Aqueous Rechargeable Batteries for Green Energy Storage: The Zinc Ion Chemistry

Rechargeable battery is the leading energy storage option for renewable power sources such as solar, wind and tidal (Park, et al., 2019, Tarascon, 2010). Furthermore, everyone owns a device powered by a rechargeable battery. Most of these devices are powered by lithium ion batteries (LIBs) owing to their rechargeability and high-energy density (Shin, et al., 2019). However, the rechargeable battery will lose its ability to retain a charge over time, forcing the consumer to discard the battery or product, which ends up in landfills. Owing to the high chemical activity of Li and the toxicity and flammability of organic solvent-based electrolytes, LIBs cause alarming safety and environmental issues (Yang, et al., 2018). Although Na+/K+ batteries are possible alternatives, these technologies also utilize organic electrolytes. Hence, there is a huge motivation to explore a battery chemistry that is long lasting, environmentally friendly, and cost-efficient. Rechargeable batteries based on water-based electrolytes are a revolutionary alternative and hold a prominent place in the energy storage research community. Along with other advantages, water also has a higher ionic conductivity (1 S cm-1) than organic electrolytes (~10-2 – 10-3 S cm-1) which is ideal for high rate cycling of batteries (Fang, et al., 2018, Winter, et al., 2004).The development of rechargeable aqueous batteries is ongoing, and there are systems based on monovalent ions (e.g. K+) and multivalent ions (e.g. Al3+, Zn2+ and Mg2+) (Liu, et al., 2014, Zhang, et al., 2017). Multivalent systems are more desirable given that their multiple redox states promise high specific capacity and energy density. Among multivalent systems, the rechargeable zinc ion battery (ZIB) has a huge potential, owing to its large overpotential for hydrogen evolution reaction (HER) (Fang, et al., 2018, Xu, et al., 2012, Glatz, et al., 2020, Zeng, et al., 2019). Apart from that, Zn holds a number of advantages over others, namely: high Earth abundance (low cost), high theoretical capacity (820 mAh g-1), low redox potential (-0.762 V vs SHE) and nontoxicity (Blanc, et al., 2020). Clearly, the electrochemical stability of Zn in aqueous solutions enlightens an opportunity to develop a “green” rechargeable battery.The aqueous ZIB consists of three main components, the Zn anode, electrolyte (e.g. Zn salts, such as ZnSO4, ZnNO3 or Zn(CF3SO3) in water) (Zhang, et al., 2016) and the cathode material (layered transition metal oxides, metal sulphides, polyaniline compounds, Prussian blue analogues etc.) (Fang, et al., 2018). Most scientific contributions on ZIB are devoted to the development of high-capacity and stable cathode materials. Owing to the cost effectiveness, environmental friendliness, and high theoretical capacity, Mn and V-based layered oxides are popular as cathode materials (Xu, et al., 2012, Alfaruqi, et al., 2015, Zhang, et al., 2019, Wei, et al., 2019). However, due to the +2 charge of Zn, it can suffer severe electrostatic interactions with the layered host material resulting in sluggish charge transfer kinetics (Yang, et al., 2018). Incorporation of metal ions (Zn2+, Mg2+, Ca2+, Li+, Na+) or structural water molecules between layers can mitigate these interactions and improve structuralstability (Zeng, et al., 2019, Lewis, et al., 2022). Dissolution of cathode material in aqueous electrolytesis another issue, which is typically addressed by electrolyte optimization (Zhao, et al., 2019).When considering the anode, growth of Zn dendrites on the anode surface is a major bottleneckfor the expansion of ZIB (Zhao, et al., 2019), i.e. localized nucleation of Zn, further aggravated by thedeposition of new Zn at preformed crystals. These Zn dendrites lead to an internal short circuit of thebattery. Furthermore, as deposited highly active Zn surface can undergo side reactions (corrosion,HER), leading to by-products and low coulombic efficiency (Zhao, et al., 2018). There have been fourmain strategies to tackle these problems: (i) electrolyte optimization, (ii) Zn anode surfacemodification, (iii) 3D Zn host design, and (iv) electrochemical protocol development (Blanc, et al.,2020). Among these, the surface passivation of Zn anode with inorganic (ZnO, TiO2, CaCO3) (Kang,et al., 2018, Kim, et al., 2020, Zhao, et al., 2020, Xie, et al., 2020) and organic (polyamide, polyvinylbutyl) (Zhao, et al., 2019, Hao, et al., 2020) coatings is a promising new approach.Although there has been some progress, effective and practically viable approaches to retardZn dendrite growth are yet insufficient. The final fate of the electrodeposited Zn critically relies on theinitial nucleation pattern and nanoscale surface kinetics (Zhao, et al., 2019, White, et al., 2012).Researchers have recognized the importance of this and have analyzed the dendrite formation viatechniques such as ex-situ atomic force microscopy (AFM), scanning electron microscopy (SEM) andtransmission electron microscopy (TEM) (Song, et al., 2016), yet these “stop-and-go” methods restrictsthe study of dynamic processes in real-time. Operando techniques are necessary to observe theevolution of micro/nanostructure of Zn deposits as it happens, which would help to establish thedeposition kinetics and transfer dynamics at the Zn anode. Hence, advanced operando characterizationtools are expected to guide the development of safe, cost-effective, and environmentally friendlyaqueous batteries and supercapacitors for future grid scale energy storage

