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At least 955 records · Page 53

Entrainment, Detrainment, and Dilution of Dry and Moist Atmospheric Thermals

Here this study examines the entrainment, detrainment, and dilution of dry and moist (cloud) atmospheric thermals in large-eddy simulations. In a neutrally stable environment (with respect to dry dynamics), moist thermals have an increase in radius R with thermal height z t (α ≡ dR/dz t ) about 4 times smaller compared to dry thermals when density stratification is considered and ~2.4 times smaller without density stratification (i.e., applying the Boussinesq approximation). An analytic expression relating α to several dimensionless parameters is derived from the thermal impulse–circulation relation to clarify the factors impacting α. This expression shows that the difference in buoyancy structure between moist and dry thermals, with buoyancy concentrated in the central cores of moist thermals owing to latent heating, explains their smaller spreading rates. Individual contributions of entrainment and detrainment are analyzed using a direct parcel-based approach in the simulations. Moist thermals have similar fractional detrainment but much smaller fractional entrainment rates compared to dry thermals, consistent with the differences in α. Despite having smaller α, moist thermals are similarly dilute (quantified by a passive tracer) as dry thermals because of their greater mixing efficiency with the environment. Thus, moist thermals are substantially dilute but expand much less in size/volume as they rise compared to dry thermals. The α values for moist thermals in (dry) neutral and statically stable environments are similar, but fractional entrainment and especially detrainment rates are greater in the stable environment. Large detrainment rates are associated with a breakdown of the broader thermal vortex ring structure, especially with low environmental relative humidity, attributed in part to evaporation and buoyancy reversal.

54 ENVIRONMENTAL SCIENCES↗

Sodium azide mutagenesis induces a unique pattern of mutations

The nature and effect of mutations are of fundamental importance to the evolutionary process. The generation of mutations with mutagens has also played important roles in genetics. Applications of mutagens include dissecting the genetic basis of trait variation, inducing desirable traits in crops, and understanding the nature of genetic load. Previous studies of sodium azide-induced mutations have reported single nucleotide variants (SNVs) found in individual genes. To characterize the nature of mutations induced by sodium azide, we analyze whole-genome sequencing (WGS) of 11 barley lines derived from sodium azide mutagenesis, where all lines were selected for diminution of plant fitness owing to induced mutations. We contrast observed mutagen-induced variants with those found in standing variation in WGS of 13 barley landraces. Here, we report indels that are two orders of magnitude more abundant than expected based on nominal mutation rates. We found induced SNVs are very specific, with C → T changes occurring in a context followed by another C on the same strand (or the reverse complement). The codons most affected by the mutagen include the sodium azide-specific CC motif (or the reverse complement), resulting in a handful of amino acid changes and few stop codons. The specific nature of induced mutations suggests that mutagens could be chosen based on experimental goals. Sodium azide would not be ideal for gene knockouts but will create many missense mutations with more subtle effects on protein function.

Genetics & Heredity↗

Reversible Ionic Liquids as Double-Action Solvents for Efficient CO 2 Capture

We have developed a novel class of CO 2 capture solvents, Reversible Ionic Liquids (RevILs), that offer high absorption capacity through two modes of capture: chemical reaction (chemisorption) and physical solubility (physisorption). These solvents are silicon containing alkaline compounds such as silylamines that form a liquid salt (ionic liquid) upon reaction with CO 2 . Subsequently, modest elevations in temperature reverse the reaction and yield pure CO 2 for sequestration. By incorporating Si in the molecules we have reduced the viscosity, thereby improving the mass transfer rates of CO 2 absorption/desorption and decreasing the processing costs for pumping the solvent. In this project, we have made systematic changes to the structure of these compounds to improve several physical and thermodynamic properties important for CO 2 capture. Through these structure-property paradigms, we have obtained a RevIL which requires only a third of the energy required by conventional aqueous MEA process for 90% CO 2 capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reversible Ionic Liquids as Double-Action Solvents for Efficient CO2 Capture

