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At least 955 records · Page 53

NASICON Li 1.2 Mg 0.1 Zr 1.9 (PO 4 ) 3 Solid Electrolyte for an All‐Solid‐State Li‐Metal Battery

Abstract A thin solid electrolyte with a high Li + conductivity is used to separate the metallic lithium anode and the cathode in an all‐solid‐state Li‐metal battery. However, most solid Li‐ion electrolytes have a small electrochemical stability window, large interfacial resistance, and cannot block lithium‐dendrite growth when lithium is plated on charging of the cell. Mg 2+ stabilizes a rhombohedral NASICON‐structured solid electrolyte of the formula Li 1.2 Mg 0.1 Zr 1.9 (PO 4 ) 3 (LMZP). This solid electrolyte has Li‐ion conductivity two orders of magnitude higher at 25 °C than that of the triclinic LiZr 2 (PO 4 ) 3 . 7 Li and 6 Li NMR confirm the Li‐ions in two different crystallographic sites of the NASICON framework with 85% of the Li‐ions having a relatively higher mobility than the other 15%. The anode–electrolyte interface is further investigated with symmetric Li/LMZP/Li cell testing, while the cathode–electrolyte interface is explored with an all‐solid‐state Li/LMZP/LiFePO 4 cell. The enhanced performance of these cells enabled by the Li 1.2 Mg 0.1 Zr 1.9 (PO 4 ) 3 solid electrolyte is stable upon repeated charge/discharge cycling.

Zhou, Qiongyu↗

Topology optimization for the full-cell design of porous electrodes in electrochemical energy storage devices

In this paper, we introduce a density-based topology optimization framework to design porous electrodes for maximum energy storage. We simulate the full cell with a model that incorporates electronic potential, ionic potential, and electrolyte concentration. The system consists of three materials, namely pure liquid electrolyte and the porous solids of the anode and cathode, for which we determine the optimal placement. We use separate electronic potentials to model each electrode, which allows interdigitated designs. As a result, a penalization is required to ensure that the anode and cathode do not touch, i.e., causing a short circuit. We compare multiple 2D designs generated for different fixed conditions, e.g. material properties. A 3D design with complex channel and interlocked structure is also created. All optimized designs are far superior to the traditional monolithic electrode design with respect to energy storage metrics. We observe up to a 750% increase in energy storage for cases with slow effective ionic diffusion within the porous electrode.

25 ENERGY STORAGE↗

Multisublattice cluster expansion study of short-range ordering in iron-substituted strontium titanate

Owing to the challenges in obtaining realistic atomic configurations in large chemical phase spaces, it is not straightforward to describe structure–property relations in materials exhibiting configurational disorder. One example is iron-substituted strontium titanate (SrTi 1–x Fe x O 3–d , STF), a promising perovskite-derivative cathode material in solid oxide fuel cells that exhibits full solid solubility 0 ≤ x ≤ 1 and a tendency to exhibit short-range order. Here we demonstrate a multisublattice cluster expansion (CE) framework and apply it to STF across the full composition range. The CE approach is distinct from more traditional CE formulations in that clusters are defined explicitly by the chemical species distributed among multiple sublattices, rather than via cluster functions of occupation variables with decoration. The modified CE approach makes it easy to distinguish meaningful chemical interactions that are harder to extract from conventional CE, since for the latter chemical identity in a cluster is expressed as a product of site occupations. The least absolute shrinkage and selection operator (LASSO) is implemented as a regression analysis tool to select key clusters and avoid overfitting. We demonstrate this formulation on STF, and show that it can accurately predict configurational energies in comparison to conventional CE. From the key clusters, we identify that short-range ordering between substitutional Fe and oxygen vacancies (V O ) results in the formation of Fe–VO strings. In addition, we consider the stability of STF through CE-based Monte Carlo (MC) simulations and confirm the presence of superstructures that were previously observed in transmission electron microscopy. In this work, analysis of atomic configurations from MC samples reveals variations in the oxidation state of Fe atoms, which can be explained by the ordering tendency of Fe and V O . The cluster description and selection formalism described here may be applied to other disordered multisublattice systems for accurate and efficient material modeling.

