非水四乙基氯化铵体系中电溶解耦合铪醇盐合成的电化学机理与动力学

作为一种具有广泛应用前景的高效电合成技术,耦合电溶解的铪醇盐合成(EHS)基于铪溶解/乙醇脱氢的同时非均相反应以及溶液中Hf^(4+)阳离子和烷氧阴离子的自发结合反应。为了阐明EHS过程的机制和动力学,通过电化学测试、扫描电镜、气相色谱和微观动力学模拟等手段,探究阳极铪溶解和阴极乙醇脱氢的电化学行为。结果表明,优选的支持电解质四乙基氯化铵(Et_(4)NCl)展现了钝化膜击穿与铪溶解协同的剧烈点蚀机制以及两段脱氢机制。为量化钝化膜击穿和铪点蚀的动力学参数,提取与钝化速率、钝化膜击穿敏感性和点蚀速率相关的3个指标,并通过建立微观动力学模型评估基于Et_(4)NCl体系的EHS工艺,其电能消耗为1.53~1.83 k W·h/kg Hf(OC_(2)H_(5))_(4)。

添加In对SAC305焊料显微组织和性能的影响

在Sn-3.0Ag-0.5Cu(SAC305)焊料中熔入0.5%~10%(质量分数)的In粉以改变钎料的显微组织,进而改善焊料的性能。实验结果表明:β-Sn(In)、Ag_(3)(Sn,In)和Cu_(6)(Sn,In)_(5)相存在于所有的含In钎料中,在SAC305-10In焊料中发现了InSn_(4)物相。随着In含量的增加,β-Sn晶粒形核点增加,其形核模型由{101}转变为{301},从而细化β-Sn晶粒,使得β-Sn的形态由粗大晶粒转变为交错晶粒,最后转变为多晶粒。结果表明,这种β-Sn晶粒形态转变引起细晶强化与固溶强化的联合作用,使得SAC305-xIn焊料的显微硬度随着In添加量的增加而显著升高。

电场对废旧锂离子电池中有价金属浸出的影响

提出一种电场强化浸出工艺,用于提高废旧锂离子电池提取Li、Ni、Co以及Mn过程中的浸出效率。通过产品表征和浸出动力学等手段,对浸出工艺参数进行优化并对浸出机制进行研究。在优化浸出条件下,超过98%Li、97%Ni和Co以及93%Mn被浸出进入到溶液中。浸出动力学研究表明,Li、Ni、Co和Mn的浸出过程由基于核缩减模型的化学反应控制,并确定浸出活化能分别为42.4、46.1、46.2和47.3k J/mol。浸出过程中,施加电场为溶液中Fe^(2+)和Cl^(-)的循环利用提供了便利通道,减少了还原剂的添加量,同时保证了高的金属浸出率。

Reductive acid leaching of valuable metals from spent lithium-ion batteries using hydrazine sulfate as reductant

Hydrazine sulfate was used as a reducing agent for the leaching of Li,Ni,Co and Mn from spent lithium-ion batteries.The effects of the reaction conditions on the leaching mechanism and kinetics were characterized and examined.97%of the available Li,96%of the available Ni,95%of the available Co,and 86%of the available Mn are extracted under the following optimized conditions:sulfuric acid concentration of 2.0 mol/L,hydrazine sulfate dosage of 30 g/L,solid-to-liquid ratio of 50 g/L,temperature of 80℃,and leaching time of 60 min.The activation energies of the leaching are determined to be 44.32,59.37 and 55.62 k J/mol for Li,Ni and Co,respectively.By performing X-ray diffraction and scanning electron microscopy in conjunction with energy dispersive X-ray spectroscopy,it is confirmed that the main phase in the leaching residue is MnO2.The results show that hydrazine sulfate is an effective reducing agent in the acid leaching process for spent lithium-ion batteries.

Thermodynamics and kinetics of fluoride removal from simulated zinc sulfate solution by La(Ⅲ)-modified zeolite

To understand the mechanism of fluoride removal from the simulated zinc sulfate solution by the La(III)-modified zeolite,the adsorbent was characterized by XRD,SEM and EDS.The effects of absorbent dose and contact time,the adsorption isotherms and the sorption kinetics were investigated.The experimental results were compatible with the Langmuir isotherm model.The theoretical maximum adsorption capacities are 20.83 and 23.04 mg/g at 303 and 313 K,respectively.And the physisorption is revealed using the Temkin isotherm model and the D-R isotherm model.The sorption process is more suitable by the pseudo-second-order kinetic models.Thermodynamic parameters such as standard free energy change(ΔGΘ<0 kJ/mol),standard enthalpy change(ΔHΘ=8.28 kJ/mol)and standard entropy change(ΔSΘ=0.030 kJ/(mol?K))indicate the spontaneity of adsorption and endothermic physical sorption.Furthermore,the fluoride concentration in the industrial zinc sulfate solution decreases from 98.05 to 44.09 mg/L with the adsorbent dosage of 15 g/L.

Sb_(2)S_(3) nanorods/porous-carbon composite from natural stibnite ore as high-performance anode for lithium-ion batteries

To avoid the high purity reagents and high energy consumption involved in the manufacturing of lithium-ion battery anode materials,Sb_(2)S_(3) nanorods/porous-carbon anode was prepared by remodeling natural stibnite ore with porous carbon matrix via a simple melting method.Due to the nanostructure of Sb_(2)S_(3) nanorods and synergistic effect of porous carbon,the Sb_(2)S_(3) nanorods/porous-carbon anode achieved high cyclic performance of 530.3 mA·h/g at a current density of 100 mA/g after 150 cycles,and exhibited a reversible capacity of 130.6 mA·h/g at a high current density of 5000 mA/g for 320 cycles.This shows a great possibility of utilizing Sb_(2)S_(3) ore as raw material to fabricate promising anodes for advanced lithium-ion batteries.