We have developed a novel class of CO 2 capture solvents, Reversible Ionic Liquids (RevILs), that offer high absorption capacity through two modes of capture: chemical reaction (chemisorption) and physical solubility (physisorption). These solvents are silicon containing alkaline compounds such as silylamines that form a liquid salt (ionic liquid) upon reaction with CO 2 . Subsequently, modest elevations in temperature reverse the reaction and yield pure CO 2 for sequestration. By incorporating Si in the molecules we have reduced the viscosity, thereby improving the mass transfer rates of CO 2 absorption/desorption and decreasing the processing costs for pumping the solvent. In this project, we have made systematic changes to the structure of these compounds to improve several physical and thermodynamic properties important for CO 2 capture. Through these structure-property paradigms, we have obtained a RevIL which requires only a third of the energy required by conventional aqueous MEA process for 90% CO 2 capture.

20 FOSSIL-FUELED POWER PLANTS↗

Microchannel spatial light modulator

The Microchannel Spatial Light Modulator (MSLM), a versatile, highly sensitive, and optically addressed device being developed for real time optical information processing is discussed. The MSLM operates by converting an input optical image into a charge distribution at the surface of an electro-optic crystal. The charge distribution generates an electric field which modulates the refractive index of the crystal and thereby the phase or intensity of an image readout beam. Prototype devices employing 250 micron thick crystals exhibited a spatial resolution of 5 cycles/mm at 50% contrast, an exposure sensitivity of 2.2 nJ/cu cm and framing rates of 40 Hz with full modulation depth. The image processing operations that have been achieved using the internal processing mode of the MSLM include contrast reversal, contrast enhancement, edge enhancement, image addition and subtraction, analog and digital intensity thresholding, and binary level logic operations such as AND, OR, EXCLUSIVE OR, and NOR.

Warde, C.↗

An Encounter with the Ion and Electron Diffusion Regions at a Flapping and Twisted Tail Current Sheet

We analyze data returned by the Magnetospheric Multiscale mission (MMS) constellation during a rapid (~1.5 s) traversal of a flapping and reconnecting current sheet (CS) in the near-Earth magnetotail (X ~ -20 RE). The CS was highly tilted, with its normal pointing strongly duskward. Its extreme thinness was confirmed by a curvature analysis of the magnetic field lines. The event was associated with a guide field of 8% of the reconnecting components. From the pitch angle distributions of low-energy electrons we infer that the crossing occurred earthward of the X-line. Traveling practically normal to the CS, MMS encountered an ion diffusion region (IDR) in which was embedded an electron diffusion region (EDR). IDR signatures included breaking of the ion frozen-in condition in the presence of Hall B and E fields. EDR signatures included a strong out of-plane current associated with a super-Alfvenic electron jet, evidence of positive energy transfer, and a temperature anisotropy (TeII > Te1) which disappeared at the field reversal. Derived scale sizes normal to the CS are: ~6.9 de (EDR) and ~0.4 di (IDR) (40 and 100 km). We estimate the average dimensionless reconnection rate as 0.077 + 0.050. The observations and inferences are supported by PIC numerical simulations. We find very good agreement in the reconnection rates. We also discuss the effects of asymmetries in the density, temperature and magnetic field strength on the Hall fields and length of the outflow jets. The event is associated with a substorm onset which began 7 min after the MMS observations.

