diffusion, and their impacts on sulfur reactions in Li–S cells by explicitly considering the electrode wettability impacts and electrode morphologies. The study elucidates the critical impact of low tortuosity and large channel pore design for promoting electrode wetting and species diffusion. It is suggested that the secondary particle size should be comparable with the electrode thickness to effectively promote electrolyte wettability and sulfur reactivity. This study provides new insights into the low‐porosity electrode material and designs and is expected to accelerate the development of practical high‐energy Li–S batteries.

25 ENERGY STORAGE↗

Superlattice-Structured Films by Magnetron Sputtering as New Era Electrodes for Advanced Lithium-ion Batteries

Sustaining sound structures in Si-based anodes is extremely challenging because of the high volumetric expansion that occurs upon cycling. To maintain high capacities over cycles, new designs rely on engineering-specific hierarchical geometries and/or optimized composite compositions such that at least one of the multiple elements serves as buffer and/or electron conductive pathways in the electrodes. In this paper, we report an innovative design in which alternating layers of periodic atomic structures involving multiple elements form a new anode material for lithium-ion batteries. In this work, a superlattice-structured amorphous film made using Si, Mo, and Cu is fabricated by a simple and scalable magnetron sputtering process for the first time. This continuous and repetitive superlattice formation along the film thickness provides a homogeneous stress-strain distribution. The Mo-Cu layer in the superlattice acts as an inactive-conductive layer and as a backbone to handle the volume expansion of active Si upon cycling. This nano-functional superlattice approach enables harnessing the high energy density of Si while maintaining its structural stability. As a result, the electrode exhibits high specific capacity and capacity retention even at high cycling rates. The possible use of the film in a full cell is also evaluated by cycling it vs. the LiMn 1.5 Ni 0.5 O 4 cathode. The full cell maintains a stable capacity of about 900 mAh g anode -1 over 150 cycles, at ~600 mA g -1 rate. The remarkable performance of this nano-functional superlattice film is found to be promising as anodes for applications that require high energy, long calendar life, and excellent abuse tolerance such as electric vehicle batteries.

25 ENERGY STORAGE↗

NEPP Evaluation of Automotive Grade Tantalum Chip Capacitors

Automotive grade tantalum (Ta) chip capacitors are available at lower cost with smaller physical size and higher volumetric efficiency compared to military/space grade capacitors. Designers of high reliability aerospace and military systems would like to take advantage of these attributes while maintaining the high standards for long-term reliable operation they are accustomed to when selecting military-qualified established reliability tantalum chip capacitors (e.g., MIL-PRF-55365). The objective for this evaluation was to assess the long-term performance of off-the-shelf automotive grade Ta chip capacitors (i.e., manufacturer self-qualified per AEC Q-200). Two (2) lots of case size D manganese dioxide (MnO2) cathode Ta chip capacitors from 1 manufacturer were evaluated. The evaluation consisted of construction analysis, basic electrical parameter characterization, extended long-term (2000 hours) life testing and some accelerated stress testing. Tests and acceptance criteria were based upon manufacturer datasheets and the Automotive Electronics Council's AEC Q-200 qualification specification for passive electronic components. As-received a few capacitors were marginally above the specified tolerance for capacitance and ESR. X-ray inspection found that the anodes for some devices may not be properly aligned within the molded encapsulation leaving less than 1 mil thickness of the encapsulation. This evaluation found that the long-term life performance of automotive grade Ta chip capacitors is generally within specification limits suggesting these capacitors may be suitable for some space applications.

Automotive↗

Cooling plate assembly for plasma windows positioned in a beam accelerator system

A beam accelerator system operable to produce a medical isotope, including an ion accelerator that generates an ion beam; a low-pressure chamber; an anode adjacent and fluidly connected to the low-pressure chamber; a plasma window adjacent and fluidly connected to the anode; and a cathode housing adjacent and fluidly connected to the plasma window. The plasma window has a plurality of plates, each plate having an aperture that is aligned with an aperture in one or more adjacent plates to form a plasma channel. One or more plates in the plurality of plates includes a unitary plate having an aperture therein, and one or more cooling channels entering the unitary plate at a first side of the unitary plate and exiting the unitary plate at a second side of the unitary plate. The one or more cooling channels run through a thickness of the unitary plate.

Gribb, Tye↗

Dual-shell silicate and alumina coating for long lasting and high capacity lithium ion batteries

In this work we demonstrate a theory-driven, novel dual-shell coating system of Li 2 SrSiO 4 and Al 2 O 3 , achieved via a facile and scalable sol-gel technique on LiCoO 2 electrode particles. The optimal thickness of each coating can lead to increased specific capacity (~185 mAh/g at 0.5 C-rate) at a cut-off potential of 4.5 V, and greater cycling stability at very high C rates (up to 10 C) in half-cells with lithium metal. The mechanism of this superior performance was investigated using a combination of X-ray and electron characterization methods. It shows that the results of this investigation can inform future studies to identify still better dual-shell coating schemes, achieved by such industrially feasible techniques, for application on similar, nickel-rich cathode materials.

25 ENERGY STORAGE↗

Industrialization of the ion plating process

A new process referred to as ion plating by induction heating (IPIH) is described, which combines the advantages of both ion plating and induction heating. The IPIH apparatus consists of the specimen (cathode) to be coated and the evaporation heating source, which is a ceramic crucible containing the metal to be heated. The specimen is an internal part of the high-voltage ceramic-metal vacuum feedthrough and is connected to the negative terminal of the high-voltage power supply, the positive terminal of the power supply being grounded. The plating conditions are the same as those most commonly used in industrial ion plating. A number of metals - such as nickel, iron, platinum - which were practically impossible to deposit by resistance heating evaporation can now be effectively evaporated and deposited to any desired thickness. Excellent adherence is observed for many metals deposited on various metal surfaces in thicknesses from 0.15 to 50 microns, regardless of the materials selected for coating and substrate.

