Novel copper redox-based cathode materials for room-temperature sodium-ion batteries

Layered oxides of P2-type Nao.68Cuo.34Mno.6602, P2-type Nao.68Cuo.34Mno.50Tio.1602, and O＇3-type NaCuo.67Sbo.3302 were synthesized and evaluated as cathode materials for room-temperature sodium-ion batteries. The first two materials can deliver a capacity of around 70 mAh/g. The Cu2＋ is oxidized to Cu3＋ during charging, and the Cu3＋ goes back to Cu2＋ upon discharging. This is the first demonstration of the highly reversible change of the redox couple of Cu2＋/Cu3＋ with high storage potential in secondary batteries.

Iron and copper recovery from copper slags through smelting with waste cathode carbon from aluminium electrolysis

To recover metal from copper slags,a new process involving two steps of oxidative desulfurization followed by smelting reduction was proposed in which one hazardous waste(waste cathode carbon)was used to treat another(copper slags).The waste cathode carbon is used not only as a reducing agent but also as a fluxing agent to decrease slag melting point.Upon holding for 60 min in air atmosphere first and then smelting with 14.4 wt%waste cathode carbon and 25 wt%CaO for 180 min in high purity Ar atmosphere at 1450℃,the recovery rates of Cu and Fe reach 95.89%and 94.64%,respectively,and meanwhile greater than 90%of the fluoride from waste cathode carbon is transferred into the final slag as CaF_(2) and Ca_(2)Si_(2)F_(2)O_(7),which makes the content of soluble F in the slag meet the national emission standard.Besides,the sulphur content in the obtained Fe-Cu alloy is low to 0.03 wt%.

High area-capacity Mg batteries enabled by sulfur/copper integrated cathode design

Rechargeable Mg batteries potentially display lower cost and competitive energy density compared with their Li-ion counterparts.However,the practical implementation of high area-capacity cathodes still remains a formidably challenging task.This work presents the sulfur/copper integrated cathodes fabricated by the conventional blade-coating process and slurry-dipping method.The sulfur/copper foil integrated cathodes deliver a high area-capacity of 2.6 mAh cm^(-2)after 40 cycles,while the sulfur/copperfoam integrated cathode exhibits an ultrahigh area-capacity of 35.4 mAh cm^(-2),corresponding to 743.1 Wh L^(-1)at the electrode level(1.5 times higher than the LiCoO_(2)-graphite system).The in-situ formed copper sulfide intermediates with sufficient cation defects can act as functional intermediates to regulate the sulfur electrochemistry during the first discharge process.The subsequent cycles are operated by the reversible displacement reaction between Mg-ions and copper sulfide active substances.In particular,the copper ions prefer to extrude along the[001]direction in copper sulfides lattice and simultaneously the rock-salt MgS crystals are generated.Besides,the nonuniform surface topography of the cycled Mgmetal anode,caused by the spatial inhomogeneity in current distribution,is demonstrated to lead to the battery performance degradation for high area-capacity Mg batteries.

Copper Ions Removal from Wastewater by Electrocoagulation Using Cement-based Cathode Plates

The present work uses PEO solution to well disperse carbon fiber and identifies percolation thresholds of carbon fiber and carbon black which are used as conductive fillers.The resultant cathode plates have an average compressive strength of 27.3 MPa and flexural strength of 29.09 MPa,which demonstrate excellent mechanical properties.The Cu^(2+)removal efficiency was measured at different current densities in EC process with cement-based cathode plate,while the voltage changes were recorded.The results showed that the cement-based cathode plate operated stably and achieved 99.7%removal of 1 L of simulated wastewater with a Cu^(2+)concentration of 200 ppm at a current density of 8 m A/cm^(2)for 1 h.Characterization of floc and tested cathode plates,SEM and EDS analyses,and repeatability testing of the tested plates demonstrate the reusability of the plates,proving that cement-based plates can effectively replace metal cathode plates,reduce the cost of EC and improve the applicability of EC devices.

