二元溶剂[Bmim]Cl+NMP对褐煤的溶胀及电解液化的影响

本文在课题组已有的离子液体对煤进行溶胀预处理的研究基础上,进一步研究了多种含离子液体的二元混合溶剂.结果表明,[Bmim]Cl+NMP对神华褐煤的溶胀效果最佳.通过研究二元溶剂中[Bmim]Cl的体积分数、溶胀温度及时间对煤的溶胀度及其电化学还原反应的影响,发现[Bmim]Cl的体积分数为0.5时,煤的溶胀度较高.神华煤在[Bmim]Cl+NMP中溶胀12h即可达到平衡.提高温度不仅可以缩短达到溶胀平衡所需的时间,还可以进一步破坏煤的结构,提高溶胀度.神华褐煤在150℃下溶胀12h,溶胀度可达到3.93.通过二元溶剂[Bmim]Cl+NMP对煤的溶胀处理能提高煤电解加氢还原的反应活性,有利于提高煤的液化率,使电解液化率从31.66%提高到62.27%.

氢氧化钠法炼锌废电解液苛化处理工艺

提出了氢氧化钠法炼锌废电解液苛化处理工艺,确定了工艺参数,通过小型综合实验验证工艺的可行性。结果表明:该工艺再生碱的同时还能去除废电解液中的杂质,1m3的废电解液可苛化出约28kg碱,废电解液中铁、铜、镁、锰、镉、铬等重金属的去除率在10%～40%,砷的去除率可达62%,具有较好的净化除杂效果。

双有机溶剂杂化电解液用于高稳定水系锌金属电池

提出一种双有机溶剂,碳酸丙烯酯(PC)和N,N-二甲基甲酰胺(DMF)杂化的水系电解液新体系,用于水系锌金属电池。实验结果表明,5%DMF+2%PC杂化2 M ZnSO_(4)水系电解液,不但明显减低了锌负极的析氢,而且促进锌的三维沉积,抑制了锌负极枝晶,同时双有机溶剂可以降低水系电解液的凝固点到-20℃。基于合成的新电解液体系,在1 m A/cm^(2)的电流密度下,Zn||Zn对称电池能够稳定循环500 h以上,Zn||Cu非对称电池能够稳定循环1000圈以上,平均库伦效率为99.06%。并且Zn||MnO_(2)全电池在1 A/g的大电流密度下,循环2000圈后,仍保持着210 mAh/g的高比容量。

锂金属电池用高浓度电解液体系研究进展

锂金属二次电池具有极高的能量密度,是下一代储能电池的研究热点。然而,金属锂负极在传统碳酸酯电解液1 mol·L^(−1) LiPF6-EC/DEC(ethylene carbonate/diethyl carbonate)中充放电时,存在严重的枝晶生长和循环效率低下等问题,阻碍了其商业化应用。因此,开发与锂负极兼容的新型电解液体系是目前重要的研究任务。与传统稀溶液相比,高浓度电解液体系具有独有的物化性质和优异的界面相容性,并且能有效抑制锂枝晶生长、显著提升锂负极的循环可逆性,因而格外受到关注。本文综述了高浓度电解液及局部高浓电解液体系的最新研究进展,分析了其溶液化学结构和物化性质,对其与锂负极的界面相容性、枝晶抑制效果、效率提升能力及界面稳定性机制进行了探讨;文章着重介绍了高浓与局部高浓电解液体系在锂金属二次电池中的应用,同时从基础科学研究和应用研究两个层面对高浓电解液和局部高浓电解液存在的主要问题进行了简要分析,并对其未来发展方向进行了展望。

高性能水系锌基杂化电池的构筑及性能研究

水系锌离子电池由于其来源丰富、安全性高、高能量密度和双电子转移等诸多优势,受到研究者的广泛关注。本文通过使用KVPO4F(KVPF)作为锌基双离子杂化电池的正极材料,研究其在不同浓度水系电解液中的性能表现,最终选择出最优浓度的杂化电解液(3 M+0.2 M),并获得了约1.66V的还原峰对应电压,放电比容量最高达90mAh∙g-1,库伦效率稳定在96%以上。