36 MATERIALS SCIENCE↗

Hybrid bilayered vanadium oxide electrodes with large and tunable interlayer distances in lithium-ion batteries

The interlayer distances in layered electrode materials, influenced by the chemical composition of the confined interlayer regions, have a significant impact on their electrochemical performance. Chemical preintercalation of inorganic metal ions affects the interlayer spacing, yet expansion is limited by the hydrated ion radii. Herein, we demonstrate that using varying concentrations of decyltrimethylammonium (DTA + ) and cetyltrimethylammonium (CTA + ) cations in chemical preintercalation synthesis followed by hydrothermal treatment, the interlayer distance of hybrid bilayered vanadium oxides (BVOs) can be tuned between 11.1 Å and 35.6 Å. Our analyses reveal that these variations in interlayer spacing are due to different amounts of structural water and alkylammonium cations confined within the interlayer regions. Increased concentrations of alkylammonium cations not only expand the interlayer spacing but also induce local bending and disordering of the V-O bilayers. Electrochemical cycling of hybrid BVO electrodes in non-aqueous lithium-ion cells show that specific capacities decrease as interlayer regions expand, suggesting that the densely packed alkylammonium cations obstruct intercalation sites and hinder Li + ion transport. Furthermore, we found that greater layer separation facilitates the dissolution of active material into the electrolyte, resulting in rapid capacity decay during extended cycling. In conclusion, this study emphasizes that layered electrode materials require both spacious interlayer regions as well as high structural and chemical stabilities, providing guidelines for structural engineering of organic–inorganic hybrids.

25 ENERGY STORAGE↗

Enabling selective zinc-ion intercalation by a eutectic electrolyte for practical anodeless zinc batteries

Abstract Two major challenges hinder the advance of aqueous zinc metal batteries for sustainable stationary storage: (1) achieving predominant Zn-ion (de)intercalation at the oxide cathode by suppressing adventitious proton co-intercalation and dissolution, and (2) simultaneously overcoming Zn dendrite growth at the anode that triggers parasitic electrolyte reactions. Here, we reveal the competition between Zn 2+ vs proton intercalation chemistry of a typical oxide cathode using ex-situ/ operando techniques, and alleviate side reactions by developing a cost-effective and non-flammable hybrid eutectic electrolyte. A fully hydrated Zn 2+ solvation structure facilitates fast charge transfer at the solid/electrolyte interface, enabling dendrite-free Zn plating/stripping with a remarkably high average coulombic efficiency of 99.8% at commercially relevant areal capacities of 4 mAh cm −2 and function up to 1600 h at 8 mAh cm −2 . By concurrently stabilizing Zn redox at both electrodes, we achieve a new benchmark in Zn-ion battery performance of 4 mAh cm −2 anode-free cells that retain 85% capacity over 100 cycles at 25 °C. Using this eutectic-design electrolyte, Zn | |Iodine full cells are further realized with 86% capacity retention over 2500 cycles. The approach represents a new avenue for long-duration energy storage.

25 ENERGY STORAGE↗

Lattice engineering of high-entropy olivine-type lithium metal phosphate as high-voltage cathodes

Engineering of high-entropy cathode materials for lithium-ion batteries has been actively pursued owing to the outstanding conductivity of high-entropy materials benefited from the maximum entropy and unique antisite disordering structure. Olivine lithium metal phosphates such as LiMnPO 4 and LiNiPO 4 feature high working voltages but low capacities due to their insulation nature. Here in this work, the synthesis of the high-entropy lithium metal phosphate materials (HELMPs) is realized by combining mechanochemistry with a calcination method. By regulating lattice of HELMPs, the high-entropy Li(Mn 0.35 Fe 0.35 Co0.1Mg 0.1 Ca 0.1 )PO 4 reveals three typical high-voltage plateaus in charge–discharge curves corresponding to the redox of Fe, Mn, and Co in the voltage range of 2.0–4.9 V vs Li + /Li, and a much higher initial capacity than LiMnPO 4 (104 vs 15 mAh g -1 ).