Scanning the Landscape of Flux Compactifications: Vacuum Structure and Soft Supersymmetry Breaking

We scan the landscape of flux compactifications for the Calabi-Yau manifold $\mathbb{P}^4_{[1,1,1,6,9]}$ with two K\" ahler moduli by varying the value of the flux superpotential $W_0$ over a large range of values. We do not include uplift terms. We find a rich phase structure of AdS and dS vacua. Starting with $W_0\sim 1$ we reproduce the exponentially large volume scenario, but as $W_0$ is reduced new classes of minima appear. One of them corresponds to the supersymmetric KKLT vacuum while the other is a new, deeper non-supersymmetric minimum. We study how the bare cosmological constant and the soft supersymmetry breaking parameters for matter on D7 branes depend on $W_0$, for these classes of minima. We discuss potential applications of our results.Comment: draft format remove

Kahler Moduli Inflation

We show that under general conditions there is at least one natural inflationary direction for the Kahler moduli of type IIB flux compactifications. This requires a Calabi-Yau which has h^{2,1}>h^{1,1}>2 and for which the structure of the scalar potential is as in the recently found exponentially large volume compactifications. We also need - although these conditions may be relaxed - at least one Kahler modulus whose only non-vanishing triple-intersection is with itself and which appears by itself in the non-perturbative superpotential. Slow-roll inflation then occurs without a fine tuning of parameters, evading the eta problem of F-term inflation. In order to obtain COBE-normalised density perturbations, the stabilised volume of the Calabi-Yau must be O(10^5-10^7) in string units, and the inflationary scale M_{infl} ~ 10^{13} GeV. We find a robust model independent prediction for the spectral index of 1 - 2/N_e = 0.960 - 0.967, depending on the number of efoldings.Comment: 17 pages, 1 figure; v2. references adde

Sensitization to gliadin induces moderate enteropathy and insulitis in nonobese diabetic-DQ8 mice

