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At least 451 records · Page 25

Chrysler Upset Protrusion Joining Techniques for Joining Dissimilar Metals

The project goal was to develop and demonstrate a robust, cost effective, and versatile joining technique, known as Upset Protrusion Joining (UPJ), for joining challenging dissimilar metal com-binations, especially those where one of the metals is a die cast magnesium (Mg) component. Since two of the key obstacles preventing more widespread use of light metals (especially in high volume automotive applications) are 1) a lack of robust joining techniques and 2) susceptibility to galvanic corrosion, and since the majority of the joint combinations evaluated in this project include die cast Mg (the lightest structural metal) as one of the two materials being joined, and since die casting is the most common and cost effective process for producing Mg components, then successful project completion provides a key enabler to high volume application of lightweight materials, thus potentially leading to reduced costs, and encouraging implementation of lightweight multi-material vehicles for significant reductions in energy consumption and reduced greenhouse gas emissions. Eco-nomic benefits to end-use consumers are achieved primarily via the reduction in fuel consumption. Unlike currently available commercial processes, the UPJ process relies on a very robust mechanical joint rather than intermetallic bonding, so the more cathodic material can be coated prior to joining, thus creating a robust isolation against galvanic attack on the more anodic material. Additionally, since the UPJ protrusion is going through a hole that can be pre-drilled or pre-punched prior to coating, the UPJ process is less likely to damage the coating when the joint is being made. Further-more, since there is no additional cathodic material (such as a steel fastener) used to create the joint, there is no joining induced galvanic activity beyond that of the two parent materials. In accordance with its originally proposed plan, this project has successfully developed process variants of UPJ to enable joining of Mg die castings to aluminum (Al) and steel sheet components of various thicknesses, strengths and coating configurations. While most development focused on the simpler round boss version of the process, an additional phase of the work focused on devel-opment of an oval boss version to support applications with narrow flanges, while yet another vari-ant of the process, known as Upset Cast Riveting (UCR), was developed and evaluated for joining mixed metals that may not necessarily include Mg or Al die cast components. Although each varia-tion posed unique challenges described later in the report, all variations were successfully produced and evaluated, and each could be further developed for specific types of commercial applications. In this project, UPJ performed favorably against the benchmark self-pierce riveting (SPR) process in Mg AM60B to Al 6013 combinations although significant corrosion challenges were observed in both processes, especially for the bare Mg to bare Al configurations. Additional challenges were observed in joining Mg to steel with the UPJ process (SPR was not evaluated for this combination as it was not considered viable). To pass FCA’s specified corrosion tests with Mg/steel combina-tions, new steel treatments were evaluated, as well as adhesives and sealed edges. These showed significant improvement. In general, UPJ performed very well in Mg to Al 6016 combinations, even in corrosion evaluation of the bare Mg to bare Al configuration (again, SPR was not evaluated for this material combination as the 1.1 mm thick Al6016 sheet thickness was considered too thin for the SPR process). The improvement in corrosion performance of the Mg to Al 6016 combina-tion over the Mg to Al 6013 combination was thought to be a result of the lower copper content in the Al 6016 alloy. Oval boss joints showed substantial improvement in all joint strength criteria compared to 8.0-mm diameter round boss joints but were not evaluated for corrosion performance. The improved joint strength is likely a result of larger shear area. Cosmetic corrosion performance of all test assemblies (UPJ, UCR and SPR) was a challenge due to exposed edges and crevices al-lowing undercutting of the coatings. In real world component applications, the exposed edges, so prevalent on the joining test coupons, would be less prevalent and easier to protect.

