Cathode active materials using rare metals recovered from waste lithium-ion batteries: A review.

Large-scale lithium-ion batteries (LIBs) are overtaking as power sources for electric vehicles and grid-scale energy-storage systems for renewable sources. Accordingly, large amounts of LIBs are expected to be discarded in the near future. Recycling technologies for waste LIBs, particularly for valuable rare metals (Li, Co, and Ni) used in cathode active materials, need to be developed to construct continuous LIB supply chains. Various recovery methodologies, such as pyrometallurgy, hydrometallurgy, and direct recycling, as well as their advantages, disadvantages, and technical features, are briefly introduced. We review the electrochemical performances of these cathode active materials based on recycled rare metals from LIB waste. Moreover, the physicochemical properties and electrochemical performance of the cathode active materials with impurities incorporated during recycling, which have high academic significance, are outlined. In hydrometallurgy-based LIB recycling, the complete removal of impurities in cathode active materials is not realistic for the mass and sustainable production of LIBs; thus, optimal control of the impurity levels is of significance. Meanwhile, the studies on the direct recycling of LIB showed the necessity of almost complete impurity removal and restoration of physicochemical properties in cathode active materials. This review provides a survey of the technological outlook of reusing cathode active materials from waste LIBs.

Development of Magnetocardiograph without Magnetically Shielded Room Using High-Detectivity TMR Sensors.

A magnetocardiograph that enables the clear observation of heart magnetic field mappings without magnetically shielded rooms at room temperatures has been successfully manufactured. Compared to widespread electrocardiographs, magnetocardiographs commonly have a higher spatial resolution, which is expected to lead to early diagnoses of ischemic heart disease and high diagnostic accuracy of ventricular arrhythmia, which involves the risk of sudden death. However, as the conventional superconducting quantum interference device (SQUID) magnetocardiographs require large magnetically shielded rooms and huge running costs to cool the SQUID sensors, magnetocardiography is still unfamiliar technology. Here, in order to achieve the heart field detectivity of 1.0 pT without magnetically shielded rooms and enough magnetocardiography accuracy, we aimed to improve the detectivity of tunneling magnetoresistance (TMR) sensors and to decrease the environmental and sensor noises with a mathematical algorithm. The magnetic detectivity of the TMR sensors was confirmed to be 14.1 pTrms on average in the frequency band between 0.2 and 100 Hz in uncooled states, thanks to the original multilayer structure and the innovative pattern of free layers. By constructing a sensor array using 288 TMR sensors and applying the mathematical magnetic shield technology of signal space separation (SSS), we confirmed that SSS reduces the environmental magnetic noise by -73 dB, which overtakes the general triple magnetically shielded rooms. Moreover, applying digital processing that combined the signal average of heart magnetic fields for one minute and the projection operation, we succeeded in reducing the sensor noise by about -23 dB. The heart magnetic field resolution measured on a subject in a laboratory in an office building was 0.99 pTrms and obtained magnetocardiograms and current arrow maps as clear as the SQUID magnetocardiograph does in the QRS and ST segments. Upon utilizing its superior spatial resolution, this magnetocardiograph has the potential to be an important tool for the early diagnosis of ischemic heart disease and the risk management of sudden death triggered by ventricular arrhythmia.

Role of SiOx in rice-husk-derived anodes for Li-ion batteries.

The present study investigated the role of SiOx in a rice-husk-derived C/SiOx anode on the rate and cycling performance of a Li-ion battery. C/SiOx active materials with different SiOx contents (45, 24, and 5 mass%) were prepared from rice husk by heat treatment and immersion in NaOH solution. The C and SiOx specific capacities were 375 and 475 mAh g-1, respectively. A stable anodic operation was achieved by pre-lithiating the C/SiOx anode. Full-cells consisting of this anode and a Li(Ni0.5Co0.2Mn0.3)O2 cathode displayed high initial Coulombic efficiency (~ 85%) and high discharge specific capacity, indicating the maximum performance of the cathode (~ 150 mAh g-1). At increased current density, the higher the SiOx content, the higher the specific capacity retention, suggesting that the time response of the reversible reaction of SiOx with Li ions is faster than that of the C component. The full-cell with the highest SiOx content exhibited the largest decrease in cell specific capacity during the cycle test. The structural decay caused by the volume expansion of SiOx during Li-ion uptake and release degraded the cycling performance. Based on its high production yield and electrochemical benefits, degree of cycling performance degradation, and disadvantages of its removal, SiOx is preferably retained for Li-ion battery anode applications.