Separation and recovery of Cu and As during purification of copper electrolyte

Cu, As, Sb and Bi in copper electrolyte could be efficiently removed by reducing with SO2 followed by evaporative crystallization. As2O3 and CuSO4·5H2O were obtained after crystallized product was treated by dissolution, oxidation, neutralization, sedimentation, filtration and evaporative crystallization. The removal rates of Cu, As, Sb and Bi are 87.1%, 83.9%, 21.0% and 84.7%, respectively, when As （Ⅴ） in copper electrolyte is fully reduced to As （Ⅲ） by SO2, and the H2SO4 in concentrated copper electrolyte is 645 g/L. The removal rate of As is 92.81% when 65 g crystallized product is dissolved in 200 mL water at 30 ℃. The CuSO4·5H2O content is 98.8% when the filtrate is purified under the conditions that n（Fe）：n（As） is 1.2, the dosage of H2O2 is 19 times the stoichiometric needed, temperature is 45 ℃, time is 40 min, pH is 3.7, and then is evaporation crystallized.

Optimization of dual electrolyte and characteristic of micro-arc oxidation coating fabricated on ZK60 Mg alloy

Micro-arc oxidation （MAO） process was carried out in a dual electrolyte system of NaAlO 2 and Na 3 PO 4 to develop compact, smooth and corrosion-resistant coatings on ZK60 Mg alloy by single factor experiments. The microstructural characteristics of coatings were investigated by X-ray diffractometry （XRD） and scanning electron microscopy （SEM） coupled with energy dispersive X-ray spectroscopy （EDS）. Test of mass loss was conducted at a 3.5% NaCl solution to assess the resistance to corrosion. The effect of every element in the dual electrolyte system on voltage—time responses during MAO process and the coating characteristic were also analyzed and discussed systematically via single factor experiments. The results reveal that the main components of NaAlO 2 and Na 3 PO 4 as well as additives of NaOH, NaB4O7 and C6H5Na3O7 demonstrate different effects on MAO process and coating characteristics. By means of single factor experiments, an optimized dual electrolyte system was developed, containing 17.5 g/L NaAlO 2, 5.0 g/LNa3 PO4, 5.0 g/L NaOH, 3.0 g/L NaB4O7 and 4.2g/LC6H5Na3O7 .

Role of Sb(V) in removal of As, Sb and Bi impurities from copper electrolyte

The function mechanism of Sb（V） in As, Sb and Bi impurities removal from copper electrolyte was investigated by adding Sb（V） ion in a synthetic copper electrolyte containing 45 g/L Cu2＋, 185 g/L H2SO4, 10 g/L As and 0.5 g/L Bi. The electrolyte was filtered, and the precipitate structure, morphology and composition were characterized by chemical analysis, SEM, TEM, EDS, XRD and FTIR. The results show that the precipitate is in the shape of many irregular lumps with size of 50-200 μm, and it mainly consists of As, Sb, Bi and O elements. The main characteristic bands in the FTIR spectra of the precipitate are As-O-As, As-O-Sb, Sb-O-Bi, Sb-O-Sb and Bi-O-Bi. The precipitate is the mixture of microcrystalline of AsSbO4, BiSbO4 and Bi3SbO7 by XRD and electronic diffraction. The removal of As, Sb and Bi impurities by Sb（V） ion can be mainly ascribed to the formation of antimonate in copper electrolytes.

Research progress of magnesium anodes and their applications in chemical power sources

Magnesium is a promising metal used as anodes for chemical power sources. This metal could theoretically provide negative discharge potential and exhibit large capacity during the discharge process. However, when the magnesium anode is adopted for practical applications, several issues, such as the discharge products adhered to the electrode surface, the self-discharge occurring on the anode material, and the detachment of metallic particles, adversely affect its inherently good discharge performance. In this work, the types of chemical power sources using magnesium as anodes were elaborated, and the approaches to enhance its anode performance were analyzed.