36 MATERIALS SCIENCE↗

Titanium Niobium Oxide: From Discovery to Application in Fast-Charging Lithium-Ion Batteries

Lithium-ion batteries are essential for portable technology and are now poised to disrupt a century of combustion-based transportation. The electrification revolution could eliminate our reliance on fossil fuels and enable a clean energy future; advanced batteries would facilitate this transition. However, owing to the demanding performance, cost, and safety requirements, it is challenging to translate new materials from laboratory prototypes to industrial-scale products. This Perspective describes that journey for a new lithium-ion battery anode material, TiNb 2 O 7 (TNO). TNO is intended as an alternative to graphite or Li 4 Ti 5 O 12 with better rate and safety characteristics than the former and higher energy density than the latter. The high capacity of TNO stems from the multielectron redox of Nb 5+ to Nb 3+ , its operating voltage window well above the Li + /Li reduction potential prevents lithium dendrite formation, and its open crystal structure leads to high-power performance. Nevertheless, the creation of a practical TNO anode was nonlinear and nontrivial. Its history is built on 30 years of fundamental science that preceded its application as a battery anode, and its battery development included a nearly 30-year gap. The insights and lessons contained in this Perspective, many of them acquired firsthand, serve two purposes: (i) to unite the disparate studies of TiNb 2 O 7 into a coherent modern understanding relevant to its application as a battery material and (ii) to highlight briefly some of the challenges faced when scaling up a new material that affect TiNb 2 O 7 as well as new electrode candidates more generally.

25 ENERGY STORAGE↗

Translating a Material Discovery into a Commercial Product in the Modern Lithium-ion Battery Market

Lithium-ion batteries are essential for portable technology and are now poised to disrupt a century of combustion-based transportation. The electrification revolution could eliminate our reliance on fossil fuels and enable a clean energy future; advanced batteries would facilitate this transition. However, owing to the demanding performance, cost, and safety requirements, it is challenging to translate new materials from laboratory prototypes to commercial products. This Perspective describes that journey toward commercialization for a new lithium-ion battery anode material, TiNb2O7 (TNO). TNO is intended as an alternative to graphite or Li4Ti5O12 with better rate and safety characteristics than the former, and higher energy density than the latter. The high capacity of TNO stems from multielectron redox of Nb5+ to Nb3+, its operating voltage window well above Li+/Li reduction potential prevents lithium dendrite formation, and its open crystal structure leads to high-power performance. Nevertheless, the creation of a practical TNO anode was non-linear and non-trivial. Its history is built on 30 years on fundamental science that preceded its application as a battery, and its battery development included a nearly 30-year gap. The insights and lessons 2 contained in this Perspective, many of them acquired firsthand, serve two purposes: (i) to unite the disparate studies of TiNb2O7 into a coherent modern understanding relevant to its application as a battery material and (ii) to highlight some of the considerations of commercializing a new material that affect TiNb2O7 as well as new electrode candidates more generally.

Griffith, Kent J.↗

Comparative study of bulk and nano-structured mesoporous SnO 2 electrodes on the electrochemical performances for next generation Li rechargeable batteries

For next generation Li-ion batteries, advanced electrode materials with high energy densities are mightily important issue. Since the partial oxidation of Sn with Li 2 O to form SnO x was demonstrated upon delithiation in SnO 2 anode, the additional conversion reaction has contributed that the theoretical capacity of SnO 2 can be extended from 783 to 1494 mAh g -1 . Herein, with the design of additional conversion reaction, we discuss key factors for high electrochemical performances of the SnO 2 anodes through comparative analysis between nano-structured mesoporous SnO 2 and conventional bulk SnO 2 , based on synchrotron radiation-based techniques, quantitative analysis of extended X-ray absorption fine structure spectra, and bond strength calculation. In this way, we demonstrate that the mesoporous SnO 2 has a nano-engineering structure, inducing the facilitated electrochemical reaction and the weak Sn-O bond strength that would have an advantage in the additional conversion reaction as well as a void structure, relieving the severe volume changes during lithiation/delithiation. Consequently, excellent electrochemical performance is obtained in the mesoporous SnO 2 . Furthermore, insight from this research enables important advance in the development of metal oxide-based anode materials by making irreversible reaction reversible, providing a realizable strategy for the design and creation of high-energy storage devices.