25 ENERGY STORAGE↗

Fabrication of Advanced Nanocarbon-Metal Composites for Improved Energy Efficiency

We fabricated nanocarbon metal composites (NCMC) of Al alloys with a process called “electrocharging assisted process” (EAP). This method consists of the application of a high current to a mixture of liquid metal and carbon particles. We investigated aluminum alloys (6061 and 1350) and used activated carbon and graphite powder as the source of carbon. The high current induces the formation of carbon chains and ribbons in the liquid metal. Upon solidification of the metal an epitaxial relation between the carbon nanostructures and the metal lattice is produced. The purpose of the project was to find the parameters during the reaction that would give rise to a high density of nanoribbons extending throughout the metal such that the electrical conductivity and the mechanical strength of the composite increased and that the method could be extended to large scale manufacturing. For this purpose, we designed two reactors for the incorporation of nanocarbon ribbons in aluminum metal. The first reactor was designed to have more control of the region with the high current density. However, there were problems with getting good mixing of the carbon in small volumes. A second reactor was designed with a stirrer that allowed for better mixing of the carbon by the introduction of argon gas through the shaft of the stirrer. NCMC were fabricated with a series of parameters to understand the role of current, time of applied current, type and shape of the cathode electrode and stirring speed of the mixture. We analyzed the composites by Raman scattering to gain information on the crystallite size of the nanocarbon, XRD to obtain the crystal structure of the composite, SEM and TEM to characterize the grain size of the aluminum grains and the quality of the crystal structure. We also measured the electrical conductivity and mechanical properties of selected samples. The nanocomposites showed increase in crystallite size of the nanocarbon with a linear dependence of the crystallite size on the duration of the applied current. There is a minimum current density necessary for the crystallite size to increase compared to the ~ 10 nm size of the activated carbon source used in the fabrication. The electrical conductivity of the nanocomposites increased with crystallite size of the nanocarbon and with the concentration of converted carbon. The maximum increase in electrical conductivity was 5.7% above the baseline for samples with ~ 4 wt % nanocarbon with crystallite size larger than 30 nm. These samples presented a hardness ~ 8% higher than the baseline samples with no carbon.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Development of a high power 12GHz PPM focused traveling wave tube

An analytical and experimental program to demonstrate the technical feasibility of a high efficiency coupled cavity traveling wave tube with periodic permanent magnetic focusing operating at 12.06 GHz, with 1 to 2 kilowatts CW power is described. Such a tube would ultimately be used for broadcasting power transmission from a satellite. The electron gun was designed to be demountable with a replaceable cathode, and the tube to be operable in a bakeable vacuum chamber with its collector replaced by a collector. Therefore, the high efficiency design was concerned with the slow wave structure only, utilizing velocity resynchronization. A special adapter was designed which incorporated an electromagnet refocusing section and a collector baseplate to facilitate testing the collector. CW output power of 1000 watts yielding 21.5% electronic efficiency was demonstrated, with a minimum output power of 525 watts across the specified 160 MHz bandwidth.

Lewis, R.↗

Recognition of V3+/V4+/V5+ Multielectron Reactions in Na3V(PO4)2: A Potential High Energy Density Cathode for Sodium-Ion Batteries

Na3V(PO4)2 was reported recently as a novel cathode material with high theoretical energy density for Sodium-ion batteries (SIBs). However, whether V3+/V4+/V5+ multielectron reactions can be realized during the charging process is still an open question. In this work, Na3V(PO4)2 is synthesized by using a solid-state method. Its atomic composition and crystal structure are verified by X-ray diffraction (XRD) and neutron diffraction (ND) joint refinement. The electrochemical performance of Na3V(PO4)2 is evaluated in two different voltage windows, namely 2.5–3.8 and 2.5–4.3 V. 51V solid-state NMR (ssNMR) results disclose the presence of V5+ in Na2-xV(PO4)2 when charging Na3V(PO4)2 to 4.3 V, confirming Na3V(PO4)2 is a potential high energy density cathode through realization of V3+/V4+/V5+ multielectron reactions.

