电解铜箔添加剂的研究进展及应用现状

随着锂离子电池用阴极铜箔对其性能要求的提高,迫切需要制造出厚度在6μm以下、抗拉强度在300～350 MPa同时延伸率在10%以上的双光铜箔来满足锂电池的需要。已有的研究发现,通过向电解液中添加适合的添加剂可有效提升铜箔的各项性能。阐述了三种有机添加剂及Cl-在铜沉积过程中的作用,又对不同添加剂之间产生的协同作用进行了归纳。因此,合理利用各类添加剂之间的协同作用,可有效控制铜箔性能,为设计组合添加剂提供了思路与依据。     

PEG及其复合添加剂对电解铜箔后处理的影响

为提高电解铜箔在粗化处理后的抗剥离强度。选择添加剂聚乙二醇-8000 (PEG-8000)及PEG和钨酸钠的复合添加剂对12μm电解铜箔进行电镀处理，采用扫描电子显微镜（SEM）、粗糙度检测、电化学分析、X射线衍射分析（XRD）、抗剥离强度及导电性测试来分析添加剂对铜箔表面形貌、性能及添加剂的作用机理分析。随着PEG加入基础镀液，后处理铜箔表面形貌从粗大的树枝晶逐渐转变为短小的粒状晶粒，后处理铜箔粗糙度呈上升趋势。当PEG浓度为0.09g/L时，相较不含添加剂的镀液体系，后处理铜箔抗剥离强度提升达103%，粗糙度升高，PEG的加入会起到促进铜形核和抑制沉积的双重作用。PEG和钨酸钠的复合添加剂加入基础镀液后，当PEG浓度为0.005g/L时，铜箔的抗剥离强度较单一PEG体系提升约21.35%，粗糙度降低约20.34%，由于复合添加剂抑制了铜离子的沉积和形核，并促进了(200)晶面的沉积，铜箔表面晶粒沉积均匀，但晶粒粗大化。PEG单独加入可以大幅提升铜箔的抗剥离强度，且提高粗糙度，PEG和钨酸钠的复合添加剂抗剥离强度进一步提升，且粗糙度下降，深镀能力大幅提升。     

电沉积Zn-Sn合金工艺的研究

在电解铜箔上采用碱性焦磷酸盐体系电镀Zn-Sn合金,可改善铜箔表面的综合性能.研究了配位剂、pH值、温度、电流密度等对镀层质量的影响,选择了合适的添加剂,并对其极化行为进行了研究,优化确定了电镀Zn-Sn合金的镀液组成和工艺条件.经过处理后的电解铜箔耐蚀性、耐热性和粘合强度等性能均有明显提高.     

新型添加剂提高锂电铜箔高温延伸率的研究

针对目前现有铜箔延伸率较低造成锂电池负极出现断带情况,为解决断带造成电池断路及寿命短的问题,采用生产试验系统制备高延伸率锂电铜箔,主要研究了新型添加剂E-P和E-M对锂电铜箔高温延伸率性能的影响。结果表明,添加剂E-M光亮效果良好,可以作为一种光亮剂来替代常用光亮剂;添加剂E-P或E-M单独作用时,可以一定程度提高延伸率,但作用不明显。然而2种添加剂共同作用时,锂电铜箔的表面形貌更加平整,高温延伸率可提高45%～46%,且表观及其它性能均良好,可以满足客户的要求。     

锂离子电池电解液SEI成膜添加剂的研究进展

稳定的固体电解质界面（SEI）是提高锂离子电池电化学性能的关键,用电解液添加剂是改善锂离子电池性能最经济有效的方法之一。本文综述了近五年间包括不饱和酯化合物、含硫化合物、锂盐、无机化合物等作为电解液成膜添加剂在锂离子电池中的研究进展和作用机理,对它们的优缺点进行了评价,最后进行了总结和展望。未来成膜类添加剂的研究思路应该为：（1）应以有机物种为主,能够形成弹性模量小的SEI膜,便于适应阳极材料产生的膨胀行为。（2）添加剂要尽量保证形成的SEI膜与石墨等阳极材料产生良好的黏结,因此添加剂形成的聚合物的聚合度不能太小。（3）在没有性能极其优秀的成膜添加剂出现之前,添加剂的分子结构可以在现有的添加剂的基础上进行结构的优化或者官能团的设计。（4）重点攻关当前添加剂的应用的问题,提高添加剂的合成技术,降低合成成本。     