25 ENERGY STORAGE↗

Synthesis of new two-dimensional titanium carbonitride Ti 2 C 0.5 N 0.5 T x MXene and its performance as an electrode material for sodium-ion battery

Two-dimensional (2D) layered transition metal carbides/nitrides, called MXenes, are attractive alternative electrode materials for electrochemical energy storage. Owing to their metallic electrical conductivity and low ion diffusion barrier, MXenes are promising anode materials for sodium-ion batteries (SIBs). Herein, we report on a new 2D carbonitride MXene, viz ., Ti 2 C 0.5 N 0.5 T x (T x stands for surface terminations), and the only second carbonitride after Ti 3 CNT x so far. A new type of in situ HF (HCl/KF) etching condition was employed to synthesize multilayer Ti 2 C 0.5 N 0.5 T x powders from Ti 2 AlC 0.5 N 0.5 . Spontaneous intercalation of tetramethylammonium followed by sonication in water allowed for large-scale delamination of this new titanium carbonitride into 2D sheets. Multilayer Ti 2 C 0.5 N 0.5 T x powders showed higher specific capacities and larger electroactive surface area than those of Ti 2 CT x powders. Multilayer Ti 2 C 0.5 N 0.5 T x powders show a specific capacity of 182 mAh g -1 at 20 mA g -1 , the highest among all reported MXene electrodes as SIBs with excellent cycling stability.

25 ENERGY STORAGE↗

Mechanical studies of the solid electrolyte interphase on anodes in lithium and lithium ion batteries

A stable solid electrolyte interphase (SEI) layer is key to high performing lithium ion batteries for metrics such as calendar and cycle life. The SEI must be mechanically robust to withstand large volumetric changes in anode materials such as lithium and silicon, so understanding the mechanical properties and behavior of the SEI is essential for the rational design of artificial SEI and anode form factors. The mechanical properties and mechanical failure of the SEI are challenging to study, because the SEI is thin at only ~ 10 – 200 nm thick and is air sensitive. Furthermore, the SEI changes as a function of electrode material, electrolyte and additives, temperature, potential, and formation protocols. A variety of in situ and ex situ techniques have been used to study the mechanics of the SEI on a variety of lithium ion battery anode candidates; however, there hasn't been a succinct review of the findings thus far. Because of the difficultly of isolating the true SEI and its mechanical properties, there have been a limited number of studies that can fully de-convolute the SEI from the anode it forms on. A review of past research will be helpful for culminating current knowledge and helping to inspire new innovations to better quantify and understand the mechanical behavior of the SEI. This review will summarize the different experimental and theoretical techniques used to study the mechanics of SEI on common lithium ion battery anodes and their strengths and weaknesses.

25 ENERGY STORAGE↗

Study of Cu-Ni-Fe Alloys as Inert Anodes for Al Production in Low-Temperature KF-AlF{sub 3} Electrolyte

Cu-Ni-Fe-based alloys are considered as promising O{sub 2}-evolving anode materials for CO{sub 2}-free Al production. In the present study, biphased (as-cast) and monophased (postcasting homogenized) Cu{sub 65}Ni{sub 20}Fe{sub 15}, alloys, and monophased Ni{sub 65}Fe{sub 25}Cu{sub 10} alloy (in wt pct) are evaluated as O{sub 2}-evolving anodes for Al production in potassium cryolite at 700 °C. The produced Al purity is 99.6 wt pct, and the erosion rate is estimated at 0.4 cm year{sup −1} for both Cu{sub 65}Ni{sub 20}Fe{sub 15} anodes compared to 95.2 wt pct and 3.2 cm year{sup −1} for the Ni{sub 65}Fe{sub 25}Cu{sub 10} anode. The compositions, and morphologies of the surface oxide layer and the metal fluoride layer present at the oxide/alloy interface are compared for the three anodes. The deleterious impact of electrolyte infiltration on the surface oxide building is highlighted.

36 MATERIALS SCIENCE↗

Enhanced electrochemical performance of an electrospun carbon/MoO2 composite nanofiber membrane as self-standing anodes for lithium-ion batteries

