Poly(Ionic Liquid) as an Anion Exchange Membrane for a 3.3 V Copper–Lithium Battery

Metal–metal battery bears great potential for next-generation large-scale energy storage system because of its simple manufacture process and low production cost.However,the cross-over of metal cations from the cathode to the anode causes a loss in capacity and influences battery stability.Herein,a coating of poly(ionic liquid)(PIL)with poly(diallyldimethylammonium bis(trifluoromethanesulfonyl)imide)(PDADMA^(+)TFSI^(−))on a commercial polypropylene(PP)separator serves as an anion exchange membrane for a 3.3 V copper–lithium battery.The PIL has a positively charged polymer backbone that can block the migration of copper ions,thus improving Coulombic efficiency,long-term cycling stability and inhibiting self-discharge of the battery.It can also facilitate the conduction of anions through the membrane and reduce polarization,especially for fast charging/discharging.Bruce-Vincent method gives the transport number in the electrolyte to be 0.25 and 0.04 for PP separator without and with PIL coating,respectively.This suggests that the PIL layer reduces the contribution of the internal current due to cation transport.The use of PIL as a coating layer for commercial PP separator is a cost-effective way to improve overall electrochemical performance of copper–lithium batteries.Compared to PP and polyacrylic acid(PAA)/PP separators,the PIL/PP membrane raises the Coulombic efficiency to 99%and decreases the average discharge voltage drop to about 0.09 V when the current density is increased from 0.1 to 1 mA cm^(−2).

Structure and resistance of concentration polar layer on cation exchange membrane-solution interface

Membrane/solution interface consists of a neutral concentration polar layer(CPL)and a charge layer(CL)under external electrical field,and the neutral CPL can be neglected under high frequency AC electrical field.The relationship of CL thickness e with electrolyte concentration C and fixed ion exchange sites density σ in membrane surface layer can be expressed as e=σ/C.According to this model,the thickness of the CL on Nafion1135 membrane/solution interface(ec)was calculated under different membrane surface charge quantity Q and variable electrolyte concentration C.The membrane/solution interface CL thickness(em)is obviously related with the membrane properties,and decreases dramatically in a higher electrolyte concentration.em values are 76.3 nm and 110.3 nm respectively for Nafion1135 and PE01 ion exchange membrane in 0.05 mol/L H2SO4 solution,and em values for both membrane tend to 2 nm in 2 mol/L H2SO4 solution.For Nafion1135 membrane,the comparison of ec and em gives the result that CL thickness em obtained by resistance measurement fits well with the calculated CPL thickness ec while proton in CL transferred to membrane surface is 14.56×10?10 mol,which corresponds to the fixed exchange group number in a surface layer with a thickness τ=2 nm for Nafion1135 membrane.

Radiation synthesis and characteristics of PTFE-g-PSSA ion exchange membrane applied in vanadium redox battery

Radiation-induced grafting of styrene onto polytetrafluoroethylene (PTFE) membranes was studied by a simultaneous irradiation technique.Grafting was carded out usingγ-radiation from a ^(60)Co source at room temperature. Effects of absorbed dose,atmosphere,dose rate,and the concentration of initial monomer on the degree of grafting (DOG) were investigated and the most appropriate grafting condition was obtained.Subsequently,sulphonation of the grafted PTFE membrane (PTFE-g-PS) was carried out and a series of ion exchange membranes (PTFE-g-PSSA) was prepared.Further characterizations of FTIR,TGA,and SEM testified that grafting and sulphonation of the membranes were successfully processed;moreover,grafting of styrene not only occurred in the surface of PTFE membrane,but also in the micropores of the membrane.Ion exchange capacity (IEC) and conductivity were found increase with the grafting yield.The results suggest that at a low dose,such as 17 kGy,the ion exchange membrane (IEM) which will be suitable for vanadium redox battery (VRB) use can be obtained.