Celiac disease (CD) is frequently diagnosed in patients with type 1 diabetes (T1D), and T1D patients can exhibit Abs against tissue transglutaminase, the auto-antigen in CD. Thus, gliadin, the trigger in CD, has been suggested to have a role in T1D pathogenesis. The objective of this study was to investigate whether gliadin contributes to enteropathy and insulitis in NOD-DQ8 mice, an animal model that does not spontaneously develop T1D. Gliadin-sensitized NOD-DQ8 mice developed moderate enteropathy, intraepithelial lymphocytosis, and barrier dysfunction, but not insulitis. Administration of anti-CD25 mAbs before gliadin-sensitization induced partial depletion of CD25+Foxp3+ T cells and led to severe insulitis, but did not exacerbate mucosal dysfunction. CD4+T cells isolated from pancreatic lymph nodes of mice that developed insulitis showed increased proliferation and proinflammatory cytokines after incubation with gliadin but not with BSA. CD4+ T cells isolated from nonsensitized controls did not response to gliadin or BSA. In conclusion, gliadin sensitization induced moderate enteropathy in NOD-DQ8 mice. However, insulitis development required gliadin-sensitization and partial systemic depletion of CD25+Foxp3+ T cells. This humanized murine model provides a mechanistic link to explain how the mucosal intolerance to a dietary protein can lead to insulitis in the presence of partial regulatory T cell deficiency.Facultad de Ciencias Exacta

Astrophysical and Cosmological Implications of Large Volume String Compactifications

We study the spectrum, couplings and cosmological and astrophysical implications of the moduli fields for the class of Calabi-Yau IIB string compactifications for which moduli stabilisation leads to an exponentially large volume V ~ 10^{15} l_s^6 and an intermediate string scale m_s ~ 10^{11}GeV, with TeV-scale observable supersymmetry breaking. All K\"ahler moduli except for the overall volume are heavier than the susy breaking scale, with m ~ ln(M_P/m_{3/2}) m_{3/2} ~ (\ln(M_P/m_{3/2}))^2 m_{susy} ~ 500 TeV and, contrary to standard expectations, have matter couplings suppressed only by the string scale rather than the Planck scale. These decay to matter early in the history of the universe, with a reheat temperature T ~ 10^7 GeV, and are free from the cosmological moduli problem (CMP). The heavy moduli have a branching ratio to gravitino pairs of 10^{-30} and do not suffer from the gravitino overproduction problem. The overall volume modulus is a distinctive feature of these models and is an M_{planck}-coupled scalar of mass m ~ 1 MeV and subject to the CMP. A period of thermal inflation can help relax this problem. This field has a lifetime ~ 10^{24}s and can contribute to dark matter. It may be detected through its decays to 2\gamma or e^+e^-. If accessible the e^+e^- decay mode dominates, with Br(\chi \to 2 \gamma) suppressed by a factor (ln(M_P/m_{3/2}))^2. We consider the potential for detection of this field through different astrophysical sources and find that the observed gamma-ray background constrains \Omega_{\chi} <~ 10^{-4}. The decays of this field may generate the 511 keV emission line from the galactic centre observed by INTEGRAL/SPI.Comment: 31 pages, 2 figures; v2. refs adde

Large-Volume Flux Compactifications: Moduli Spectrum and D3/D7 Soft Supersymmetry Breaking

We present an explicit calculation of the spectrum of a general class of string models, corresponding to Calabi-Yau flux compactifications with h_{1,2}>h_{1,1}>1 with leading perturbative and non-perturbative corrections, in which all geometric moduli are stabilised as in hep-th/0502058. The volume is exponentially large, leading to a range of string scales from the Planck mass to the TeV scale, realising for the first time the large extra dimensions scenario in string theory. We provide a general analysis of the relevance of perturbative and non-perturbative effects and the regime of validity of the effective field theory. We compute the spectrum in the moduli sector finding a hierarchy of masses depending on inverse powers of the volume. We also compute soft supersymmetry breaking terms for particles living on D3 and D7 branes. We find a hierarchy of soft terms corresponding to `volume dominated' F-term supersymmetry breaking. F-terms for Kahler moduli dominate both those for dilaton and complex structure moduli and D-terms or other de Sitter lifting terms. This is the first class of string models in which soft supersymmetry breaking terms are computed after fixing all geometric moduli. We outline several possible applications of our results, both for cosmology and phenomenology and point out the differences with the less generic KKLT vacua.Comment: 64 pages, 4 figures; v2. references added; v3. typos, reference added, matches published versio