Highlights: • Flexible C/MoO{sub 2} NFM was prepared by electrospinning and controlled heat treatment. • C/MoO{sub 2} NFM was used directly as self-standing and binder-free anodes for LIBs. • The electrode exhibits good capacity retention, rate performance and cyclability. • A high reversible capacity (811 mAh g{sup –1}) is obtained at 100 mA g{sup –1} after 100 cycles. • The possible mechanisms of the superior electrochemical performance are discussed. - Abstract: A flexible carbon nanofiber membrane (NFM) containing uniformly dispersed MoO{sub 2} nanoparticles is facilely fabricated via electrospinning and subsequent controlled reduction-carbonization. This NFM is used directly as a binder-free anode in lithium-ion batteries (LIBs). The self-standing carbon/MoO{sub 2} (C/MoO{sub 2}) NFM electrode has a good capacity retention, a satisfactory rate capability and a high reversible capacity of 811 mAh g{sup –1} after 100 cycles at a current density of 100 mA g{sup –1}, which is superior to most other MoO{sub 2}-based anodes. The superior electrochemical properties of the resultant C/MoO{sub 2} NFM are attributed to the cooperative effects from the excellent conductivity of the carbon nanofiber matrix, the high electrochemical performance of MoO{sub 2}, the unique one-dimensional nanofiber structure and the three-dimensional porous network structure. The present C/MoO{sub 2} NFM may be an attractive candidate as an anode material for LIBs.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Tin Oxynitride Anodes by Atomic Layer Deposition for Solid-State Batteries

Major advances in thin-film solid-state batteries (TFSSBs) may capitalize on 3D structuring using high-aspect-ratio substrates such as nanoscale pits, pores, trenches, flexible polymers, and textiles. This will require conformal processes such as atomic layer deposition (ALD) for every active functional component of the battery. In this paper, we explore the deposition and electrochemical properties of SnO 2 , SnN y , and SnO x N y thin films as TFSSB anode materials, grown by ALD using tetrakisdimethylamido(tin), H 2 O, and N 2 plasma as precursors. By controlling the dose ratio between H 2 O and N 2 , the N–O fraction can be tuned between 0% N and 95% N. The electrochemical properties of these materials were tested across a composition range varying from pure SnO 2 , to SnON intermediates, and pure SnNy. In TFSSBs, the SnNy anodes are found to be more stable during cycling than the SnO 2 or SnO x N y films, with an initial reversible capacity beyond that of Li–Sn alloying, retaining 75% of their capacity over 200 cycles compared to only 50% for SnO 2 . Lastly, the performance of the SnO x N y anodes indicates that SnN y anodes should not be negatively impacted by small levels of O contamination.

36 MATERIALS SCIENCE↗

Scale-Up of Novel Li-Conducting Halide Solid State Battery Electrolyte

LBNL and project partner Saint Gobain (SG) demonstrated scalable processing of halide-based solid state batteries. SG’s innovative halide-based SSE utilized in this project is inherently scalable: it can be compressed into a dense electrolyte sheet at room temperature under moderate pressure, can be processed in dry air, and does not present any safety issues during processing or end use. The halide material forms the dense electrolyte layer, and is dispersed in the thick cathode to form a highly conductive path for Li ions. The halide also comes in contact with various environments and other materials (solvents, binders, processing equipment, etc.) throughout the battery manufacturing process, and must be stable in contact with cathode and anode materials during operation.

25 ENERGY STORAGE↗

Li-ion battery material under high pressure: amorphization and enhanced conductivity of Li 4 Ti 5 O 12

Lithium titanium oxide (Li 4 Ti 5 O 12 , LTO), a 'zero-strain' anode material for lithium-ion batteries, exhibits excellent cycling performance. However, its poor conductivity highly limits its applications. Here, the structural stability and conductivity of LTO were studied using in situ high-pressure measurements and first-principles calculations. LTO underwent a pressure-induced amorphization (PIA) at 26.9 GPa. The impedance spectroscopy revealed that the conductivity of LTO improved significantly after amorphization and that the conductivity of decompressed amorphous LTO increased by an order of magnitude compared with its starting phase. Furthermore, our calculations demonstrated that the different compressibility of the LiO 6 and TiO 6 octahedra in the structure was crucial for the PIA. The amorphous phase promotes Li + diffusion and enhances its ionic conductivity by providing defects for ion migration. Our results not only provide an insight into the pressure depended structural properties of a spinel-like material, but also facilitate exploration of the interplay between PIA and conductivity.