An environmentally benign and sustainable process for carbon recovery and efficient defluorination of spent carbon cathode

A systematic and green low-temperature sulfation roasting−water leaching strategy was put forward to achieve a very high fluorine removal rate of 97.82%for spent carbon cathode(SCC),which was believed as a hazardous solid waste.And the carbon could be recycled with a purity of 90.29 wt.%in the flaky microstructure.Thermodynamic analysis and the results of SEM,XRD and EDS indicate that most of the fluoride could convert into water-soluble sulfate at low temperature.And the highest fluorine removal rate could be obtained when<0.15 mm SCC particles were mixed with sulfuric acid at a liquid-to-solid ratio of 1:1,and then roasted at 300℃ for 0.5 h.The sulfate was removed to purify the carbon via water-leaching process.Avrami exponents and corresponding activation energy for the roasting and leaching process demonstrated that both processes are controlled by diffusion.

Performance of carbon-coated nano-ZnO prepared by carbonizing gel precursor as anodic material for secondary alkaline Zn batteries

Although carbon coating can improve the cycle life of anode for alkaline Zn batteries, the specific capacity reported is still lower compared with nanosized ZnO. Herein, carbon-coated nanosized ZnO(nano-ZnO@C) was synthesized by one-step heat treatment from a gel precursor in N2. Commercial ZnO and homemade ZnO prepared similarly in air atmosphere were studied for comparison. Structure analysis displayed that both nano-ZnO@C and homemade ZnO had a porous hierarchical agglomerated architecture produced from primary nanoparticles with a diameter of approximately 100 nm as building blocks. Electrochemical performance measurements showed that nano-ZnO@C displayed the highest electrochemical activity, the lowest electrode resistance, the highest discharge capacity(622 m A·h/g), and the best cyclic stability. These properties were due to the combination of nanosized ZnO and the physical capping of carbon, which maintained the high utilization efficiency of nano-ZnO, and simultaneously prevented dendrite growth and densification of the anode.

Catalytic effects of NH4+ on hydrogen evolution and manganese electrodeposition on stainless steel

The effects of(NH4)2SO4 concentration(c((NH4)2SO4))on hydrogen evolution and Mn electrodeposition on stainless steel(SS)in different potential ranges were investigated by linear sweep voltammetry(LSV),electrochemical impedance spectroscopy(EIS),potentiostatic polarization,chronoamperometry,scanning electron microscope(SEM)and X-ray diffraction(XRD)techniques.The results show that the NH4^+discharge reaction(NDR)intensifies the overall hydrogen evolution kinetics,and the NDR is catalyzed by increasing c((NH4)2SO4)and over-potential.The electro-crystallization of Mn on SS follows a three-dimensional progressive nucleation and diffusion-limited growth mechanism.Increasing the over-potential could accelerate the nucleation rate and also cause the decline of the nucleation density.The absorbed Mn^2+preferably discharges at low over-potential.Increasing c((NH4)2SO4)at medium over-potential could improve the current efficiency and produce more block-like grains.The nucleation process is suppressed by increasing c((NH4)2SO4)at high over-potential,at which the formation of columnar grains with higher hydrogen contents becomes prevailing.

Three-dimensional antimony sulfide anode with carbon nanotube interphase modified for lithium-ion batteries

Antimony sulfide(Sb_(2)S_(3))is a promising anode for lithium-ion batteries due to its high capacity and vast reserves.However,the low electronic conductivity and severe volume change during cycling hinder its commercialization.Herein our work,a three-dimensional(3D)Sb_(2)S_(3) thin film anode was fabricated via a simple vapor transport deposition system by using natural stibnite as raw material and stainless steel fiber-foil(SSF)as 3D current collector,and a carbon nanotube interphase was introduced onto the film surface by a simple dropping-heating process to promote the electrochemical performances.This 3D structure can greatly improve the initial coulombic efficiency to a record of 86.6% and high reversible rate capacity of 760.8 mAh·g^(-1) at 10 C.With carbon nanotubes interphase modified,the Sb_(2)S_(3) anode cycled extremely stable with high capacity retention of 94.7% after 160 cycles.This work sheds light on the economical preparation and performance optimization of Sb_(2)S_(3)-based anodes.

Synthesis of Cu_2ZnSnS_4 thin film from mixed solution of Cu_2SnS_3 nanoparticles and Zn ions

The Cu2ZnSnS4 thin film was prepared by a facile solution method without vacuum environment and toxic substance. The formation mechanism of the film was studied by transmission electron microscopy (TEM), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and Raman scattering measurements. Through cyclic voltammetry and photo-electricity tests, the electrocatalytic activity of the prepared film as the counter electrode of dye-sensitizedsolar cell was also studied. The results show that the mixed precursor solution mainly consists of Cu2SnS3 nanoparticles and Zn ions.After 550 °C annealing process on the precursor film prepared from the mixed solution, Cu2ZnSnS4 thin film is obtained. Besides, itis found that the prepared Cu2ZnSnS4 thin film has the electrocatalytic activity toward the redox reaction of I3?/I? and the dye-sensitized solar cell with the prepared Cu2ZnSnS4 thin film as the counter electrode achieves the efficiency of 1.09%.