25 ENERGY STORAGE↗

In situ visualization of multicomponents coevolution in a battery pouch cell

Lithium-ion battery (LIB) is a broadly adopted technology for energy storage. With increasing demands to improve the rate capability, cyclability, energy density, safety, and cost efficiency, it is crucial to establish an in-depth understanding of the detailed structural evolution and cell-degradation mechanisms during battery operation. Here, we present a laboratory-based high-resolution and high-throughput X-ray micro–computed laminography approach, which is capable of in situ visualizing of an industry-relevant lithium-ion (Li-ion) pouch cell with superior detection fidelity, resolution, and reliability. This technique enables imaging of the pouch cell at a spatial resolution of 0.5 μm in a laboratory system and permits the identification of submicron features within cathode and anode electrodes. We also demonstrate direct visualization of the lithium plating in the imaged pouch cell, which is an important phenomenon relevant to battery fast charging and low-temperature cycling. Our development presents an avenue toward a thorough understanding of the correlation among multiscale structures, chemomechanical degradation, and electrochemical behavior of industry-scale battery pouch cells.

25 ENERGY STORAGE↗

A Multidimensional Operando Study Showing the Importance of the Electrode Macrostructure in Lithium Sulfur Batteries

Lithium sulfur batteries are one of the most promising next-generation energy storage technologies, because of their impressive theoretical energy density, low materials cost, and relative safety. However, incomplete understanding of their underlying operation mechanisms has hindered their further development and commercialization. In this work, to gain a better understanding of the operation mechanisms in the lithium sulfur battery, three macroscopically different (woven and nonwoven) and microscopically similar (made from the same carbon fibers) free-standing carbon felts are used as the conductive matrices to show how the macrostructure influences the redox reactions and the electrochemical performance. Additionally, an operando radiography and simultaneous in situ electrochemical impedance spectroscopy study are performed to highlight the differences of the carbon hosts and how they compare electrochemically in a lithium sulfur battery. The electrochemical results show that the carbon host with a more open structure results in increased capacity as well as a higher diffusion coefficient. The operando radiography shows that the open structures are more conducive to efficient redox reactivity in forming solid sulfur species, mostly in the form of elongated needlelike structures identified as β-S8, near the end of charge, which is corroborated by the impedance data. The data also reveal a “breathing” mechanism, where the polysulfides are pushed to the edges during discharge and pulled back during charge. Furthermore, it is also revealed that the “breathing” process is a limiting factor in the high rate performance. Overall, this study shows that there is a close relationship between the macrostructure of the carbon matrix and the electrochemical performance of the sulfur cathode.

25 ENERGY STORAGE↗

Template Assisted Lithium Superoxide Growth for Lithium-Oxygen Batteries

Developing batteries with energy densities comparable to internal combustion technology is essential for a worldwide transition to electrified transportation. Li-O2 batteries are seen as the ‘holy grail’ of battery technologies since they have the highest theoretical energy density of all battery technologies. Current lithium-oxygen (Li-O2) batteries suffer from large charge overpotentials related to electronic resistivity of the insulating lithium peroxide (Li2O2) discharge product. One potential solution is the formation and stabilization of a lithium superoxide (LiO2) discharge intermediate that exhibits good electronic conductivity. However, LiO2 is reported to be unstable at ambient temperature despite its favorable formation energy at -1.0 eV/atom. In this paper, based on our recent work on the development of cathode materials for aprotic lithium oxygen batteries including two intermetallic compounds, LiIr3 and LiIr, that are found to form good template interfaces with LiO2, a simple goodness of fit R factor to gauge how well a template surface structure can support LiO2 growth is developed. The R factor is a quantitative measurement to calculate the geometric difference in the unit cells of specific Miller Index 2D planes of the template surface and LiO2. Using this as a guide, the R factors for LiIr3, LiIr, and La2NiO4+, are found to be good. This guide is attested by simple extension to other noble metal intermetallics with electrochemical cycling data including LiRh3, LiRh, and Li2Pd. Finally, the template concept is extended to main group elements and the R factors for LiO2 (111) and Li2Ca suggest that Li2Ca is a possible candidate for the template assisted LiO2 growth strategy.

