Rational Design Toward Advanced Non-Flow Aqueous Zinc-Bromine Systems Boosted by Alkaline-Neutral Decoupling Electrolytes.

Non-flow aqueous zinc-bromine batteries (AZBBs) are highly attractive owing to their lightweight construction and largely reduced cost compared with the flow ones. Yet, their development is restricted by the sluggish reaction kinetics of Br2/Br-, the shuttle of soluble polybromide species (Brn -, n is odd), and the poor stability of Zn-based anode. Herein, an effective alkaline-neutral electrolyte decoupling system is constructed to mitigate these issues, where nitrogen-doped carbon felt with high catalytic activity to Br2/Br- reaction is developed for cathode, a cost-effective cation exchange membrane (CEM) of polyethersulfone/sulfonated polyether ether ketone (PES/SPEEK-M) that can stop Brn - is used as separator, and glucose that can inhibit dendrites is introduced as anolyte additive. The constructed flowless AZBB mainly consists of two separate redox couples, including Zn/Zn(OH)4 2- in alkaline anolyte and Br2/Br- in neutral media, where non-cations (e.g. OH-, Zn(OH)4 2-, H2O,  and Brn -) can be restricted to their respective chamber by the PES/SPEEK-M while cations can pass by. In the optimized system, good electrochemical performance is achieved, mainly including a surprising discharge voltage of 2.01 V, a high average Coulombic efficiency of 96.7%, and a good cycling life of ≈1000 cycles without obvious capacity decay at a fixed charge capacity of 2 mAh cm-2.

Achievement of Efficient and Stable Nonflow Zinc-Bromine Batteries Assisted by Rational Decoration upon the Two Electrodes.

Aqueous zinc-bromine batteries (ZBBs) are highly promising because of the advantages of safety and cost. Compared with flow ZBBs, static ones without the assistance of pumping and tank components possess decreased cost and increased energy density and efficiency. Yet, the issues of Zn dendrites and shuttle effect of polybromide ions (Brn-) are more serious in nonflow ZBBs. Meanwhile, the hydrogen evolution reaction (HER) and the sluggish kinetics of the Br2/Br- couple are also in-negligible. Herein, a compressive approach, the cation-exchange membrane (CEM) coating on Zn anodes and N-defect decoration toward carbon felt cathodes, is developed. The CEM with cation-only function can inhibit the formation of Zn dendrites via tuning the Zn2+ flow at the interface, block the noncationic substances, and hence prevent the shuttle of Br2/Brn- and the water decomposition-concerned HER. The optimized nonflow ZBBs can deliver high Coulombic, voltage, and energy efficiencies of 94.1, 92.8, and 87.4%, respectively, which can be well remained in 1000 cycles. Meanwhile, the output voltage is as high as 1.7 V at 10 mA cm-2 with a high areal capacity of 2 mA h cm-2, and a LED with a rated voltage of 1.6 V can be powered successfully, exhibiting high application value.

Construction of Cation-Sieving Function Layers Enabling Dendrite-Free Zinc Metal Anodes for Durable Aqueous Systems.

Rechargeable aqueous zinc-ion batteries are considered as promising candidates for safe and green energy storage. Yet, Zn anodes still suffer from serious challenges. Herein, an effective cation-sieve of polyethersulfone-modified sulfonated polyether ether ketone is developed as protective coating layer of the Zn anodes. Cation-only transmission and dense property of the layer can protect the Zn from active water and anions, inhibiting corrosion, hydrogen evolution reaction (HER), and passivation. Zincophilic property of the layer can homogenize Zn2+ flow, and promote uniform plating of Zn. Therefore, protected symmetric Zn||Zn cell can maintain as long as 5600 h with a low polarization at 1.0 mA cm-2 and 0.5 mAh cm-2 , and still long as 800 h at 5.0 mA cm-2 and 5.0 mAh cm-2 . It is found that not only the dendrites but also the popular existed passivation product of Zn4 SO4 (OH)6 ·5H2 O can be inhibited effectively. In asymmetric Zn||Ti cells, average Coulombic efficiency can reach 98.2%, suggesting corrosion and HER are restrained effectively. Matched with MnO2 cathode, full cells using coated Zn exhibit much better cycling performance than that using bare Zn. Moreover, Zn4 O3 (SO4 )·7H2 O (ZSH)-assisted reversible conversion mechanism between the ZSH and Znx Hy MnO2 is revealed through operando Raman.