Use of various MgO resources for high-purity Mg metal production through molten salt electrolysis and vacuum distillation

A green and effective electrolytic process was developed to produce high-purity Mg metal using primary and secondary resources containing Mg O as a feedstock. The electrolysis of various Mg O resources was conducted using a Cu cathode in MgF2– LiF – KCl molten salt at 1043 K by applying an average current of 1.44 A for 12.5 h. The electrolysis of calcined North Korean magnesite and seawater Mg O clinker yielded Mg alloys of MgCu2and(Cu) phases with current efficiencies of 89.6–92.4%. The electrolysis of oxidized Mg O-C refractory brick, aged ferronickel slag, and ferronickel slag yielded Mg alloys of MgCu2and(Cu) phases with current efficiencies of 59.3–92.3%. The vacuum distillation of Mg alloys obtained was conducted at 1300 K for 10 h to produce high-purity Mg metal. After vacuum distillation, Mg metal with a purity of above 99.994% was obtained. Therefore, this study demonstrates the feasibility of the production of high-purity Mg metal from various Mg O resources using a novel electrolytic process with a Cu cathode, followed by vacuum distillation.

Electroreduction of Samarium Ion on Co and CuCathodes in Molten Chloride

The cyclic voltammetry was used to study the electrochemical reaction of Sm(III) in NaCl-KCl equimolar mixture on the Co and Cu cathodes. It is reasonable to presume that the reduction of Sm(III) to Sm(II) was realized on Co and Cu electrodes respectively at first step. Sm(II) was subject to the reduction and formed alloys with Co and Cu on the electrode surface.

Production of high-purity Mg metal from dolomite through novel molten salt electrolysis and vacuum distillation

In this study,a novel Mg production process for producing high-purity Mg metal from dolomite was developed.When the electrolysis of calcined dolomite was conducted using Cu cathode and C anode in MgF_(2)–LiF molten salt at 1083–1173 K by applying an average current of 1.42–1.46 A for 9.50–21.0 h,the current efficiency of 66.4–88.6%was obtained.The produced Mg alloys consisted of MgCu_(2)and Cu(Mg)or MgCu_(2)and CuMg_(2)phases,depending on the Mg concentration in the Mg alloy.When the electrolysis of calcined dolomite was conducted in MgF_(2)–LiF–CaF_(2)molten salt at 1083 K,the current efficiency was 40.9–71.4%,owing to undesired reactions such as electroreduction of Ca^(2+)or/and CO_(3)^(2−)ions.Meanwhile,the current efficiency increased from 40.9%to 63.2%by utilizing a Pt anode,because the occurrence of CO_(3)^(2−)ions in the molten salt was prevented.After vacuum distillation of the obtained Mg alloys at 1300 K for 10 h,Mg metal with a purity of 99.9996–99.9998%was produced.Therefore,the feasibility of this novel process for the production of high-purity Mg metal from dolomite was demonstrated.

Mg-doped layered oxide cathode for Na-ion batteries

Na-ion batteries(NIBs)are regarding as the optimum complement for Li-ion batteries along with the rapid development of stationary energy storage systems.In order to meet the commercial demands of cathodes for NIBs,O3-type Cu containing layered oxide Na_(0.9)0Cu_(0.22)Fe_(0.30)Mn_(0.48O_(2))with good comprehensive performance and low-cost element components is very promising for the practical use.However,only part of the Cu^(3+)/Cu^(2+)redox couple participated in the redox reaction,thus impairing the specific capacity of the cathode materials.Herein,Mg2+-doped O3-Na0.90Mg0.08Cu0.22Fe0.30Mn0.40O_(2)layered oxide without Mn3+was synthesized successfully,which exhibited improved reversible specific capacity of 118 mAh/g in the voltage range of 2.4-4.0 V at 0.2 C,corresponding to the intercalation/deintercalation of 0.47 Na+(0.1 more than that of Na_(0.9)0Cu_(0.22)Fe_(0.30)Mn_(0.48O_(2))).This work demonstrates an important strategy to obtain advanced layered oxide cathodes for NIBs.

Selection of Stainless Steel for Cathode Plate in Hydrometallurgical Process

Recently, the hydrometallurgy for metal refining is getting more and more popularin China. During a traditional hydrometallurgical process sulphuric acid is often used. In many cases, the working conditions in the solvent extraction and electro winning processes could be very tough for the commonly used material of different equipment and components, such as, austenitic stainless steels of 304/304L and 316L. In a copper refinery, a permanent cathode plate made of 316L was taken out of production due to heavy corrosion. The samples from the corroded plate were investigated thoroughly, possible reasons were pointed out and new material was suggested in this work. It is expected this research could help the copper refineries and Sanmen Sanyou to select the proper cathode plates in complicated working conditions.