C J Farrugia↗

Alfven eigenmode stability and fast ion loss in DIII-D and ITER reversed magnetic shear plasmas

Neutral beam injection into reversed-magnetic shear DIII-D plasmas produces a variety of Alfvenic activity including toroidicity-induced Alfven eigenmodes (TAEs) and reversed shear Alfven eigenmodes (RSAEs). With measured equilibrium profiles as inputs, the ideal MHD code NOVA is used to calculate eigenmodes of these plasmas. The postprocessor code NOVA-K is then used to perturbatively calculate the actual stability of the modes, including finite orbit width and finite Larmor radius effects, and reasonable agreement with the spectrum of observed modes is found. Using experimentally measured mode amplitudes, fast ion orbit following simulations have been carried out in the presence of the NOVA calculated eigenmodes and are found to reproduce the dominant energy, pitch and temporal evolution of the losses measured using a large bandwidth scintillator diagnostic. The same analysis techniques applied to a DT 8 MA ITER steady-state plasma scenario with reversed-magnetic shear and both beam ion and alpha populations show Alfven eigenmode instability. Both RSAEs and TAEs are found to be unstable with maximum growth rates occurring for toroidal mode number n = 6 and the majority of the drive coming from fast ions injected by the 1MeV negative ion beams. AE instability due to beam ion drive is confirmed by the non-perturbative code TAEFL. Initial fast ion orbit following simulations using the unstable modes with a range of amplitudes (delta B/B = 10(-5)-10(-3)) have been carried out and show negligible fast ion loss. The lack of fast ion loss is a result of loss boundaries being limited to large radii and significantly removed from the actual modes themselves.

Van Zeeland, Michael↗

High-rate and long-life lithium-ion battery performance of hierarchically hollow-structured NiCo 2 O 4 /CNT nanocomposite

In this paper, 3D-transition binary metal oxides have been considered as promising anode materials for lithium-ion batteries with improved reversible capacity, structural stability and electronic conductivity compared with single metal oxides. Here, carbon nanotube supported NiCo 2 O 4 nanoparticles (NiCo 2 O 4 /CNT) with 3D hierarchical hollow structure are fabricated via a simple one-pot method. The NiCo 2 O 4 nanoparticles with interconnected pores are consists of small nanocrystals. When used as anode material for the lithium-ion battery, NiCo 2 O 4 /CNT exhibits enhanced electrochemical performance than that of Co 3 O 4 /CNT and NiO/CNT. Moreover, ultra-high discharge/charge stability was obtained for 4000 cycles at a current density of 5 A g –1 . The superior battery performance of NiCo 2 O 4 nanoparticles is probably attributed to the special structural features and physical characteristics, including integrity, hollow structure with interconnected pores, which providing sufficient accommodation for the volume change during charge/discharge process. Besides, the consisting of ultra-small crystals enhanced the utility of active material, and intimate interaction with CNTs improved the electron-transfer rate.

36 MATERIALS SCIENCE↗

Co-sputtering of lithium vanadium oxide thin films with variable lithium content to enable advanced solid-state batteries

Advanced solid-state batteries most likely will entail aggressive structures or architectures with constraints that typically limit processing temperatures. Considering this, we have identified the importance of providing lithiated electrode materials at a modest processing temperature. Here we describe a pathway to meet this by the development of a co-sputtering process using lithium oxide and vanadium oxide targets which enables the growth of lithiated vanadium oxide (LVO) thin films for application in solid-state batteries. Analysis of the structure and film composition of samples deposited with different co-sputtering rate ratios and post-annealing shows that multiple phases of Li x V 2 O 5 likely coexist (i.e. α-, ε-, δ-, and γ-V 2 O 5 ), and that this is unchanged after electrochemical cycling. The co-sputtering process can tune the lithium content up to a highly lithiated state of at least Li 2 V 2 O 5 . Electrochemical half-cells showed a significant amount of lithium available on the first charge (delithiation of LVO). LVO samples post-annealed at 300 °C showed typical redox peaks for Li x V 2 O 5 for both one and two lithium insertion reactions, which were highly reversible in most cases. A thin-film solid-state battery prototype using LVO as a cathode had 20% of the expected capacity, although the coulombic efficiency is near 100% at a fast rate (22C). As a result, this co-sputtering technique represents an opportunity for low temperature synthesis of pre-lithiated cathodes for thin film batteries, and introduces a broader methodology of depositing metal oxides with different alkali metal contents.