STUDY ON THE DIFFUSION OF Cu^(2+)-H^+ COUPLE IN A CATION EXCHANGE MEMBRANE——A RAPID METHOD TO DETERMINE SELF-DIFFUSION COEFFICIENTS OF COUNTER-IONS WITH UNEQUAL VALENCE

1 INTRODUCTIONKnowledge of the basic transport phenomena of ions in an ion exchange membrane isimportant for the application of such a membrane.Various studies on the developmentof mathematical models for predicting and correlating membrane transport rate havebeen published in recent years.More exact estimation of the diffusion coefficientshas been the subject of chief concern in many of these papers.For a bi-ionic systemwith the same valence,Sato et al.gave a method for estimating diffusion coefficients

FREE ALKALI RECOVERY FROM NaOH LEACHING LIQUOR OF TUNGSTEN ORE BY ELECTROLYSIS WITH ION-EXCHANGE MEMBRANE

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A RAPID METHOD TO DETERMINE DIFFUSION COEFFICIENTS OF COUNTER-IONS IN AN ION-EXCHANGE MEMBRANE

1 INTRODUCTIONRapid and precise methods to obtain the diffusion coefficients of counter-ions are im-portant for the characterization of ion exchange membranes.Many theoreticaldescriptions of ion transport in ion exchange membranes have been developed by usingthe principles of irreversible thermodynamics,or the Nernst-Planck equations.Fick’s law can also be used for the description of the transport of ions with equaldiffusivity.However,for counter-ions of different diffusivities,Nerst-Planck

PREPARATION OF SA-Fe CATION EXCHANGE MEMBRANE AND IT’S APPLICATION IN ELECTRODIALYSIS FOR TREATING WASTEWATER

An insoluble SA-Fe membrane was prepared by being linked soluble sodium alginate with FeCl3. SEM was used to observe its surface structure. IR spectrum indicated that Fe3+ was linked with ?COOH and ?OH in SA membrane. As a cationic exchanging membrane in electrodialysis the membrane was applied in treating inorganic wastewater with high concentration of inorganic ammonia and azote. The results of experiment showed that it was well-selective to ammonia and azote. The percentage of the removal of ammonia and azote in wastewater was up to 80%.

Ti/(Ti,Cr)N/CrN multilayer coated 316L stainless steel by arc ion plating as bipolar plates for proton exchange membrane fuel cells

Arc ion plating (AIP) is applied to form Ti/(Ti,Cr)N/CrN multilayer coating on the surface of 316L stainless steel (SS316L) as bipolar plates for proton exchange membrane fuel cells (PEMFCs). The characterizations of the coating are analyzed by scanning electron microscopy (SEM) and X-ray diffraction (XRD). Interfacial contact resistance (ICR) between the coated sample and carbon paper is 4.9 m Omega cm(2) under 150 N/cm(2), which is much lower than that of the SS316L substrate. Potentiodynamic and potentiostatic tests are performed in the simulated PEMFC working conditions to investigate the corrosion behaviors of the coated sample. Superior anticorrosion performance is observed for the coated sample, whose corrosion current density is 0.12 mu A/cm(2). Surface morphology results after corrosion tests indicate that the substrate is well protected by the multilayer coating. Performances of the single cell with the multilayer coated SS316L bipolar plate are improved significantly compared with that of the cell with the uncoated SS316L bipolar plate, presenting a great potential for PEMFC application. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

REDUCTION OF FERRIC IRON IN THE TITANIUM SULFATE SOLUTION BY THE ION EXCHANGE MEMBRANE PRIMARY CELL METHOD

In the production process of titanium dioxide with sulfuric acid, the contamination of the titanium sulfate solution (the ilmenite leaching solution) in the Fe 3+ reduction stage by iron scraps is a practical problem because it is difficult to guarantee the quality of the iron scraps. In this research, a new method, called the ion exchange membrane primary cell method, for reduction of Fe 3+ in the titanium sulfate solution has been advanced. The positive compartment of the primary cell consists of lead (copper) electrode and the titanium sulfate solution, and the negative compartment consists of iron electrode and acidic FeSO 4 solution. The anion ion exchange membrane is used as the diaphragm between two compartments. Fe 3+ in the titanium sulfate solution is reduced by the electric discharge of the primary cell. The effects of temperature, stirring strength of the solution and membrane area on the reduction rate have been investigated. The experimental result shows that the optimum current density can be higher than 100 A/m 2.