Influence of oxidation heat on hard anodic film of aluminum alloy

The special experimental device and sulfuric acid electrolyte were adopted to study the influence of anodic oxidation heat on hard anodic film for 2024 aluminum alloy. Compared with the oxidation heat transferred to the electrolyte through anodic film, the heat transferred to the coolant through aluminum substrate is more beneficial to the growth of anodic film. The film forming speed, film thickness, density and hardness are significantly increased as the degree of undercooling of the coolant increases. The degree of undercooling of the coolant, which is necessary for the growth of anodic film, is related to the degree of undercooling of the electrolyte, thickness of aluminum substrate, thickness of anodic film, natural parameters of bubble covering and current density. The microstructure and performance of the oxidation film could be controlled by the temperature of the coolant.

Microarc oxidation coating fabricated on AZ91D Mg alloy in an optimized dual electrolyte

Microarc oxidation （MAO） process was conducted on AZ91D magnesium alloy in an electrolyte composed of NazSiO3, NaAlO2, NaEB4O7, NaOH, C3H803 and C6H5Na307 by AC pulse electrical source. The surface and cross-sectional morphologies, film thickness, chemical composition and structure of the coatings were characterized by scanning electron microscopy（SEM）, layer thickness metry, energy disperse spectroscopy（EDS） and X-ray diffraction（XRD）. The corrosiofi resistances of the coatings in a 3.5% NaC1 neutral solution were evaluated by electrochemical impedance spectroscopy （EIS） and potentiodynamic polarization test. The results showed that an optimized electrolyte with a composition of 15 g/L NazSiO3, 9 g/L NaA102, 2 g/L NazB407, 3 g/L NaOH, 5 mL/L C3H803 and 7 g/LC,HsNa307 was developed by means of orthogonal experiment. The coating obtained in the optimized electrolyte had a dense structure and revealed a lower current density, decreased by two orders of magnitude as compared with the magnesium substrate. Meanwhile, the corrosive potentials of the coated samples increased nearly by 73 inV. EIS result showed that the corrosion resistance of the coating was mainly determined by the inner dense layer. The coating primarily contained elements Mg, Al, O and Si and XRD analyses indicated that the coating was mainly composed of MgO, Mg2SiO4 and MgAl204.

Reduction and deposition of arsenic in copper electrolyte

The influences of temperature, H2SO4 concentration, CuSO4 concentration, reaction time and SO2 flow rate on the reduction of arsenic（V） with SO2 were studied and the deposition behavior of arsenic （III） under the effect of concentration and co-crystallization was investigated in copper electrolyte. The results indicate that reduction rate of arsenic （V） decreases with increasing temperature and H2SO4 concentration, but increases with increasing SO2 flow rate and reaction time, and it can reach 92% under appropriate conditions that reaction temperature is 65 °C, H2SO4 concentration is 203 g/L, CuSO4 concentration is 80 g/L, reaction time is 2 h and SO2 gas flow rate is 200 mL/min. To remove arsenic in the copper electrolyte, arsenic （V） is reduced to trivalence under the appropriate conditions, the copper electrolyte is concentrated till H2SO4 concentration reaches 645 g/L, and then the removal rates of As, Cu, Sb and Bi reach 83.9%, 87.1%, 21.0% and 84.7%. The XRD analysis shows that crystallized product obtained contains As2O3 and CuSO4·5H2O.

