Unlike the more established lithium-ion based energy storage chemistries, the complex intercalation chemistry of multivalent cations in a host lattice is not well understood, especially the relationship between the intercalating species solution chemistry and the prevalence and type of side reactions. Among multivalent metals, a promising model system can be based on nonaqueous Zn2+ ion chemistry. Several examples of these systems support the use of a Zn metal anode, and reversible intercalation cathodes have been reported. This study utilizes a combination of analytical tools to probe the chemistry of a nanostructured δ-MnO2 cathode in association with a nonaqueous acetonitrile–Zn(TFSI)2 electrolyte and a Zn metal anode. As many of the issues related to understanding a multivalent battery relate to the electrolyte–electrode interface, the high surface area of a nanostructured cathode provides a significant interface between the electrolyte and cathode host that maximizes the spectroscopic signal of any side reactions or minor mechanistic pathways. Numerous factors affecting capacity fade and issues associated with the second phase formation including Mn dissolution in heavily cycled Zn/δ-MnO2 cells are presented including dramatic mechanistic differences in the storage mechanism of this couple when compared to similar aqueous electrolytes are noted.
host lattice, [5,6] and recently proposed under-coordinated Mo metal atoms at the surface that assist as a catalyst in desolvation of the Mg 2+ in electrolyte solution. [7] In order to improve multivalent ion intercalation in oxides (intrinsically higher voltage materials with respect to sulfides), strategies including nanosizing and incorporation of water or solvent molecules into host crystalline structures have been reported to be successful. [8][9][10] The water/solvent mole cules facilitate the reaction, perhaps by coordinating (stabilizing) the Mg site location within the structure by effective charge screening. Within this context, we have recently synthesized a nanostructured bilayered hydrated V 2 O 5 (hereafter denoted as BL-V 2 O 5 ) host material with stabilizing bonded water molecules, [11] and reported the Mg 2+ intercalation followed by the demonstration of a Sn-C composite/BL-Mg x V 2 O 5 cell. [12] The ultimate goal of a rechargeable multivalent ion battery is, however, to utilize a metal anode in order to maximize the energy density of the battery, while the development of compatible multivalent ion electrolytes with a metal anode is a significant challenge. [13] the compatibility issues (e.g., a high overpotential, low Coulombic efficiency, and corrosion) of electrodes and electrolytes impedes the pairing of Mg or Ca metal anode with BL-V 2 O 5 cathode. On the other hand, the recent exploration of nonaqueous Zn ion electrolytes, which can reversibly electrodeposit on a Zn metal anode and provide wide electrochemical window (up to ≈3.8 V vs Zn 2+ /Zn), has opened a new door to build a multivalent rechargeable battery with high voltage cathode material. [13] Traditionally, nonaqueous Zn battery chemistry has been overlooked owing to its high reduction potential (−0.76 V vs NHE and 2.3 V vs Li + /Li), and lower theoretical energy densities. However, practically speaking, it warrants evaluation and battery testing since the metal possesses high volumetric energy density (Zn = 5851 mA h mL −1 , Mg = 3833 mA h mL −1 , and Li = 2073 mA h mL −1 ), and thus increases the overall full cell energy density. In addition, from a crystal chemistry point of view, Zn 2+ has a similar ionic radius and charge with respect to Mg 2+ , so it could be used as a surrogate species for pinning down multivalent rules for intercalation reactions. [14] Whilst earlier studies showed the possibility of Zn 2+ ion intercalation into manganese oxide cathodes from aqueous, molten, and polymer electrolytes, the performance of corresponding Zn ion cells were limited due to structural changes of the host material upon cycling. [15][16][17][18][19][20][21][22][23] Notable energy densities within the range of 228 to 241 Wh kg −1 for aqueous rechargeable Zn batteries including Zn/NiO [22] and Zn/Co 3 O 4 , [23] respectively, have been previously reported in the literature. Along this line, herein Expanding electrified transportation, and developing new largesize grid energy storage will require battery technologies that are scalable w...
We report on molecular classes in PWS using advanced genomic technology in the largest cohort to date. LOH patterns in UPD15 may impact the risk of having a second genetic condition if the mother carries a recessive mutant allele in the isodisomic region on chromosome 15. The risk of UPD15 may also increase with maternal age.