Study on the permselectivity of ion exchange membrane

Ion exchange membranes with high permselectivity (the character of separatingcations from anions or anions from cations) and high selectivity (the character of separatingcations or anions of different valencies) are important for electrodialysis process. The Donnanequilibrium theory, based on the equilibrium of ions and no electric field, can not exactly explainthe permselectivity of ion exchange membrane for ED process, since it is impossible to set up a ionexchange equilibrium between membrane and solution and to neglect the influence of electricaldriving force on ions during ED process. A novel model named 'anti-electric potential' isestablished to interpret the permselectivity of ion exchange membrane, according to thedetermination of electric potential between membranes and the variation of elements content insolutions and membranes. The results of experiment prove that the 'anti-electric potential' reallyexists within membranes. As for the selectivity, the results reveal that electric potential andhydration energy have great influence on the concentration and mobility of ions in membranes.

Analysis of Macro and Micronutrients in Soils from Palestine Using Ion Exchange Membrane Technology

Ion Exchange membrane technology (IEM) is a method that allowed a single extraction process and a single subsequent measurement of different elements that are available in soil. The values of the available forms of the different macro- and micronutrients obtained by IEM extraction were compared with the values of the soluble form obtained by conventional extraction methods. In surface soil sample, the concentrations of available potassium, nitrate, phosphate, iron and boron were 37.7 mg kg–1, 17.5 mg kg–1, 3.6 mg kg–1, 171.0 μg kg–1, and 4.2 μg kg–1 respectively were greater than that of soluble forms of the same elements which were 7.0 mg kg–1, 9.2 mg kg–1, 0.4 mg kg–1, 109.0 μg kg–1, and 1.9 μg kg–1 respectively.

PREPARATION AND CHARACTERIZATION OF ION EXCHANGE MEMBRANES BASED ON POLYVINYLIDENE FLUORIDE

A new ion exchange membrane based on polyvinylidene fluoride (PVDF) and sulfonated poly(styrene-divinylbenzene) was prepared by in-situ polymerization. The incorporation of sulfonic groups into the polyvinylidene fluoride composite membrane was confirmed by infrared spectroscopy (IR), ion exchange capacity (IEC) and energy dispersive X-ray analysis (EDAX). Area resistance, IEC and water uptake of the treated membrane were evaluated. When 20% of the crosslinked membrane was sulfonated at 80degreesC for 22 h, the PVDF ion exchange membrane can attain 0.8 Omega . cm(2) area resistance in NaCl aqueous solution at 25degreesC, IEC is as high as 2.43 millimoles per grain of the wet membrane. The hydrophilicity of PVDF membrane is also significantly improved after treatment. When 60% of crosslinked membrane was sulfonated at 80degreesC for 6 h, water uptake of the treated membrane can attain 64.7%.

SPES/PVDF Binary Membrane as an Alternative Proton Exchange Membrane in Vanadium Redox Flow Battery Application

SPES/PVDF blends were employed to prepare the ion exchange membranes for vanadium redox flow battery（VRB） application for the first time. The addition of the highly crystalline and hydrophobic PVDF effectively limited the swelling behavior of SPES. The vanadium ion permeability of SPES/PVDF membranes was one order of magnitude lower than that of Nafion 117 membrane and pristine SPES membrane. Single cells with SPES/PVDF composite membranes showed significantly lower capacity loss, higher coulombic efficiency and higher energy efficiency than that with Nafion117 and pristine SPES membranes. The blend membrane with 40 wt% of PVDF(denoted as S;P;) showed energy efficiency of 83.2% at 30 mA?cm;, which was superior to that of the Nafion117 and SPES membranes. In the self-discharge test, S;P;membrane showed twice longer duration in open circuit decay than that with Nafion 117 membrane. With all the good properties and low cost, the SPES/PVDF membranes are expected to have excellent commercial prospects as ion exchange membranes for VRB system.