Suitable binder for Li-ion battery anode produced from rice husk.

Rice husk (RH) is a globally abundant and sustainable bioresource composed of lignocellulose and inorganic components, the majority of which consist of silicon oxides (approximately 20% w/w in dried RH). In this work, a RH-derived C/SiOx composite (RHC) was prepared by carbonization at 1000 °C for use in Li-ion battery anodes. To find a suitable binder for RHC, the RHC-based electrodes were fabricated using two different contemporary aqueous binders: polyacrylic acid (PAA) and a combination of carboxymethyl cellulose and styrene butadiene rubber (CMC/SBR). The rate and cycling performances of the RHC electrodes with respect to the insertion/extraction of Li ions were evaluated in a half-cell configuration. The cell was shorted for 24 h to completely lithiate the RHC. Impedance analysis was conducted to identify the source of the increase in the resistance of the RHC electrodes. The RHC electrode fabricated using PAA exhibited higher specific capacity for Li-ion extraction during the cycling test. The PAA binder strengthened the electrode and alleviated the increase in electrode resistance caused by the formation of the interphase film. The high affinity of PAA for SiOx in RHC was responsible for the stabilization of the anodic performance of Li-ion batteries.

Allele frequency spectra in structured populations: Novel-allele probabilities under the labelled coalescent.

We address the effect of population structure on key properties of the Ewens sampling formula. We use our previously-introduced inductive method for determining exact allele frequency spectrum (AFS) probabilities under the infinite-allele model of mutation and population structure for samples of arbitrary size. Fundamental to the sampling distribution is the novel-allele probability, the probability that given the pattern of variation in the present sample, the next gene sampled belongs to an as-yet-unobserved allelic class. Unlike the case for panmictic populations, the novel-allele probability depends on the AFS of the present sample. We derive a recursion that directly provides the marginal novel-allele probability across AFSs, obviating the need first to determine the probability of each AFS. Our explorations suggest that the marginal novel-allele probability tends to be greater for initial samples comprising fewer alleles and for sampling configurations in which the next-observed gene derives from a deme different from that of the majority of the present sample. Comparison to the efficient importance sampling proposals developed by De Iorio and Griffiths and colleagues indicates that their approximation for the novel-allele probability generally agrees with the true marginal, although it may tend to overestimate the marginal in cases in which the novel-allele probability is high and migration rates are low.

Inductive determination of allele frequency spectrum probabilities in structured populations.

We present a method for inductively determining exact allele frequency spectrum (AFS) probabilities for samples derived from a population comprising two demes under the infinite-allele model of mutation. This method builds on a labeled coalescent argument to extend the Ewens sampling formula (ESF) to structured populations. A key departure from the panmictic case is that the AFS conditioned on the number of alleles in the sample is no longer independent of the scaled mutation rate (θ). In particular, biallelic site frequency spectra, widely-used in explorations of genome-wide patterns of variation, depend on the mutation rate in structured populations. Variation in the rate of substitution across loci and through time may contribute to apparent distortions of site frequency spectra exhibited by samples derived from structured populations.

A Bayesian Approach to Inferring Rates of Selfing and Locus-Specific Mutation.

We present a Bayesian method for characterizing the mating system of populations reproducing through a mixture of self-fertilization and random outcrossing. Our method uses patterns of genetic variation across the genome as a basis for inference about reproduction under pure hermaphroditism, gynodioecy, and a model developed to describe the self-fertilizing killifish Kryptolebias marmoratus. We extend the standard coalescence model to accommodate these mating systems, accounting explicitly for multilocus identity disequilibrium, inbreeding depression, and variation in fertility among mating types. We incorporate the Ewens sampling formula (ESF) under the infinite-alleles model of mutation to obtain a novel expression for the likelihood of mating system parameters. Our Markov chain Monte Carlo (MCMC) algorithm assigns locus-specific mutation rates, drawn from a common mutation rate distribution that is itself estimated from the data using a Dirichlet process prior model. Our sampler is designed to accommodate additional information, including observations pertaining to the sex ratio, the intensity of inbreeding depression, and other aspects of reproduction. It can provide joint posterior distributions for the population-wide proportion of uniparental individuals, locus-specific mutation rates, and the number of generations since the most recent outcrossing event for each sampled individual. Further, estimation of all basic parameters of a given model permits estimation of functions of those parameters, including the proportion of the gene pool contributed by each sex and relative effective numbers.