Intermetallics↗

Facet Impact of CuMn 2 O 4 Spinel Nanocatalysts on Enhancement of the Oxygen Reduction Reaction in Alkaline Media

Surface-structure engineering represents an attractive strategy to optimize the energy conversion performance of nanocatalysts using their deliberately controlled exposed facets. To further exploit the potential of non-PGM-based spinel catalysts for alkaline oxygen reduction reaction (ORR), a cathodic fuel cell reaction, we hereby report a strategy of ORR improvement by controlling the crystallographic facets of ultra-small CuMn 2 O 4 spinel nanocatalysts through a developed colloidal synthesis approach. The synthesis of CuMn 2 O 4 nanocrystals with morphological control relies on the design and selection of the Cu-/Mn-precursors with striking discrepancies in reaction kinetics. Following carbon loading and an annealing post-treatment of the as-synthesized nanocatalysts, the exclusively {101} facet-exposed CuMn 2 O 4 spinel nano-octahedra exhibit improved electrocatalytic activity toward ORR in 1 M KOH, when compared to their spherical counterparts, exhibiting a mass activity (MA) of 37.6 A/g at 0.85 V. After 10,000 cycles of ORR durability test, the nano-octahedra still retain an MA of 24.5 A/g, which is twice that of the CuMn 2 O 4 spinel nanospheres. Structural characterizations after durability testing indicate that the MA decay is likely associated with a decrease in the Mn 3+ fraction and the emergence of Cu + on CuMn 2 O 4 nano-octahedral surfaces. Finally, as a paradigm, this synthesis approach could be extended to other Mn-based spinel nanocatalysts with precise shape control, enabling us to understand and establish the relationship between the surface lattice/valence state and electrocatalytic properties.

36 MATERIALS SCIENCE↗

Intercalation of Mg into a Few-Layer Phyllomanganate in Non-aqueous Electrolytes at Room Temperature

The use of oxide cathodes in Mg batteries would unlock a potential energy storage system that delivers high-energy density. However, poor kinetics of Mg diffusion in known solid oxide lattices strongly limits reversible intercalation, which motivates the sustained exploration of new candidates. Herein, nanocrystals of a few-layer phyllomanganate, reminiscent of the mineral vernadite, were shown to have considerable electrochemical activity toward Mg intercalation at room temperature, where it delivered similar to 190 mAh g- 1 at similar to 1.9 V (vs Mg/Mg 2+ ) in batteries paired with a Mg metal anode. Multimodal characterization confirmed the notable degree of reversible intercalation by probing the structural, compositional, and redox changes undertaken by the oxide. Distinct levels of Mg activity were also observed while varying the content of small amounts of lattice water and the temperature of the reaction. The results reaffirm the prospects for operational Mg batteries using oxide cathode in moderate conditions, overcoming current limits of performance of this prospective technology.

25 ENERGY STORAGE↗

Neutron diffraction probing hydrogen in monoclinic H 2 VOPO 4

Light hydrogen atoms are resolvable with neutrons; however, the massive incoherent background inhibits the diffraction quality. To improve the signal, isotope treatment by deuteration becomes a prerequisite for a successful crystallographic understanding of hydrogen-containing materials by neutron diffraction. Thanks to the low-background and high-resolution time-of-flight neutron diffractometer, this work demonstrates a direct and successful measurement of high-quality neutron diffraction patterns of H 2 VOPO 4 powders, a precursor of a high-capacity alkali-ion battery cathode. The Rietveld refinement identifies the hydrogen coordinates, occupancy, and thermal parameters in the H 2 VOPO 4 lattice. Finally, the result highlights the unique capability of neutron diffraction for the structure characterization of hydrogen-containing materials, potentially without requiring costly and possibly artifact-inducing deuteration for neutron diffraction.

36 MATERIALS SCIENCE↗

Origin and regulation of oxygen redox instability in high-voltage battery cathodes

Oxygen redox at high-voltage has emerged as a transformative paradigm for high-energy battery cathodes such as layered transition-metal oxides by offering extra capacity beyond conventional transition-metal redox. However, these cathodes suffer from voltage hysteresis, voltage fade, and capacity drop upon cycling; single-crystalline cathodes have recently shown some improvements but these challenges still remain. We reveal the fundamental origin of oxygen redox instability to be originated from the domain boundaries that are present in single-crystalline cathode particles. By synthesizing single-crystalline cathodes free of domain boundaries, we show that the elimination of domain boundaries enhances the reversible lattice oxygen redox while inhibiting the irreversible oxygen release. Further, this leads to significantly suppressed structural degradation and improved mechanical integrity during battery cycling and abuse heating. The robust oxygen redox enabled through domain boundary control provides practical opportunities towards high-energy, long-cycling, and safe batteries.