25 ENERGY STORAGE↗

Electrolyte and Cutoff Potential Effects on Cycle Life of Li4Ti5O12/LiNi0.9Mn0.1O2 Batteries for Behind-the-Meter Storage Applications

Behind-the-Meter Storage (BTMS) is a stationary battery energy storage system that is connected to the electrical distribution system on the customer's side of the utility's service meter. BTMS systems are used to store electrical energy from the grid as well as inconstant, renewable energy, such as local solar and wind generation. A successful BTMS system will allow the customer to pair their energy generation and storage to optimize electrical consumption from the grid, improving reliability and minimizing cost. For BTMS applications, batteries must be designed and optimized with different set of criteria from other leading segments of the Li-ion battery market, like transportation, due the system being stationary and proximal to the residential or commercial building it's benefitting. BTMS applications prioritize safety, cost (low/no-critical materials), reliability (20-year calendar life), and durability (10,000 cycle life), while having the ability to (minimally) compromise energy density and rate capability. Lithium titanate (Li4Ti5O12-, LTO) is a promising anode candidate for BTMS applications due to its high safety and capacity retention, while maintaining a reasonable 160 mAhg-1 reversable capacity and composition of relatively abundant materials. (1) Specifically, LTO has a high working voltage which helps to prevent Li dendrite formation, improving safety. Furthermore, LTO also has negligible lithiation-based volume change, leading to less mechanical pulverization, or loss of active material, upon cycling. For the cathode, materials with little or no Co are of high interest due to the high cost and low abundance of Co. LiMn2O4 (LMO) has been paired with LTO for BTMS applications in the past due to its safety, low cost (abundancy), and reasonably high operating voltage. (2-4) However, the low capacity of LMO limits energy density and specific energy. While not the highest priority for BTMS applications, increasing energy density will enable deployment in space constrained BTMS applications and decrease total cost. LiNi0.9Mn0.1O2 (LN-MO) is a recently developed material with promise due to its high operating voltage and relatively low price. (5) However, Ni-rich layered oxides, including LNMO, tend to struggle with capacity retention during high-voltage cycling due to mechanical pulverization, irreversible phase transitions, and unstable solid-electrolyte interphase. The study presented here focuses on building an understanding of how electrolyte solvent and varied cutoff potentials will impact the cycle life of LTO/LN-MO cells. Specifically, a comparison is provided between ethylene carbonate (EC), ethyl methyl carbonate (EMC), fluoroethylene carbonate (FEC), and Gen2 electrolyte solvents with 1M Lithium hexafluorophosphate (LiPF6) salt, cycling to two upper termination potentials, 2.6V and 2.7V. Electrochemical testing and diagnostics (e.g., differential capacity analysis, area specific impedance, constant voltage hold, and rate capability) and post-mortem characterization will be used to understand the aging behavior and failure mechanisms of the 8 cell combinations (four electrolytes and two voltage cutoffs). Cells with FEC electrolyte showed a lower initial capacity compared to cells with Gen2, EMC, and EC cycling at both voltages; however, the cells with FEC showed consistent trends in capacity retention with 2.6V and 2.7V termination potentials, while the cells with the other electrolytes showed much higher rates of capacity loss when cycling to the higher voltage. These results indicate that FEC may play a role in improving durability of high-voltage, Ni-rich electrode systems for use in high-cycle applications, such as BTMS.

electrolyte↗

Electric field reversals resulting from voltage waveform tailoring in Ar/O 2 capacitively coupled plasmas sustained in asymmetric systems