While α-V2O5 has traditionally been considered as a promising oxide to reversibly intercalate high levels of Mg2+ at high potential, recent reports indicate that previously observed electrochemical activity is dominated by intercalation of H+ rather than Mg2+, even in moderately dry nonaqueous electrolytes. Consequently, the inherent functionality of oxides to intercalate Mg2+ remains in question. By conducting electrochemistry in a chemically and anodically stable ionic liquid electrolyte, we report that, at 110 °C, layered α-V2O5 is indeed capable of reversibly intercalating 1 mol Mg2+ per unit formula, to accumulate capacities above 280 mAh g–1. Multimodal characterization confirmed intercalation of Mg2+ by probing the elemental, redox, and morphological changes undergone by the oxide. After cycling at 110 °C, the electrochemical activity at room temperature was significantly enhanced. The results renew prospects for functional Mg rechargeable batteries surpassing the levels of energy density of current Li-ion batteries.
Active avoidance (AA) is an important paradigm for studying mechanisms of aversive instrumental learning, pathological anxiety, and active coping. Unfortunately, AA neurocircuits are poorly understood, partly because behavior is highly variable and reflects a competition between Pavlovian reactions and instrumental actions. Here we exploited the behavioral differences between good and poor avoiders to elucidate the AA neurocircuit. Rats received Sidman AA training and expression of the activity-dependent immediate-early gene c-fos was measured after a shock-free AA test. Six brain regions with known or putative roles in AA were evaluated: amygdala, periaqueductal gray, nucleus accumbens, dorsal striatum, prefrontal cortex (PFC), and hippocampus. Good avoiders showed little Pavlovian freezing and high AA rates at test, the opposite of poor avoiders. Although c-Fos activation was observed throughout the brain, differential activation was found only in subregions of amygdala and PFC. Interestingly, c-Fos correlated with avoidance and freezing in only five of 20 distinct areas evaluated: lateral amygdala, central amygdala, medial amygdala, basal amygdala, and infralimbic PFC. Thus, activity in specific amygdala -PFC circuits likely mediates the competition between instrumental actions and Pavlovian reactions after AA training. Individual differences in AA behavior, long considered a nuisance by researchers, may be the key to elucidating the AA neurocircuit and understanding pathological response profiles.
An investigation of the electrochemical and structural properties of layered P2–Na0.62Mn0.75Ni0.25O2 is presented. The effect of changing the Mn/Ni ratio (3:1) from what is found in Na0.67Mn0.67Ni0.33O2 (2:1) and consequently the introduction of a third metal center (Mn3+) was investigated. X-ray powder diffraction (in situ and ex situ) revealed the lack of Na+-ion/vacancy ordering at the relevant sodium contents (x = 0.33, 0.5, and 0.67). Mn3+ in Na0.62Mn0.75Ni0.25O2 introduces defects into the Ni–Mn interplane charge order that in turn disrupts the ordering within the Na-plane. The material underwent P2–O2 and P2–P2′ phase transitions at high (4.2 V) and low (∼1.85 V) voltages, respectively. The material was tested at several different voltage ranges to understand the effect of the phase transitions on the capacity retention. Interestingly, the inclusion of both phase transitions demonstrated comparable cycling performance to when both phase transitions were excluded. Last, excellent rate performance was demonstrated between 4.3 and 1.5 V with a specific capacity of 120 mA h/g delivered at 500 mA/g current density.
Stress has been shown to suppress immune function and increase susceptibility to inflammatory disease and psychiatric disease. CD4+CD25+ regulatory T (Treg) cells are prominent in immune regulation. This study was conducted to determine if anti-CD25 antibody (Ab) mediated depletion of Treg cells in mice susceptibility to stress-induced development of depression-like behaviors, as well as immunological and neurochemical activity. To accomplish this, an elevated plus-maze test (EPM), tail suspension test (TST), and forced swim test (FST) were used to examine depression-like behaviors upon chronic immobilization stress. Immune imbalance status was observed based on analysis of serum cytokines using a mouse cytometric bead array in conjunction with flow cytometry and changes in the levels of serotonin (5-HT) and dopamine (DA) in the brain were measured by high performance liquid chromatography (HPLC). The time spent in the open arms of the EPM decreased significantly and the immobility time in the FST increased significantly in the anti-CD25 Ab-treated group when compared with the non stressed wild-type group. In addition, interlukin-6 (IL-6), tumor necrosis factor-á (TNF-á), interlukin-2 (IL-2), interferon-gamma (IFN-γ), interlukin-4 (IL-4) and interlukin-17A (IL-17A) concentrations were significantly upregulated in the stressed anti-CD25 Ab-treated group when compared with the non stressed wild-type group. Furthermore, the non stressed anti-CD25 Ab-treated group displayed decreased 5-HT levels within the hippocampus when compared with the non stressed wild-type group. These results suggest that CD4+CD25+ Treg cell depletion modulated alterations in depressive behavior, cytokine and monoaminergic activity. Therefore, controlling CD4+CD25+ Treg cell function during stress may be a potent therapeutic strategy for the treatment of depression-like symptoms.
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