Fe^(3+)/Fe^(2+) redox electrolyte for high-performance polyaniline/SnO_2 supercapacitors

The Fe3＋/Fe2＋ redox electrolyte for use in polyaniline/tin oxide （PANI/SnO2）supercapacitors was reported. The influences of redox electrolyte based on different Fe3＋/Fe2＋ ion pair concentrations in 1 mol/LH2SO4 solution on the pseudocapacitive behaviors of PANI/SnO2 supercapacitor were investigated. The electrochemical properties of the supercapacitor were studied by cyclic voltammetry （CV）, galvanostatic charge discharge （GCD）, and electrochemical impedance spectroscopy （EIS） techniques. It is found that the performance of the supercapacitor is the best when the Fe3＋/Fe2＋ concentrationis 0.4 mol/L and its initial specific capacitance is 1172 F/g at an applied current density of 1 A/g. The long-term cycling experiment shows good stability with the retention of initial capacitance values of 88% after 2000 galvanostatic cycles. The experimental results testify that using Fe3＋/Fe2＋ redox electrolyte has a good prospect for improving the performances of energy-storage devices.

Effect of salt stress on activity of superoxide dismutase （SOD） in Ulmus pumila L.

The injury tolerance of cell plasma membrane and the correlative enzymes activities of plasma-membrane protection system in the Ulmuspumila leaves treated by nine concentrations （0.3%, 0.6%, 0,9%, 1,2%, 1.5%, 1.8%, 2,1%, 2.4%, 3.0%） of Na2CO3 and NaHCO3 mixtures were studied in a greenhouse of Northeast Forestry University, Harbin, China. The rate of electrolyte leakage （REL） and SOD （Superoxide dismutase） activity in leaves of different samples were determined. Results showed that the REL in leaves of U. pumila presented a slowly increasing trend at the salt concentrations less than 1.5%, which indicated that cell plasma membrane of U. pumila leaves had rather strong resistance to the injury of salt ion, and had a significant increase at the salt concentrations more than 1.5%. The SOD activities in leaves of U, pumila presented an increased trend at salt concentrations less than 1.5%, the growth of seedlings did not decline, and tress and leaves had no symptom of injury, while the salt concentrations exceeded 1.5%, SOD activities sharply decreased and REL increased promptly.

Structure characterization and electrochemical properties of new lithium salt LiODFB for electrolyte of lithium ion batteries

Lithium difluoro(axalato)borate (LiODFB) was synthesized in dimethyl carbonate (DMC) solvent and purified by the method of solventing-out crystallization. The structure characterization of the purified LiODFB was performed by Fourier transform infrared (FTIR) spectrometry and nuclear magnetic resonance (NMR) spectrometry. The electrochemical properties of the cells using 1 mol/L LiPF6 and 1 mol/L LiODFB in ethylene carbonate (EC)/DMC were investigated, respectively. The results indicate that LiODFB can be reduced at about 1.5 V and form a robust protective solid electrolyte interface (SEI) film on the graphite surface in the first cycle. The graphite/LiNi1/3Mn1/3Co1/3O2 cells with LiODFB-based electrolyte have very good capacity retention at 55 ℃, and show very good rate capability at 0.5C and 1C charge/discharge rate. Therefore, as a new salt, LiODFB is a most promising alternative lithium salt to replace LiPF6 for lithium ion battery electrolytes in the future.

Synthesis and physico-chemical properties of new green electrolyte 1-butyl-3-methylimidazolium perchlorate

1-butyl-3-methylimidazolium perchlorate([BMIM]ClO4) was synthesized by two steps with N-methylimidazolium.Some physico-chemical properties,such as density,surface tension,viscosity,electrical conductivity as well as electrochemical window,were investigated and solvent performance was also studied.The results show that this kind of ionic liquid is an excellent electrolyte with low viscosity,high electrical conductivity and wide electrochemical window.In addition,[BMIM]ClO4 is soluble in most conventional solvents and some metal oxides have high solubility in it,which lays the foundation of direct electrolysis of metal oxides in this ionic liquid.