The etching of nanometer scale high-aspect-ratio (HAR) features into dielectric materials in low pressure radio frequency excited plasmas is often accompanied by charge accumulation inside the features which can slow etching rates and produce distortions such as twisting. The intra feature charging is at least partially produced by differences in electron and ion energy and angular distributions (EADs). Positive ions, accelerated to high energies having narrow angular spreads by the sheath electric field, can penetrate deeply into HAR features. Electrons typically arrive at the wafer with nearly thermal and isotropic distributions and do not penetrate deeply into HAR features. These disparities lead to differential charging of the inside of the feature, which can lead to reductions in etch rate and feature distortion due to ion deflection. With in-creasing aspect ratio of features, charging challenges are expected to continue for the foreseeable future. In this work, the use of tailored voltage waveforms in geometrically asymmetric capacitively coupled plasmas sustained in Ar/O 2 at 40 mTorr was computationally investigated with the goal of shaping the EAD of electrons incident onto the substrate to address differential charging. The tailored waveform consisted of a sinusoidal wave and its higher harmonics with a fundamental frequency of 1 MHz. Further, we found that electric field reversals in the sheath and presheath can occur during the anodic portion of the cycle. The electric field reversal increases the energy and decreases the angular spread of electrons incident onto the substrate. The magnitude of the electric field reversal can be controlled by the phase angle of the even harmonics and the gas composition. Due to its electronegative nature, increasing mole fractions of O 2 impedes electron transport to the surface which further increases the electric field reversal.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Test of nuclear decay rate variation due to an antineutrino flux

Unexplained variations of the decay rate parameter for weak interaction decays such as β ± decay, electron capture, as well as strong interaction α decay have been reported. Because these variations have been presented by a number of groups, at various locations, using various types of detectors, different isotopes, and over extended periods of time, some researchers have interpreted the source of these variations as not from ambient environmental factors such as temperature, pressure, and humidity but via an unexplained fundamental interaction. The state of decay rate parameter variations experiments is reviewed, and the reported results are placed into a common comparable context by defining a phenomenological cross section. After that we make decay parameter measurements as a function of time at the level of 10 -5 in the presences of an antineutrino flux with an on-off cycle time of ≈ 30 days. This level of precision requires a detailed understanding of both systematic and statistical errors; otherwise, systematic errors in the measurement may mimic the decay events of fundamental interactions. The experiment searched for variation of the $^{54}_{25}$Mn, e - capture decay rate parameter and $^{137}_{55}$Cs, β - decay rate parameter both to a level of precision of 1 part in ≈10 5 by comparing the difference between the decay rate in the presence of an antineutrino flux ≈ 3 x 10 12 $\bar{ν}$ cm -2 s -1 and no flux measurements. The experiment was located 6.53 m from the reactor core of the High Flux Isotope Reactor at the Oak Ridge National Laboratory. Two weak interaction decays, one via electron capture and the other via β - decay, were selected because the final state and the time reverse state each contain a neutrino and antineutrino, covering arguments that the antineutrino flux may interact differently or not at all in one of the cases. The $\gamma$ spectra from both decays were collected and analyzed independently. The measured variation in the decay rate parameters are found to be δλ/λ =(0.034 ± 1.38) x10 -5 for $^{54}_{25}$Mn and δλ/λ =(0.67±1.56) x10 -5 for $^{137}_{55}$Cs. These results are consistent with no measurable decay rate parameter variation due to an antineutrino flux, yielding a 68% confidence level upper limit sensitivity for $^{54}_{25}$Mn δλ/λ ≤ 1.31 x 10 -5 or σ ≤ 1.29 x10 -25 cm 2 in cross section and for $^{137}_{55}$Cs δλ/λ ≤ 2.23 x 10 -5 or σ ≤ 5.69 x10 -27 cm 2 . The cross-section upper limit obtained in these null or no observable effect measurements are ≈ 10 4 times more sensitive than past experiments reporting positive results in 54 Mn and 137 Cs. . .