25 ENERGY STORAGE↗

Porous silicon oxide (SiO) anode enabled by a conductive polymer binder and performance enhancement by stabilized lithium metal power (SLMP)

The invention demonstrates that only 2% functional conductive polymer binder without any conductive additives was successfully used with a micron-size silicon monoxide (SiO) anode material, demonstrating stable and high gravimetric capacity (>1000 mAh/g) for .about.500 cycles and more than 90% capacity retention. Prelithiation of this anode using stabilized lithium metal powder (SLMP.RTM.) improves the first cycle Coulombic efficiency of a SiO/NMC full cell from .about.48% to .about.90%. This combination enables good capacity retention of more than 80% after 100 cycles at C/3 in a lithium-ion full cell. We also demonstrate the important connection between porosity and the loading of silicon electrodes. By employing a highly porous silicon electrode, a high areal capacity (3.3 mAh/cm.sup.2) is obtained. This method works well to achieve high loading of other high-capacity alloy anodes, the state-of-art graphite anode, as well as a high loading of positive electrodes for LIBs.

Liu, Gao↗

High Performance SrFe 0.2 Co 0.4 Mo 0.4 O 3–δ Ceramic Anode Supported Low-Temperature SOFCs

The development of alternative ceramic anodes for low-temperature solid oxide fuel cells (LT-SOFCs) is essential to overcome the inherent challenges such as redox instability and coking associated with Ni-based cermet anodes. Moreover, due to the large electrolyte ohmic loss at low temperature, it is critical to developing an electrode supported cell that allows electrolyte thickness reduction. Here we successfully demonstrated a high performance SrFe 0.2 Co 0.4 Mo 0.4 O 3–δ (SFCM) ceramic anode supported LT-SOFC with a peak power density of 730 mW cm –2 and 300 mW cm –2 at ambitious low temperatures of 550 °C and 450 °C, respectively, in humidified H 2 . The new anode material SFCM exhibits exceptional conductivity of over 30 S cm –1 at 450 °C in humidified H 2 , providing essential current collection capability as an anode backbone appropriate for the infiltration of Ni-gadolinia doped ceria (GDC) electrocatalysts. Compared to conventional Ni-cermet anodes, the nano-sized Ni-GDC particles in our SFCM based electrode significantly improves the cell stability in hydrocarbon gases. We demonstrated a stable long-term operation over a period of 380 h in CH 4 –containing gas mixtures at 450 °C with a voltage degradation rate of 4% per 1000 h at a constant current of 0.2 A*cm –2 . Furthermore, our results demonstrate a high performance ceramic anode with high stability for low temperature operation.

25 ENERGY STORAGE↗

Simulation of temperature dependent dielectric breakdown in n{sup +}-polySi/SiO{sub 2}/n-6H-SiC structures during Poole-Frenkel stress at positive gate bias

We present for the first time a thorough investigation of trapped-hole induced gate oxide deterioration and simulation results of time-dependent dielectric breakdown (TDDB) of thin (7–25 nm) silicon dioxide (SiO{sub 2}) films thermally grown on (0 0 0 1) silicon (Si) face of n-type 6H-silicon carbide (n-6H-SiC). Gate oxide reliability was studied during both constant voltage and current stress with positive bias on the degenerately doped n-type poly-crystalline silicon (n{sup +}-polySi) gate at a wide range of temperatures between 27 and 225 °C. The gate leakage current was identified as the Poole-Frenkel (PF) emission of electrons trapped at an energy 0.92 eV below the SiO{sub 2} conduction band. Holes were generated in the n{sup +}-polySi anode material as well as in the oxide bulk via band-to-band ionization depending on the film thickness t{sub ox} and the energy of the hot-electrons (emitted via PF mechanism) during their transport through oxide films at oxide electric fields E{sub ox} ranging from 5 to 10 MV/cm. Our simulated time-to-breakdown (t{sub BD}) results are in excellent agreement with those obtained from time consuming TDDB measurements. It is observed that irrespective of stress temperatures, the t{sub BD} values estimated in the field range between 5 and 9 MV/cm better fit to reciprocal field (1/E) model for the thickness range studied here. Furthermore, for a 10 year projected device lifetime, a good reliability margin of safe operating field from 8.5 to 7.5 MV/cm for 7 nm and 8.1 to 6.9 MV/cm for 25 nm thick SiO{sub 2} was observed between 27 and 225 °C.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Boosting the sodium storage behaviors of carbon materials in ether-based electrolyte through the artificial manipulation of microstructure