Spalvins, T.↗

Anodic Interfacial Evolution in Extremely Fast Charged Lithium-Ion Batteries

Interfacial reaction mechanisms at the anode/separator interface play a central role in the performance and safety of lithium-ion batteries during fast charging. We report a mechanistic study on the evolution and interactions of the aging mechanisms at the anode/separator interface in lithium cobalt oxide/graphite pouch cells charged with variable charging rates (1–6C) over 10 cycles. In situ electrochemical measurements, including voltage relaxation, Coulombic efficiency, and direct current internal resistance, indicated an incremental lithium loss until the C rates were ≤5C. A substantial capacity fade is observed in the first few cycles of fast charging, but the magnitude of capacity fade progressively diminishes with the number of cycles, indicating a suppression in the lithium deposition mechanism. Post-mortem film thickness, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) analyses were performed to elucidate the evolution of electrolyte decomposition, the solid–electrolyte interface (SEI), lithium plating, and film fracture mechanisms with C rate. XPS measurements confirmed an increasing lithium concentration in an SEI film with an increase in the C rate. SEM images showed a growth of dendritic lithium on the anode surface from 1C to 3C. Precrack formation leading to an interfacial film fracture was observed at higher C rates. Furthermore, a differential analysis of the discharge capacity indicated a possible two-phase delithiation from the anode and reduced cathodic lithiation due to lithium loss at high C rates.

36 MATERIALS SCIENCE↗

Alkali metal-sulfur secondary battery containing cathode material particulates

Provided is a rechargeable alkali metal-sulfur cell comprising an anode active material layer, an electrolyte, and a cathode active material layer comprising multiple particulates, wherein at least one of the particulates comprises one or a plurality of sulfur-containing material particles being embraced or encapsulated by a thin layer of a conductive sulfonated elastomer composite having from 0.01% to 50% by weight of a conductive reinforcement material dispersed in a sulfonated elastomeric matrix material, wherein the conductive reinforcement material is selected from graphene sheets, carbon nanotubes, carbon nanofibers, metal nanowires, conductive polymer fibers, or a combination thereof and the composite has a recoverable tensile strain from 2% to 500%, a lithium ion conductivity from 10−7 S/cm to 5×10−2 S/cm, and a thickness from 0.5 nm to 10 μm. This battery exhibits an excellent combination of high sulfur content, high sulfur utilization efficiency, high energy density, and long cycle life.

Zhamu, Aruna↗

Correlating the influence of porosity, tortuosity, and mass loading on the energy density of LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathodes under extreme fast charging (XFC) conditions

Extreme fast charging capabilities along with high energy density of Li-ion batteries are the key factors to increase the adoption of electric vehicles while eliminating the problem of range anxiety. The U.S Department of Energy has a goal of <12 min charging time with energy density of > 200 Wh kg -1 . A combined improvement in the electrode architecture, electrolyte properties, and separator membrane is necessary to achieve this goal. Cells with thin electrodes are capable of extreme fast charging at the expense of low energy density and high cost. Electrode engineering can maximize energy density. In this work, the influence of porosity, mass loading and charging protocols on capacity and energy density and electrode kinetics are investigated under extreme fast charging conditions. Increasing the mass loading from 11.5 mg cm -2 to 25 mg cm -2 compromises the rate performance due to the mass transport limitation and underutilization of thick electrodes. Furthermore, reducing the electrode porosity from 50% to 35% improves the rate performance ascribed to shorter Li ion diffusion length. Symmetric cells are cycled to verify the performance of the half cells, suggesting that Li metal plating is the rate limiting step under high current density.

25 ENERGY STORAGE↗

Inert-gas thruster technology

Attention is given to recent advances in component technology for inert-gas thrusters. It is noted that the maximum electron emission of a hollow cathode with Ar can be increased 60-70% by using an enclosed keeper configuration. Operation with Ar but without emissive oxide has also been attained. A 30-cm thruster operated with Ar at moderate discharge voltages is found to give double-ion measurements consistent with a double-ion correlation developed earlier on the basis of 15-cm thruster data. An attempt is made to reduce discharge losses by biasing anodes positive of the discharge plasma. The performance of a single-grid ion-optics configuration is assessed. The ion impingement on the single-grid accelerator is found to approach the value expected from the projected blockage when the sheath thickness next to the accelerator is 2-3 times the aperture diameter.

Kaufman, H. R.↗

Inert gas thrusters

Some advances in component technology for inert gas thrusters are described. The maximum electron emission of a hollow cathode with Ar was increased 60-70% by the use of an enclosed keeper configuration. Operation with Ar, but without emissive oxide, was also obtained. A 30 cm thruster operated with Ar at moderate discharge voltages give double-ion measurements consistent with a double ion correlation developed previously using 15 cm thruster data. An attempt was made to reduce discharge losses by biasing anodes positive of the discharge plasma. The reason this attempt was unsuccessful is not yet clear. The performance of a single-grid ion-optics configuration was evaluated. The ion impingement on the single grid accelerator was found to approach the value expected from the projected blockage when the sheath thickness next to the accelerator was 2-3 times the aperture diameter.

Kaufman, H. R.↗