25 ENERGY STORAGE↗

Preparation and evaluation of advanced electrocatalysts for phosphoric acid fuel cells

The highest performance fuel cell cathode electrocatalyst combination ever observed gives 755 mV vs hydrogen at 100 ASF on air at 180 C and shows a potential improvement to 775 mV vs hydrogen for better electrode structures. A pressurized fuel cell (UTC at 5 atm) would then give 805 mV at 320 ASF and 180 C. Another activity diagnostic is the performance of this electrocatalyst on oxygen at 900 mV vs hydrogen. The value for electrocatalyst is 44 mA per milligram of platinum and is projected to reach 60 mA per milligram of platinum with improved electrode structures. Since the electrocatalyst surface area and the electrode structure are not yet optimized there is considerable room for performance enhancement beyond these values, especially at higher temperatures.

Stonehart, P.↗

Z-Pinch Magneto-Inertial Fusion Propulsion Engine Design Concept

Fusion-based nuclear propulsion has the potential to enable fast interplanetary transportation. Due to the great distances between the planets of our solar system and the harmful radiation environment of interplanetary space, high specific impulse (Isp) propulsion in vehicles with high payload mass fractions must be developed to provide practical and safe vehicles for human spaceflight missions. Magneto-Inertial Fusion (MIF) is an approach which has been shown to potentially lead to a low cost, small fusion reactor/engine assembly (1). The Z-Pinch dense plasma focus method is an MIF concept in which a column of gas is compressed to thermonuclear conditions by an estimated axial current of approximately 100 MA. Recent advancements in experiments and the theoretical understanding of this concept suggest favorable scaling of fusion power output yield as I(sup 4) (2). The magnetic field resulting from the large current compresses the plasma to fusion conditions, and this is repeated over short timescales (10(exp -6) sec). This plasma formation is widely used in the field of Nuclear Weapons Effects (NWE) testing in the defense industry, as well as in fusion energy research. There is a wealth of literature characterizing Z-Pinch physics and existing models (3-5). In order to be useful in engineering analysis, a simplified Z-Pinch fusion thermodynamic model was developed to determine the quantity of plasma, plasma temperature, rate of expansion, energy production, etc. to calculate the parameters that characterize a propulsion system. The amount of nuclear fuel per pulse, mixture ratio of the D-T and nozzle liner propellant, and assumptions about the efficiency of the engine, enabled the sizing of the propulsion system and resulted in an estimate of the thrust and Isp of a Z-Pinch fusion propulsion system for the concept vehicle. MIF requires a magnetic nozzle to contain and direct the nuclear pulses, as well as a robust structure and radiation shielding. The structure, configuration, and materials of the nozzle must meet many severe requirements. The configuration would focus, in a conical manner, the Deuterium-Tritium (D-T) fuel and Lithium-6/7 liner fluid to meet at a specific point that acts as a cathode so the Li-6 can serve as a current return path to complete the circuit. In addition to serving as a current return path, the Li liner also serves as a radiation shield. The advantage to this configuration is the reaction between neutrons and Li-6 results in the production of additional Tritium, thus adding further fuel to the fusion reaction and boosting the energy output. To understand the applicability of Z-Pinch propulsion to interplanetary travel, it is necessary to design a concept vehicle that uses it. The propulsion system significantly impacts the design of the electrical, thermal control, avionics, radiation shielding, and structural subsystems of a vehicle. The design reference mission is the transport of crew and cargo to Mars and back, with the intention that the vehicle be reused for other missions. Several aspects of this vehicle are based on a previous crewed fusion vehicle study called Human Outer Planet Exploration (HOPE), which employed a Magnetized Target Fusion (MTF) propulsion concept. Analysis of this propulsion system concludes that a 40-fold increase of Isp over chemical propulsion is predicted. This along with a greater than 30% predicted payload mass fraction certainly warrants further development of enabling technologies. The vehicle is designed for multiple interplanetary missions and conceivably may be suited for an automated one-way interstellar voyage.

Miernik, Janie H.↗