碳素生产中添加剂的性能和作用

为了进一步提高碳—石墨制品的性能,取得更好的经济效果,近年来,国内外碳素生产中对各种有机物和无机物添加剂的研究,做了不少工作,得到一些成果。添加剂已成为某些产品配方中的一个组成部分,甚至成为某些产品具有特殊性能的重要因素。可以预料,添加剂的使用对于提高产品质量、降低废品率、简化生产工艺、节约原料和能源等都有一定的促进作用。本文就目前国内外已研究使用的各种添加剂的性能和作用作初步探讨。     

锂离子电池用超薄电解铜箔一体机生产技术及防氧化工艺

介绍了锂离子电池用超薄电解铜箔的一体机生产技术,研究了防氧化液中防氧化剂A和苯并三氮唑的含量对电解铜箔防氧化性能的影响。该技术工艺简单,能提高铜箔成品率,不产生废水,能降低生产成本。当防氧化液中防氧化剂A和苯并三氮唑的质量浓度分别为(10±1) g/L和(4±1) g/L时,能够保证所得6~9μm厚的电解铜箔在常温和高温下都具有合格的抗氧化性能。     

PEG和MPS对电解铜箔结构和力学性能的影响

针对目前工业生产中电解铜箔力学性能较差的问题，采用直流电沉积法制备18μm厚的电解铜箔。探究了在基础电解液(由Cu²⁺100 g/L、硫酸110 g/L和盐酸40 mg/L组成)中单独添加或同时添加聚乙二醇(PEG)和3-巯基-1-丙烷磺酸钠(MPS)时对铜箔微观形貌、力学性能和晶相结构的影响，并分析了二者对Cu²⁺电沉积形成铜箔过程中成核的影响。结果表明，PEG和MPS协同作用可以显著提高初始阶段的成核密度，减少气孔等缺陷，令铜箔的致密度和表面平整性得到改善，抗拉强度大幅提升。当同时采用2.0 mg/L MPS和1.2 mg/L PEG作为添加剂时，得到的铜箔力学性能最优，抗拉强度和延伸率分别为425 MPa和5.3%，相比于无添加剂时分别提高了57%和60%。     

锂电池用6μm电解铜箔添加剂的研究

采用正交试验法研究了羟乙基纤维素(HEC)、硫脲(N)、聚乙二醇(P6000)和N,N-二甲基二硫代甲酰胺丙烷磺酸钠(DPS)这四种添加剂对6μm电解铜箔性能的影响。最佳的添加剂配方为:HEC 1.0 mg/L,P6000 2.0 mg/L,N 0.05 mg/L,DPS 2.0 mg/L。     

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。     

化学镀铜技术的最新进展

概述了国内外关于超级化学镀铜填充技术的最新研究成果,主要包括应用于半导体铜互连线工艺的化学镀铜和以次磷酸钠作还原剂的无甲醛化学镀铜。介绍了不同添加剂在超级化学镀铜填充中的作用机理以及存在的问题,并提出了今后的研究方向。     

Quantitation of the dissolution of battery-grade copper foils in lithium-ion battery electrolytes by flame atomic absorption spectroscopy

Atomic absorption spectroscopy (AAS) was shown to be an effective method to quantitatively evaluate the stability of battery-grade copper foils in lithium-ion battery electrolytes at open-circuit. The results showed that copper stability was different between “fresh” electrolyte and electrolytes that had been “aged” for 6 months. In the “fresh” electrolyte, the copper foils showed a small amount of dissolution (up to ∼50 ppm) during their storage for up to 20 weeks. In the “aged” electrolyte, a large amount of copper dissolution (up to several hundred ppm) was found. The study showed that the condition of the electrolytes was critical to the stability of the copper foils.     