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Resilient NdFeB magnet recycling under the impacts of COVID-19 pandemic: Stochastic programming and Benders decomposition

Neodymium-iron-boron (NdFeB) magnets are the most powerful magnets per unit volume sold in the commercial market. Despite the increasing demand for clean energy applications such as electric vehicles and wind turbines, disruptive events including the COVID-19 pandemic have caused significant uncertainties in the supply and demand for NdFeB magnets. Therefore, this study aims to alleviate the risk of supply shortage for NdFeB magnets and the containing critical materials, rare-earth elements (REEs), through the development of a resilient reverse supply chain and logistics network design. We develop scenarios to model the unique impact of the COVID-19 pandemic on the proposed business, incorporating both disruption intensity and recovery rate. We formulate a chance-constrained two-stage stochastic programming model to maximize the profit while guaranteeing the network resiliency against disruption risks. To solve the problem in large-scale instances, we develop an efficient Benders decomposition algorithm that reduces the computational time by 98.5% on average compared to the default CPLEX algorithm. When applied to the United States, the model suggests the optimal facility locations, processing capacities, inventory levels, and material flows for NdFeB magnet recyclers that could meet 99.7% of the demand. To the best of our knowledge, this study is the first to incorporate the impacts of the COVID-19 pandemic to design a resilient NdFeB magnet recycling supply chain and logistics network, leveraging risk-averse stochastic programming.

42 ENGINEERING↗

Biological Mechanisms May Contribute to Soil Carbon Saturation Patterns: Modeling Archive

This Modeling Archive is in support of a TES-SFA publication “Biological Mechanisms May Contribute to Soil Carbon Saturation Patterns” (Craig et al., 2021). We ran and evaluated a multi-assumption soil organic carbon (SOC) model to investigate whether alternative assumptions regarding constraints on soil microbial biomass could lead to soil carbon saturation patterns. We developed this model in the Multi-Assumption Architecture and Testbed (MAAT, https://github.com/walkeranthonyp/MAAT, tag: v1.2.1_Craig2021; Walker et al. 2018). Using MAAT, we embedded three alternative hypotheses in a microbially explicit three-pool SOC model: 1) the efficiency of mineral-associated SOC formation decreases as mineral-associated SOC approaches a maximum value (“Mineral saturation”), 2) the microbial biomass turnover rate increases with increasing microbial biomass (“Density-dependent turnover”), and 3) community carbon use efficiency decreases as microbial biomass increases toward an upper limit (“Density-dependent growth”). We ran a factorial combination of these hypotheses resulting in eight models for three different classes of model (linear decay, Michaelis-Menten decay, or reverse Michaelis-Menten decay), resulting in 24 models, 12 of which are presented or discussed in the related publication. Models were parameterized using values from previous studies with similar models (Wang et al. 2013, Wieder et al. 2014, Li et al. 2014, Georgiou et al. 2017, Hassink and Whitmore 1997) and ran to an approximate steady state (200 years) at six (6) different C input rates corresponding to 0.5, 1, 2, 4, 7, and 10 times the default input value. Further model details are available in the related publication. This archive contains output from three MAAT simulations, and scripts to run these simulations and process and plot the data. Simulations are labeled “lin”, “MM_highKm”, and “RMM_highKm” reflecting factorial runs for linear, Michealis-Menten, and reverse Michaelis-Menten models, respectively. This archive contains: • 3 R scripts prepended with “init_MAAT_” to initialize runs (1 for each simulation), • 1 csv file containing years over which to run simulations (“met_year.csv”), • 1 bash script (.bs) to run MAAT, • 6 XML files that are output from MAAT describing a run (2 for each simulation), • 3 model output csv files prepended by “out_” (1 for each simulation), and • 1 analysis R script for reproducing figures 3 and 4 in Craig et al. 2021. See included user guide (Craig_2021_modeling_archive_20210315.pdf) for file organization details.