Separation and recovery of Cu and As from copper electrolyte through electrowinning and SO_2 reduction

Cu and As were separated and recovered from copper electrolyte by multiple stage electrowinning, reduction with SO2and evaporative crystallization. Experimental results showed that when the current density was 200 A/m2, the electrolyte temperature was 55 °C, the electrolyte circulation rate was about 10 mL/min and the final Cu concentration was higher than 25.88 g/L, the pure copper cathode was recovered. By adjusting the current density to 100 A/m2 and the electrolyte temperature to 65 °C, the removal rate of As was 18.25% when the Cu concentration decreased from 24.69 g/L to 0.42 g/L. After As（V） in Cu-depleted electrolyte was fully reduced to As（Ⅲ） by SO2, the resultant solution was subjected to evaporative crystallization, then As2O3 was produced, and the recovery rate of As was 59.76%. The cathodic polarization curves demonstrated that both Cu2＋ concentration and As（V） affect the limiting current of Cu2＋ deposition.

Recovery of cathode copper and ternary precursors from CuS slag derived by waste lithium-ion batteries:Process analysis and evaluation

The efficient and environmentally friendly recycling technology of waste residue that including abundant heavy metal produced during the recovery of lithium batteries has become a research hotspot.Herein,a novelty process of acid leaching-selective electrodeposition-deep impurity removal-regeneration was proposed to recovery of the CuS slag,which has been efficient transferred to high purity cathode copper and commercially available ternary precursors.Copper cathode with a purity of 99.67%was prepared under electrochemical reaction conditions at-0.55 V for 2 h.A novel impurity remover-Mn powder,which was used to remove the residual impurities and as a feedstock for the ternary precursor.Finally,NCM523 was regenerated by co-precipitation.The process is superior to the traditional process in economy,energy consumption,CO_(2)emissions,product purity and process duration.This study provides a new approach for solid waste recovery and precious metal enrichment.

CATHODIC REDUCTION OF METAL-CHLORIDE COORDINATION IONS

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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).

纳米FeSe_(2)正极材料制备与镁电池中性能表征

采用溶剂热法,利用表面活性剂的分散作用成功合成了FeSe_(2)纳米颗粒,将其作为正极材料组装可充镁电池,并进行电化学性能测试。结果显示,FeSe_(2)正极在100 mA/g电流密度下首次放电比容量为119 mAh/g,并在循环过程中展现出比容量的逐渐升高,在循环48次后获得最大放电比容量628 mAh/g,同时具有良好的循环稳定性,在100次循环后仍保持581 mAh/g的放电比容量。非原位TEM、XPS和同步辐射软X射线吸收谱分析表明,FeSe_(2)正极在循环过程中,铜集流体会参与正极电化学反应并形成含铜化合物,在正极材料中形成导电通路,这有利于电化学反应过程中电子的转移。因此,FeSe_(2)纳米颗粒充分参与正极转化反应,并展现出高容量和长循环稳定性,为镁电池中的集流体和硒族化合物的匹配性设计提供了新的思路。

阴极钛材表面处理工艺对其表面状态及铜离子电沉积初期行为的影响

目的研究表面处理工艺对钛材表面状态的影响,进一步探究阴极钛材表面状态对铜离子电沉积初期形核行为的影响。方法利用砂纸研磨、机械/电解抛光、化学腐蚀等不同的表面处理工艺,制备出不同表面状态的钛材,对钛材的表面粗糙度和形貌分别进行测试和扫描电镜观察。以不同表面状态的钛材作为阴极,进行铜离子的电沉积实验,对初始沉积层组织进行扫描电镜观察,并统计铜晶核的尺寸、覆盖率。结果砂纸研磨的钛材表面粗糙度最大,随着砂纸目数的增加,粗糙度降低,划痕变得细密,沉积的铜晶核尺寸较小、分布均匀、面覆盖率较高;抛光可显著降低钛材表面粗糙度,电解抛光的粗糙度最低,但铜晶核难以牢固附着;化学腐蚀会在钛材表面残留金属颗粒或暴露晶界组织,沉积的铜晶核分布不均匀且易发生团簇。结论铜离子的初始沉积形核行为与阴极钛材的表面粗糙度和缺陷状态密切相关,采用3000#~4000#砂纸精细研磨的方式,可使钛材表面粗糙度Rz保持在1~1.2μm,且表面覆盖有高密度均匀细小的划痕缺陷,最有利于铜离子的高密度均匀形核。