Effective Solution toward the Issues of Zn-Based Anodes for Advanced Alkaline Ni-Zn Batteries.

Alkaline nickel-zinc (Ni-Zn) batteries, as traditional rechargeable aqueous batteries, possess an obvious advantage in terms of energy density, but their development has been hindered by the anode-concerned problems, Zn dendrites, self-corrosion, passivation, deformation, and hydrogen evolution reaction (HER). Herein, to solve these problems, a dual protective strategy is proposed toward the anode using ZnO as an initial active material, including a C coating on ZnO (ZnO@C) and a thin poly(vinyl alcohol) (PVA) layer coating on the electrode (ZnO@C-PVA). In a three-electrode configuration, the reversible capacity can reach 600 mAh g-1 for the ZnO@C-PVA. Using excessive commercial Ni(OH)2 as the cathode, the alkaline Ni-Zn cells exhibit good electrochemical performance: Discharge capacity can be as high as 640-650 mAh g-1 at 4 A g-1 with a Coulomb efficiency (CE) as high as 97-99% after activity, suggesting low self-corrosion and HER. Capacity retention is 97% after 1200 cycles, indicating rather good durability. The discharge capacity is even slightly increased with the increase of charge/discharge current density (≤8 A g-1), implying good rate performance. Additionally, the discharge voltage can reach 1.8 V (midpoint value) at various current densities, reflecting the fast reaction kinetics of the anode. Most importantly, no Zn dendrites and passivation are observed after long-term cycling. The strategy proposed here can solve the anode-concerned problems effectively, exhibiting a high application prospect.

Fabrication of a Cation Exchange Membrane with Largely Reduced Anion Permeability for Advanced Aqueous K-ion Battery in an Alkaline-Neutral Electrolyte Decoupling System.

Herein, an efficient method to prepare sulfonated polyether ether ketone (SPEEK) based cation exchange membranes (CEMs) is developed, where polyethersulfone (PES) is used as an additive. The optimized membrane of 30 wt.%PES/SPEEK-M exhibits a rather low anion permeability and a high ionic conductivity of 9.52 mS cm-1 together with low volume swelling in water. Meanwhile, tensile strength of the membrane is as high as 31.4 MPa with a tensile strain of 162%. As separators for aqueous K-ion batteries (AKIBs) with decoupled gel electrolytes (Zn anode in alkaline and Prussian blue (FeHCF) cathode in neutral). Discharge voltage of the AKIB can reach 2.3 V. Meanwhile, Zn dendrites can be effectively suppressed in the gel anolyte. Specific capacities of the FeHCF cathode are 116.7 mAh g-1 at 0.3 A g-1 (close to its theoretical value), and 95.0 mAh g-1 at 1.0 A g-1 , indicating good rate performance. Capacity retention of the cathode is as high as 91.2% after 1000 cycles' cycling owing to the well remained neutral environment of the catholyte. There is almost no pH change for the catholyte after cycling, indicating good anion-blocking or cation-selecting ability of the 30 wt.%PES/SPEEK-M, much better than other membranes.

Relationship between plasma levels of 25-hydroxyvitamin D and arterial stiffness in elderly Chinese with non-dipper hypertension: An observational study.