Towards Realistic String Vacua From Branes At Singularities

We report on progress towards constructing string models incorporating both realistic D-brane matter content and moduli stabilisation with dynamical low-scale supersymmetry breaking. The general framework is that of local D-brane models embedded into the LARGE volume approach to moduli stabilisation. We review quiver theories on del Pezzo $n$ ($dP_n$) singularities including both D3 and D7 branes. We provide supersymmetric examples with three quark/lepton families and the gauge symmetries of the Standard, Left-Right Symmetric, Pati-Salam and Trinification models, without unwanted chiral exotics. We describe how the singularity structure leads to family symmetries governing the Yukawa couplings which may give mass hierarchies among the different generations. We outline how these models can be embedded into compact Calabi-Yau compactifications with LARGE volume moduli stabilisation, and state the minimal conditions for this to be possible. We study the general structure of soft supersymmetry breaking. At the singularity all leading order contributions to the soft terms (both gravity- and anomaly-mediation) vanish. We enumerate subleading contributions and estimate their magnitude. We also describe model-independent physical implications of this scenario. These include the masses of anomalous and non-anomalous U(1)'s and the generic existence of a new hyperweak force under which leptons and/or quarks could be charged. We propose that such a gauge boson could be responsible for the ghost muon anomaly recently found at the Tevatron's CDF detector.Comment: 40 pages, 10 figure

A rare variant of the superficial ulnar artery, and its clinical implications: a case report

The superficial ulnar artery is a rare variation of the upper limb arterial system that arises from the brachial or axillary artery and runs superficial to the muscles arising from the medial epicondyle [1-3]. The incidence is about 0.7 to 7% [1,4,5]. In our routine dissections we found a superficial ulnar artery, which crossed the cubital fossa superficial to the bicipital aponeurosis making it highly vulnerable to intra-arterial injection. This is a rare variation that every medical and nursing staff member should know about

Genetic Analysis of Hematological Parameters in Incipient Lines of the Collaborative Cross

Hematological parameters, including red and white blood cell counts and hemoglobin concentration, are widely used clinical indicators of health and disease. These traits are tightly regulated in healthy individuals and are under genetic control. Mutations in key genes that affect hematological parameters have important phenotypic consequences, including multiple variants that affect susceptibility to malarial disease. However, most variation in hematological traits is continuous and is presumably influenced by multiple loci and variants with small phenotypic effects. We used a newly developed mouse resource population, the Collaborative Cross (CC), to identify genetic determinants of hematological parameters. We surveyed the eight founder strains of the CC and performed a mapping study using 131 incipient lines of the CC. Genome scans identified quantitative trait loci for several hematological parameters, including mean red cell volume (Chr 7 and Chr 14), white blood cell count (Chr 18), percent neutrophils/lymphocytes (Chr 11), and monocyte number (Chr 1). We used evolutionary principles and unique bioinformatics resources to reduce the size of candidate intervals and to view functional variation in the context of phylogeny. Many quantitative trait loci regions could be narrowed sufficiently to identify a small number of promising candidate genes. This approach not only expands our knowledge about hematological traits but also demonstrates the unique ability of the CC to elucidate the genetic architecture of complex traits

Second Chances: Subprime Mortgage Modification and Re-Default

Mortgage modifications have become an important component of public interventions designed to reduce foreclosures. In this paper, we examine how the structure of a mortgage modification affects the likelihood of the modified mortgage re-defaulting over the next year. Using data on subprime modifications that precede the government's Home Affordable Modification Program, we focus our attention on those modifications in which the borrower was seriously delinquent and the monthly payment was reduced as part of the modification. The data indicate that the re-default rate declines with the magnitude of the reduction in the monthly payment, but also that the re-default rate declines relatively more when the payment reduction is achieved through principal forgiveness as opposed to lower interest rates