铜电解阴极钛板碳化硅悬浮液超声波协同清洗研究

铜电解阴极钛板作为铜电解工艺的重要组成部分,其表面质量对电解质量和效率及钛板本身使用寿命有显著影响。针对此问题,采用碳化硅悬浮液超声波协同清洗技术对钛板进行简单、高效、环保的表面处理。通过铝箔腐蚀法探究了最佳清洗参数,分析了清洗过程中的协同效应及其作用机理。通过SEM+EDS和接触角测量仪对钛板表面清洁度、微观形貌和湿润性进行表征和评价。结果表明:距离换能器78 mm、碳化硅颗粒质量分数为0.05%,粒径为70 nm、p H值为中性、温度为55℃时清洗效果最佳;碳化硅悬浮液作为清洗介质,其协同效应可以明显提高清洗效率,改善钛板表面质量;清洗前后的对比表明,协同清洗能够有效地去除钛板表面的污染物,提高表面洁净度和湿润性,恢复钛板表面微观形貌及金属光泽。研究为优化钛板清洗工艺提供参考依据。

阴极辊在线抛磨参数对电解铜箔性能的影响

[目的]阴极辊的表面状态会影响电解铜箔的品质,抛磨处理能够令阴极辊保持较佳的表面状态。[方法]通过对日常生产中阴极辊抛磨参数的跟踪与铜箔性能的分析,探究了电解铜箔生产中阴极辊在线抛磨对铜箔粗糙度、拉伸强度、延伸率等性能的影响。[结果]适当提升抛磨刷的摆动频率,降低抛磨刷与阴极辊间的接触压力,增大阴极辊抛磨长度,以及使用小粒度的抛磨刷均能降低铜箔的粗糙度,提高铜箔的常温拉伸强度,减小铜箔纵向与横向延伸率的差异,提高产品合格率。[结论]控制好阴极辊的在线抛磨参数有助于获得品质良好的电解铜箔。

用Cyanex 302萃取废三元正极材料浸出液中铁铜试验研究

研究了用Cyanex 302(主要成分为二(2,4,4-三甲基戊基)单硫代次磷酸)萃取分离废三元正极材料浸出液中的铁和铜,考察了H+浓度、萃取剂浓度、温度对Cyanex 302萃取分离性能的影响,确定了反萃取负载有机相中铁、铜的工艺条件,在此基础上设计了从废三元正极材料浸出液中萃取铁和铜的工艺流程。结果表明:最佳萃取条件为Cyanex 302浓度0.1 mol/L,H^(+)浓度0.1 mol/L,室温;在该条件下,铁、铜萃取率均大于99.9%,镍、钴、锰、锂萃取率均低于0.003%;铁的最佳反萃取剂为1 mol/L H_(2)SO_(4),铜的最佳反萃取剂为1.5 mol/L HNO_(3)。该工艺能有效萃取分离浸出液中的铜、铁。

基于阴极往复运动的TGV电铸铜实心填充工艺

玻璃通孔(TGV)转接板因其具有优良的高频电学特性,在先进封装领域受到广泛关注。然而随着TGV深宽比的不断增加,采用传统的阴极定轴旋转式电铸工艺,其填充难度与成本将随之提高。为实现高深宽比TGV的无缺陷填充,减少电铸耗时和成本,提出一种基于阴极往复运动的TGV无缺陷镀铜填充新工艺。在仿真和实验的基础上,系统研究了阴极运动方式对TGV孔内电铸液传质、离子浓度、填充速率的影响。仿真和实验结果均表明,采用阴极往复运动能有效地保证TGV孔内各处离子浓度分布的均匀一致性,减缓浓差极化,从而提高沉积速率及其上限值。在不含任何添加剂的体系中,同等沉积电位条件下平均填充速率从阴极定轴旋转式电铸工艺的6.1μm/h提高至9.2μm/h。当电位为0.5 V时,阴极往复运动方式下平均填充速率达到45.2μm/h,且电铸铜填充层中未发现孔隙缺陷。这为在无添加剂电铸铜体系中实现高深宽比TGV的无缺陷电铸铜填充提供了一种可行的低成本方案。

铜电解精炼技术研究现状及展望

铜电解精炼是铜产业链中决定铜产品质量和性能的重要环节。本文总结和分析了传统电解精炼法、永久不锈钢阴极法、周期性反向电流法、脉冲电流法、平行流电解精炼法、外场强化电解精炼法等阴极铜电解精炼技术和一次或多次电解精炼制备高纯铜电解精炼技术的原理、研究进展及存在问题,并对铜电解精炼技术进行了展望,指出阴极铜电解技术将朝着原料适应性强、金属回收率高、生产成本和能耗低以及环境友好等方向发展,而高纯铜电解精炼技术则朝着工艺简单化、节能减排、大规模生产以及产品高纯化等方向发展。