Elderly individuals with non-dipper hypertension are at high risk of cardiovascular disease because of increased stiffness of peripheral arteries. Since, vitamin D deficiency is prevalent in elderly Chinese. We examined whether reduced plasma levels of 25-hydroxyvitamin D [25(OH)D] may help promote this stiffness.Hypertensive patients at least 60 years old without history of peripheral arterial disease at our hospital were retrospectively divided into dipper and non-dipper groups according to the results of 24-hour ambulatory blood pressure monitoring. Plasma levels of 25(OH)D were measured by enzyme immunoassay. Peripheral arterial stiffness was measured based on the cardio-ankle vascular index (CAVI).Of the 155 patients enrolled, 95 (61.3%) were diagnosed with non-dipper hypertension and these patients had significantly lower plasma levels of 25(OH)D than the 60 patients with dipper hypertension (19.58 ±â€Š5.97 vs 24.36 ±â€Š6.95 nmol/L, P < .01) as well as significantly higher CAVI (8.46 ±â€Š1.65 vs 7.56 ±â€Š1.08 m/s, P < .01). Vitamin D deficiency was significantly more common among non-dipper patients (57.9% vs 31.7%, P < .01). Multivariate regression showed that age and 25(OH)D were independently related to CAVI, with each 1-ng/ml decrease in 25(OH)D associated with a CAVI increase of +0.04 m/s.Non-dipper hypertension is associated with vitamin D deficiency and reduced plasma levels of 25(OH)D. The latter may contribute to stiffening of peripheral arteries, increasing the risk of cardiovascular disease.

One-pot hydrothermal synthesis of uniform ß-MnO2 nanorods for nitrite sensing.

A simple hydrothermal method was developed for the synthesis of uniform single-crystal ß-MnO(2) nanorods only using potassium permanganate and sodium nitrite in acidic solution, without any seed or template. The as-prepared ß-MnO(2) nanorods have the average diameter of 300±20 nm and a length up to 1.2±0.2 µm. Moreover, the effects of pH, temperature, and reactant molar ratios on the morphology of the final product were studied in detail. In addition, the catalytic ability of the as-prepared ß-MnO(2) nanorods was tested for the electrooxidation of nitrite. The resulting sensor showed a wide linear range from 0.29 µM to 26.09 mM (R=0.9986), high sensitivity (1.21 µA mM(-1), S/N=3), low detection limit (0.29 µM), and fast response (less than 5 s).

Spermine-graft-dextran non-covalent copolymer as coating material in separation of basic proteins and neurotransmitters by capillary electrophoresis.

Spermine-graft-dextran (Spe-g-Dex) copolymer was synthesized and used as a non-covalent coating for the separation of proteins and neurotransmitters by capillary electrophoresis. The coating was obtained via flushing the capillary with 1.0% Spe-g-Dex copolymer solution for 2min. Electroosmotic flow (EOF) was strongly suppressed, ranging from -1.60x10(-9) to 3.65x10(-9)m(2)V(-1)s(-1). Effect of experimental conditions, such as the copolymer concentration, the concentration and pH of the background electrolyte (BGE), on the Spe-g-Dex coating was investigated. Separation of lysozyme, cytochrome c, ribonuclease A and alpha-chymotrypsinogen yielded high separation efficiencies ranging from 141000 to 303000plates/m and recoveries from 85.4% to 98.3% at pH 4.0 (284.0mM sodium acetate-acetic acid buffer, I=50mM). Run-to-run repeatabilities and day-to-day, and capillary-to-capillary reproducibilities were all below 1.7%. In addition, Spe-g-Dex coating allowed the successful separation of five neurotransmitters, 5-hydroxytryptamine, dopamine, epinephrine, isoprenaline, dobuamine at pH 4.0 with high separation efficiencies of 290000-449000plates/m.

[Determination of phytate and phosphate in plant samples by suppressed conductivity ion chromatography].

Determination of phytate and phosphate by suppressed conductivity ion chromatography was investigated. Plant samples were extracted with 1% (mass fraction) trichloroacetic acid (TCA). After centrifugal settling, the supernatant was filtered with a 0.45 microm filter membrane before injected into the ion chromatographic system and detected by suppressed conductivity. The gradient eluent was composed of 0.22 mol/L sodium hydroxide solution, water and 50% (v/v) isopropyl alcohol solution. Phytate and phosphate were determined within 15 min, and no interference was found in the presence of fluorate, chlorate, nitrate, sulphate and TCA. Good linearities for phytate and phosphate were obtained in the ranges of 5-400 mg/L (r2 = 0.9994) and 5-500 mg/L (r2 = 0.9999), and the detection limits (S/N = 3) were 3.5 mg/L and 1.5 mg/L, respectively. The average recoveries for phytate and phosphate were 99.8% and 98.4%, and their relative standard deviations were 1.98% and 2.09%, respectively.