Genealogical histories in structured populations.

In genealogies of genes sampled from structured populations, lineages coalesce at rates dependent on the states of the lineages. For migration and coalescence events occurring on comparable time scales, for example, only lineages residing in the same deme of a geographically subdivided population can have descended from a common ancestor in the immediately preceding generation. Here, we explore aspects of genealogical structure in a population comprising two demes, between which migration may occur. We use generating functions to obtain exact densities and moments of coalescence time, number of mutations, total tree length, and age of the most recent common ancestor of the sample. We describe qualitative features of the distribution of gene genealogies, including factors that influence the geographical location of the most recent common ancestor and departures of the distribution of internode lengths from exponential.

Low-reflective wire-grid polarizers with absorptive interference overlayers.

Wire-grid (WG) polarizers with low reflectivity for visible light have been successfully developed. We theoretically consider the optical properties of simple sandwich structures of absorptive layer/transparent layer (gap layer)/high-reflective mirrors and found that it is possible to develop an antireflection (AR) coating owing to the interference along with the absorption in the absorptive layer. A wide variety of materials can be used for AR coatings by tuning the thicknesses of both the absorptive and the gap layers. This AR concept has been applied to reduce the reflectance of WG polarizers of Al. FeSi(2) as an absorptive layer has been deposited by the glancing angle deposition technique immediately on the top of Al wires covered with a thin SiO(2) layer as a gap layer. For the optimum combination of the thicknesses of FeSi(2) and SiO(2), the reflectance becomes lower than a few per cent, independent of the polarization, whereas the transmission polarization properties remain good. Because low-reflective (LR) WG polarizers are completely composed of inorganic materials, they are useful for applications requiring high-temperature durability such as liquid crystal projection displays.

Quantifying interactions within the NADP(H) enzyme network in Drosophila melanogaster.

In this report, we use synthetic, activity-variant alleles in Drosophila melanogaster to quantify interactions across the enzyme network that reduces nicotinamide adenine dinucleotide phosphate (NADP) to NADPH. We examine the effects of large-scale variation in isocitrate dehydrogenase (IDH) or glucose-6-phosphate dehydrogenase (G6PD) activity in a single genetic background and of smaller-scale variation in IDH, G6PD, and malic enzyme across 10 different genetic backgrounds. We find significant interactions among all three enzymes in adults; changes in the activity of any one source of a reduced cofactor generally result in changes in the other two, although the magnitude and directionality of change differs depending on the gene and the genetic background. Observed interactions are presumably through cellular mechanisms that maintain a homeostatic balance of NADPH/NADP, and the magnitude of change in response to modification of one source of reduced cofactor likely reflects the relative contribution of that enzyme to the cofactor pool. Our results suggest that malic enzyme makes the largest single contribution to the NADPH pool, consistent with the results from earlier experiments in larval D. melanogaster using naturally occurring alleles. The interactions between all three enzymes indicate functional interdependence and underscore the importance of examining enzymes as components of a network.

Carbon/silica composite fabricated from rice husk by means of binderless hot-pressing.

A carbon/silica composite designed for use under compressive loads was fabricated from rice husk (RH), an agricultural waste material. RH was pulverized by using a planetary ball mill, then carbonized and molded into the precursor by means of hot-pressing without using any binders. A compression of 100 MPa was intermittently applied to the RH powder heated from room temperature to 150 degrees C, and then to 280 degrees C. The precursor, the bulk density of which was 1.37 g/cm(3), was sintered for further densification at up to 1400 degrees C without compression, in nitrogen gas. The smaller particle size of the pulverized RH was beneficial for densifying the carbon/silica composite and increasing its compressive strength. Sintering at 800 degrees C for 1h in nitrogen gas provided the maximum bulk density of 1.52 g/cm(3) and the maximum Vickers hardness at the surface of 343 HV. The maximum compressive strength was measured to be 55.7 MPa using a sintering temperature of 1200 degrees C.