Influence of solvent on ion conductivity of polybenzimidazole proton exchange membranes for vanadium redox flow batteries

Polybenzimidazole(PBI)is a kind of proton transport membrane material,and its ion conductivity is a key factor affecting its application in vanadium redox flow batteries(VRFBs).The casting solvent of PBI has a significant influence on the acid doping level of PBI membranes which is closely related to ionic conductivity.In this paper,3,3′-diaminobenzidine(DABz)and 4,4′-Dicarboxydiphenylether(DCDPE)were used as raw materials by solution condensation to prepare the PBI with ether bond groups.The chemical structure of PBI was determined by1H NMR and FT-IR,and the prepared PBI had good solubility which can be dissolved in a variety of solvents.The PBI proton exchange membranes were prepared by solution coating with 5 different solvents of N,N-dimethylformamide(DMF),N,N-dimethylacetamide(DMAc),dimethyl sulfoxide(DMSO),1-methyl-2-pyrrolidone(NMP),methane sulfonic acid(MSA).The effects of different solvents on the ion conductivity and physicochemical properties were discussed in detail.The results showed that the PBI membrane prepared by using MSA as solvent(the PBI+MSA membrane)exhibits high water uptake,acid doping level and low vanadium ion permeability.The VRFB assembled with the PBI+MSA membrane exhibited higher coulombic efficiency(CE)99.87%and voltage efficiency(VE)84.50%than that of the commercial Nafion115 membrane at100 m A·cm-2,and after 480 cycles,the EE value can still be maintained at 83.73%.The self-discharge time of a single battery was recorded to be as long as 1000 h.All experimental data indicated that MSA is the best solvent for casting PBI membrane.

STUDY ON THE ELECTROCHEMICAL BEHAVIOR OF ION EXCHANGE MEMBRANE IN PREPARING POTASSIUM CARBONATE

This investigation describes the one step preparation of potassium carbonate by electrolysis of potas-sium chloride solution in electrolyzers with various Nation membranes.Potassium bicarbonate solution wasfed to the cathode compartment,where it was converted into carbonate by reaction with the hydroxideformed at cathode.Because of the low OH^- concentration in the cathode compartment,the back migrationof OH^- through the membrane was almost negligible,resulting in a higher current efficiency,say 90% or more.In this study,electroconductivity,mass transfer,current efficiency and cell voltage were measured.Thefeasibility of the process was discussed and the optimal conditions examined.

Monovalent cation perm-selective membranes(MCPMs)"New developments and perspectives

As one of the most typical and promising membrane processes, electrodialysis(ED) technique plays a more and more significant role in industrial separation. Especially, the separation of monovalent cations and multivalent cations is currently a hot topic, which is not only desirable for many industries but also challenging for academic explorations. The main aim of the present contribution is to view the advances of a wide variety of monovalent cation perm-selective membranes(MCPMs) and their preparation technologies including(1) covalent crosslinking,(2) surface modification,(3) polymer blending,(4) electrospinning,(5) nanofiltration alike membrane,and(6) organic–inorganic hybrid. The relevant advantages and disadvantages with respect to some specific cases have been discussed and compared in detail. Furthermore, we elaborately discuss the opportunities and challenges of MCPMs, the fabricating strategies to take and the future perspectives.