54 ENVIRONMENTAL SCIENCES↗

Protein Crystal Growth Under Forced Solution Flow: Experimental Setup and General Response of Lysozyme

We have experimentally studied the effects of solution flow on the growth kinetics of the protein lysozyme. To this end, we have expanded our interferometry setup by a novel crystallization cell and solution recirculation system. This combination permits monitoring of interface morphology and kinetics with a depth resolution of 200 A at bulk flow rates of up to 2000 micron/s. Particular attention was paid to the prevention of protein denaturation that is often associated with the pumping of protein solutions. We found that at bulk flow rates it less than 250 microns/s the average growth rate and step velocity, R(sub avg) and upsilon(sub avg) increase with increasing it. This can be quantitatively understood in terms of the enhanced, convective solute supply to the interface. With high-purity solutions, it u greater than 250 microns/s lead to growth deceleration, and, at low supersaturations sigma, to growth cessation. When solutions containing approx. 1% of other protein impurities were used, growth deceleration occurred at any u greater than 0 and cessation in the low sigma experiments was reached at about half the it causing cessation with pure solution. The flow-induced changes in R(sub avg) and upsilon(sub avg) including growth cessation, were reversible and reproducible, independent of the direction of the u-changes and solution purity. Hence, we attribute the deceleration to the convection-enhanced supply of impurities to the interface, which at higher flow rates overpowers the effects of enhanced interfacial solute concentration. Most importantly, we found that convective transport leads to a significant reduction in kinetics fluctuations, in agreement with our earlier expectations for the lysozyme system. This supports our hypothesis that these long-term fluctuations represent an intrinsic response feature of the coupled bulk transport-interfacial kinetics system in the mixed growth control regime.

Vekilov, P. G.↗

20-kV GaN Switch Technology Demonstrated in High-Efficiency Medium-Voltage Power Module

GaN holds significant potential as a material for vertical p-n diodes, enabling the realization of devices with reverse breakdown voltages of 5 kV or higher. Carbon serves as the primary compensating dopant in the growth process, incorporated into GaN during metalorganic chemical vapor deposition (MOCVD) growth. The level of carbon incorporation depends on several factors, including growth rate, ammonia flow, temperature, pressure, and trimethylgallium (TMGa) flow. Through guided empirical modeling, the carbon incorporation in GaN growth could be predicted using a single parameter based on the ratio of ammonia flow to the growth rate. This model accurately predicts carbon concentrations ranging from 1x10 17 to 5x10 14 cm -3 while maximizing growth rates. Other extrinsic dopants have either been reduced below the threshold of consideration or modeled using similar single-parameter relationships. By identifying the dominant extrinsic dopants and accounting for them, an intrinsic defect with a concentration of 2.2x10 15 cm -3 was identified. By combining these relationships, growth conditions for n-GaN were optimized, resulting in electron concentrations as low as 1x10 15 cm -3 . Leveraging these techniques, p-n diodes were grown, achieving a reverse breakdown voltage as high as 3.1 kV.

36 MATERIALS SCIENCE↗

Lithium Manganese Spinel Cathodes for Lithium-Ion Batteries

Spinel LiMn 2 O 4 , whose electrochemical activity was first reported by Professor John B. Goodenough’s group at Oxford in 1983, is an important cathode material for lithium-ion batteries, which attracts continuous academic and industrial interests. It is cheap and environmentally friendly, and has excellent rate performance with 3-dimensional (3D) Li + diffusion channels. However, it suffers from severe degradations, especially under extreme voltages and during high-temperature operations. In this review, the current understanding and future trends of the spinel cathode and its derivatives with cubic lattice symmetry (LiNi 0.5 Mn 1.5 O 4 that shows high-voltage stability, and Li-rich spinels that show reversible hybrid anion- and cation-redox activities) shall be discussed. Special attention is given to the degradation mechanisms, further development of spinel cathodes, and concepts of utilizing the cubic spinel structure to stabilize high-capacity layered cathodes and as robust framework for high-rate electrodes. Lastly, “Good spinel” surface phases like LiNi 0.5 Mn 1.5 O 4 are distinguished from “bad spinel” surface phases like Mn 3 O 4 .

25 ENERGY STORAGE↗