Direct evidence that genetic variation in glycerol-3-phosphate and malate dehydrogenase genes (Gpdh and Mdh1) affects adult ethanol tolerance in Drosophila melanogaster.

Many studies of alcohol adaptation in Drosophila melanogaster have focused on the Adh polymorphism, yet the metabolic elimination of alcohol should involve many enzymes and pathways. Here we evaluate the effects of glycerol-3-phosphate dehydrogenase (Gpdh) and cytosolic malate dehydrogenase (Mdh1) genotype activity on adult tolerance to ethanol. We have created a set of P-element-excision-derived Gpdh, Mdh1, and Adh alleles that generate a range of activity phenotypes from full to zero activity. Comparisons of paired Gpdh genotypes possessing 10 and 60% normal activity and 66 and 100% normal activity show significant effects where higher activity increases tolerance. Mdh1 null allele homozygotes show reductions in tolerance. We use piggyBac FLP-FRT site-specific recombination to create deletions and duplications of Gpdh. Duplications show an increase of 50% in activity and an increase of adult tolerance to ethanol exposure. These studies show that the molecular polymorphism associated with GPDH activity could be maintained in natural populations by selection related to adaptation to alcohols. Finally, we examine the interactions between activity genotypes for Gpdh, Mdh1, and Adh. We find no significant interlocus interactions. Observations on Mdh1 in both Gpdh and Adh backgrounds demonstrate significant increases in ethanol tolerance with partial reductions (50%) in cytosolic MDH activity. This observation strongly suggests the operation of pyruvate-malate and, in particular, pyruvate-citrate cycling in adaptation to alcohol exposure. We propose that an understanding of the evolution of tolerance to alcohols will require a system-level approach, rather than a focus on single enzymes.

Oil adsorbent produced by the carbonization of rice husks.

In this study, rice husks considered to be agricultural waste are converted into an adsorbent intended for use in the disposal of oil spills. The raw and refined (defiberized) husks of Japanese Akita Komachi rice were pyrolyzed in a vacuum (500 Pa) at 300-800 degrees C. The amount of A-heavy and B-heavy oils adsorbed on the carbonized rice husk were then evaluated. Oil adsorption is dependent on the type of oil. Rice husks refined and then pyrolyzed at 600-700 degrees C (1.0 g) adsorbed >6.0 g of B-heavy oil and <1.5 g of water, which indicates their usefulness as an adsorbent for oil spill cleanup in Japan. The refining process contributes to an improvement in the oil adsorption capacity, while the carbonization time (at 600 degrees C) has only a minor influence. The residual fluid components in the carbonized rice husks, rather than their porosity, are closely related to oil adsorption capacity.

Flux control and excess capacity in the enzymes of glycolysis and their relationship to flight metabolism in Drosophila melanogaster.

An important question in evolutionary and physiological genetics is how the control of flux-base phenotypes is distributed across the enzymes in a pathway. This control is often related to enzyme-specific levels of activity that are reported to be in excess of that required for demand. In glycolysis, metabolic control is frequently considered vested in classical regulatory enzymes, each strongly displaced from equilibrium. Yet the contribution of individual steps to control is unclear. To assess enzyme-specific control in the glycolytic pathway, we used P-element excision-derived mutagenesis in Drosophila melanogaster to generate full and partial knockouts of seven metabolic genes and to measure tethered flight performance. For most enzymes, we find that reduction to half of the normal activity has no measurable impact on wing beat frequency. The enzymes catalyzing near-equilibrium reactions, phosphoglucose isomerase, phosphoglucomutase, and triosephosphate isomerase fail to show any decline in flight performance even when activity levels are reduced to 17% or less. At reduced activities, the classic regulatory enzymes, hexokinase and glycogen phosphorylase, show significant drops in flight performance and are nearer to saturation. Our results show that flight performance is canalized or robust to the activity variation found in natural populations. Furthermore, enzymes catalyzing near-equilibrium reactions show strong genetic dominance down to low levels of activity. This implies considerable excess enzyme capacity for these enzymes.