The porous carbon blacks rationally designed by a facile yet efficient NH 3 thermal etching route have been investigated as anode materials in an ether-based electrolyte for sodium-ion batteries. The as-synthesized CBN35 carbon black with a 35% weight loss after NH3 thermal etching exhibited a large specific charge capacity of 352 mAh g -1 at 50 mA g -1 and a superior rate capability of 101 mAh g -1 at 16000 mA g -1 , due to its highest microporosity, an appropriate surface area, a desirable microstructure, and a promising hybrid intercalation mechanism. Impressively, even cycled at 1600 mA g -1 over 3200 cycles, an outstanding reversible capacity of 103 mAh g -1 with a negligible 0.0162% capacity loss per cycle can still be achieved. Based on the multimodal characterizations including the structural probes of phase evolution for carbon materials, the electrochemical techniques, and the surface-sensitive XAS measurements, the exceptional electrochemical properties should stem from several merits of modified carbon black system. While the particular microporous structure provides relatively more accessible sodium storage sites, a novel hybrid intercalation mechanism in ether-based electrolyte would incorporate the sodium ion insertion into the disordered structure with the solvated sodium ion species co-intercalation into the graphitic phase. In addition to the diffusion-controlled redox reactions, the noticeable surface-induced pseudocapacitive reactions also significantly contribute to the charge storage upon sodiation and guarantee the rapid migrations of sodium ions/solvated compounds. In conclusion, this system further features a controlled emergence of a robust but thin solid electrolyte interphase layer, which could suppress the side reactions of active electrode with reactive electrolyte, maintain the fragile porous structure upon cycling, and facilitate the migrations of sodium ions and solvated sodium ion compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lithiophilic 3D Porous CuZn Current Collector for Stable Lithium Metal Batteries

Lithium (Li) dendrites formed from nonuniform Li deposition limit potential uses of Li metal as an anode material. Here, we report a lithiophilic 3D porous CuZn current collector that mitigates dendrite formation and realizes the high stability of Li anodes. As opposed to the common metal current collector of copper (Cu), calculations and in situ experiments demonstrate that copper zinc (CuZn) alloys found in commercially available brass are lithiophilic and promote uniform Li deposition. Facile dealloying methods are applied to provide sufficient Li deposition and volume expansion space in brass sheets. Residual CuZn alloys in the framework are found to induce uniform Li deposition and stabilize Li dendrite growth. The optimal current collector (2h-3D CuZn) runs smoothly over 220 cycles at 0.5 mA cm –2 with improved Coulombic efficiencies at high current density. Lastly, this demonstrates an economic and facile CuZn preparation method that unlocks the full potential of Li anodes and provides new Li battery stabilization approaches.

25 ENERGY STORAGE↗

α-Fe2O3/SnO2 heterostructure composites: A high stability anode for lithium-ion battery

Highlights: • α-Fe{sub 2}O{sub 3}/SnO{sub 2} composites decorated with SnO{sub 2} nanocrystals were successfully synthesized. • The composites show high stability lithium storage performance as anode material. • The SnO{sub 2} layer serves as an inactive matrix for Fe{sub 2}O{sub 3} particles to avoid agglomeration and keep structural integrity. - Abstract: α-Fe{sub 2}O{sub 3} microoval structure decorated with SnO{sub 2} nanocrystals are fabricated by hydro-thermal process. The composite heterostructure has a uniform size of 310 nm in length and 110 nm in width, and SnO{sub 2} shell thickness is ∼10 nm. The SnO{sub 2} shell acts as a conductive layer to offer fast pathways for transport of electrons and ions. What is more, the SnO{sub 2} layer serves as an inactive matrix for α-Fe{sub 2}O{sub 3} particles, avoiding agglomeration and keeping structural integrity. Benefiting from the smart design, the hierarchical α-Fe{sub 2}O{sub 3}/SnO{sub 2} composite as anode exhibits a higher specific capacity and a better rate performance than those of pristine α-Fe{sub 2}O{sub 3} structures. The stability electrochemical performance of the hierarchical composite can be put down to the core-shell architecture, which improves the conductivity and stability of the electrodes. The heterostructure design in our work provides a possible approach to synthesis high stability materials for electrochemical energy storage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