Statistical evaluation and optimization of zinc electrolyte hot purification process by Taguchi method

The neutral zinc sulfate solution obtained from hydrometallurgical process of Angouran zinc concentrate has cadmium, nickel and cobalt impurities, that must be purified before electrowinning. Therefore, cadmium and nickel are usually cemented out by addition of zinc dust and remained nickel and cobalt cemented out at second stage with zinc powder and arsenic trioxide. In this research, a new approach is described for determination of effective parameters and optimization of zinc electrolyte hot purification process using statistical design of experiments. The Taguchi method based on orthogonal array design（OAD） has been used to arrange the experimental runs. The experimental conditions involved in the work are as follows： the temperature range of 70-90 ℃ for reaction temperature（T）, 30-90 min for reaction time（t）, 2-4 g/L for zinc powder mass concentration（M）, one to five series for zinc dust particle size distributions（S1-S5）, and 0.1-0.5 g/L（C） for arsenic trioxide mass concentration. Optimum conditions for hot purification obtained in this work are T4（85 ℃）, t4=75 min, M4=3.5 g/L, S4（Serie 4）, and C2=0.2 g/L.

Influence of CsNO_3 as electrolyte additive on electrochemical property of lithium anode in rechargeable battery

Lithium metal is one of the most promising anode materials for rechargeable battery with high energy density,but its practical use is still hindered by two main problems,namely,lithium dendrite growth and low Coulombic efficiency.To address the issues,cesium nitrate(CsNO3)is selected as the additive to modify the electrolyte for lithium secondary battery.Here we report electrochemical performance of lithium secondary battery with different concentration of CsNO3 as electrolyte additive.The study result demonstrates that Coulombic efficiency of Li–Cu cells and the lifetime of symmetric lithium cells contained CsNO3 additive are improved greatly.Li–Cu cell with 0.05 mol/L CsNO3 and 0.15 mol/L LiNO3 as electrolyte additive presents the best electrochemical performance,having the highest Coulombic efficiency of around 97%and the lowest interfacial resistance.With increasing the concentration of CsNO3 as electrolyte additive,the electrochemical performance of cells becomes poor.Meanwhile,the morphology of lithium deposited films with CsNO3-modified electrolyte become smoother and more uniform compared with the basic electrolyte.

Influence of Electrolyte on ESR of Medium Voltage Wet Tantalum Capacitors

In this paper, the influence of working electrolyte on high-frequency electrical performance of wet tantalum capacitors is studied. Emphasis is especially put on the study of the contribution of depolariser in reducing Equivalent Series Resistance(ESR). According to the theory of depolarization in electrochemistry and the theory of cathode capacitance of electrolytic capacitor, different kinds of depolarisers are added separately into the foregone electrolyte. Then capacitors are assembled with tantalum cores dipped with the compounded electrolytes. The best depolariser and its concentration in the whole electrolyte could be selected according to the test results of the capacitance and ESR of the capacitors. The results of our experiment show that depolariser Fe 2(SO 4) 3 used in working electrolyte of 100 V/100 μF wet tantalum capacitors can help to obtain lower ESR and higher capacitance at frequency from 0.1 kHz to 100 kHz.

Anodic behavior and microstructure of Al/Pb-Ag-Co anode during zinc electrowinning

In order to study the anodic behavior and microstmctures of A1/Pb-Ag-Co anode during zinc electrowinning, by means of potentiodynamic investigations, scanning electron microscopy （SEM） and X-ray diffraction （XRD） analyses, the mechanism of the anodic processes playing on the surface of A1/Pb-0.8%Ag and A1/Pb-0.75%Ag-0.03%Co anodes prepared by electro-deposition from methyl sulfonic acid bath for zinc electrowinning from model sulphate electrolytes have been measured. On the basis of the cyclic voltammograms obtained, information about the corrosion rate of the composite in PbO2 region has been concluded. The microstructures were also observed by means of SEM and XRD which showed Pb-0.75%Ag-0.03%Co alloy composite coating has uniform and chaotic orientation tetragonal symmetry crystallites of PbSO4, but Pb-0.8%Ag alloy composite coating has well-organized orientation crystallites of PbSO4 concentrated in the certain zones after 24 h of anodic polarization. It is important that Al/Pb-0.75%Ag-0.03%Co anode oxide film consists of non-conductive dense MnO2 and PbSO4 and a, fl-PbO2 penetrated into which, in fact, are the active centers of the oxygen evolution after 24 h of anodic polarization.