The Insulator-to-Conductor Transition in Sulphonated Poly(Phenylene Oxide)Polymer membranes:Percolation Theory Approach

In this paper the percolation theory is employed to study the insulator-to-conductortransition in sulphonated poly（phenylene oxide）（SPPO） polymer membranes.The membranes withdifferent sulphonation degree were prepared and infrared characterized.The transition thresholdwas calculated by the experimental data of membrane conductivities and the coordination numberwas thus estimated.The functional group-SO3H distribution in the membrane was evaluated inaccordance with the calculations and showed a non-random dispersion on the microscopic scale.

Development of Hydrogel Polyelectrolyte Membranes with Fixed Sulpho-Groups via Radical Copolymerization of Acrylic Monomers

Electrolyte hydrogels are perspective materials for applications in electrochemical devices, which work at ambient temperatures. In this work, hydrogel sulpho-modified membranes were formed by radical co-polymerization of sodium styrensulphonate and potassium sulphopropyl acrylate with acrylamide and acrylonitrile. The hydrogel membranes were obtained in the form of thin films. Properties of the membranes were studied by thermogravimetry, mass-spectrometry and IR-spectrometry. The prepared membranes were thermally stable up to 70°C - 90°C, and showed ion exchange capacity and swelling coefficients sufficient for use as ion-exchange or proton-conducting membranes.

基于膜分离-树脂吸附的黄酒降酸工艺及风味评价

该实验在优化膜分离预处理工艺参数的基础上,考察了采用膜分离-树脂吸附的物理方法来调整黄酒酸度指标的工艺过程,并对降酸黄酒的风味品质进行了比较分析。结果表明,在料液温度25℃,运行压力1.0 MPa,截留分子质量为200、1000、2000 Da的不同膜预处理条件下,D354树脂对高酸黄酒的降酸率分别达到47.0%、53.8%、68.1%。降酸黄酒样品中共检测到32种挥发性风味物质,200、1000 Da膜预处理组获得的降酸黄酒样品中挥发性风味物质总含量分别达到1975.89、1919.80 mg/L,均显著高于未过膜处理组(1727.04 mg/L)。层次聚类分析表明,1000 Da和2000 Da组之间的风味相似度更高,正交偏最小二乘判别分析表明11种化合物对降酸黄酒的风味差异贡献较高。选用1000 Da膜预处理,结合10%填充比的D354树脂处理50 L高酸黄酒,总酸下降率达57.7%,氨基酸态氮保留率达98.8%,挥发性风味物质的保留率达80.0%。该研究为高酸黄酒的物理降酸提供了新的视角和应用场景。

Multidimensional network of polypyrrole nanotubes loaded with ZIF-67 to construct multiple proton transport channels in composite proton exchange membranes for fuel cells

Due to the designability of their proton transport channels,high-performance long-lasting composite proton exchange membranes(PEMs)are currently the subject of extensive research.However,the compatibility and channel order of the internal components of the composite membranes are still challenging.In this work,hollow polypyrrole(PPy)nanotube structures were obtained to provide a nitrogen source and to act as a skeleton to confine and separate cobalt nanoparticles on the surface of PPy nanotubes.Finally,zeolitic imidazolate framework material-67(ZIF-67)was attached to the surface.By using this method,PPy@ZIF-67 filler can minimize the particle size and inhibit Co^(2+)ions from aggregating,thus constructing a reasonably distributed transport channel and improving the proton transport capacity.As a result,the synthesized polymer nanotubes loaded metal-organic framework(MOF)nanofiber network can enhance the physicochemical properties and stability of the membrane by providing a more extensive interfacial interaction.In addition,the composite membrane has excellent ionic conductivity and power density,reaching 233.7 mS cm^(–1) and 837 mW cm^(–2) at 80℃ and 100%humidity.It indicates that the nanofibrous MOF structure not only improves the compatibility with the substrate but also provides sufficient leap points for proton transport via the interfacial conduction pathway between the PPy@ZIF-67 filler and the substrate,thus allowing the resulting composite membrane to facilitate proton transfer via the Vehicle and Grotthuss mechanisms synergistically.