The effect of pulsed reverse current on the polarization behaviour of acid copper plating solutions containing organic additives

The polarization behaviour of acid copper solutions containing polyethers, sulphopropyl sulphides and chloride ions was studied using both direct and pulsed reverse current. The effect of these additives on the rest potentials of copper foils immersed in the electrolyte was also studied. Polyethers were found to have an inhibiting effect on the deposition of copper whereas the sulphopropyl sulphides produced a stimulating (i.e. depolarizing) effect. Chloride ion concentration was found to have an influence on the adsorption characteristics of the polyether. The use of pulsed reverse current in solutions containing both polyether and sulphopropyl sulphide was found to inhibit the adsorption/diffusion of the sulphopropyl sulphide at the cathode surface. Thus at higher current densities, above 2 A dm^–2, the inihibiting effect of the polyether produced a shift in the cathodic polarization potential to more negative values as compared with an equivalent current density using direct current. At lower current densities, below 2 A dm^–2, the depolarization effect of the sulphopropyl sulphide was still effective. This effect of pulsed current on additive containing solutions can improve dramatically the metal distribution in low current density areas on plated items. This was illustrated by plating Hull cell panels using both pulsed and direct current.     

Influence of organic additives on the initial stages of copper electrodeposition on polycrystalline platinum

Effects of two additives, thiourea and saccharin, on copper electrodeposition from acid sulphate solutions were investigated by different electrochemical methods (cyclic voltammetry, chronoamperometry, and electrochemical quartz crystal microbalance) as well as by different observation techniques (scanning electron microscopy and atomic force microscopy). The morphology of copper coating obtained with thiourea leads to a smooth and bright deposit whereas it is only slightly modified by saccharin. The electrochemical reactions of copper electrodeposition were modified by the formation of complexes between thiourea and copper. However, in presence of saccharin, the kinetics and morphology of copper coating remain unchanged. From X-ray photoelectron spectroscopy analysis, thiourea was found to react with copper or copper ions by strong bond formation between the sulphur atoms of thiourea molecule and copper. This is the evidence of the adsorption of thiourea on the coating. Moreover, the thiourea action starts in the initial stages, allowing a homogeneous nuclei size and a large nuclei density. Finally, the nucleation mechanism of electrodeposition appears to be modified according to the additives used.     

NSAID-Based Coordination Compounds for Biomedical Applications: Recent Advances and Developments

After the serendipitous discovery of cisplatin, a platinum-based drug with chemotherapeutic effects, an incredible amount of research in the area of coordination chemistry has been produced. Other transition metal compounds were studied, and several new relevant metallodrugs have been synthetized in the past few years. This review is focused on coordination compounds with first-row transition metals, namely, copper, cobalt, nickel or manganese, or with zinc, which have potential or effective pharmacological properties. It is known that metal complexes, once bound to organic drugs, can enhance the drugs’ biological activities, such as anticancer, antimicrobial or anti-inflammatory ones. NSAIDs are a class of compounds with anti-inflammatory properties used to treat pain or fever. NSAIDs’ properties can be strongly improved when included in complexes using their compositional N and O donor atoms, which facilitate their coordination to metal ions. This review focuses on the research on this topic and on the promising or effective results that complexes of first-row transition metals and NSAIDs can exhibit.     

Copper electrodeposition from an acidic plating bath containing accelerating and inhibiting organic additives

Copper electrodeposition on copper from still plating solutions of different compositions was investigated utilising electrochemical impedance spectroscopy (EIS), cyclic voltammetry, and scanning electron microscopy (SEM). An acid copper sulphate plating base solution was employed either with or without sodium chloride in the presence of a single additive, either polyethylene glycol (PEG) or 3-mercapto-2-propanesulphonic acid (MPSA), and their mixture. Thallium underpotential deposition/anodic stripping was employed to determine the adsorption capability of additives on copper. In the absence of chloride ions, MPSA shows a moderate adsorption on copper, whereas PEG is slightly adsorbed. At low cathodic overpotentials, the simultaneous presence of MPSA and chloride ions accelerates copper electrodeposition through the formation of an MPSA-chloride ion complex in the solution, particularly for about 220 μM sodium chloride. The reverse effect occurs in PEG-sodium chloride plating solutions. In this case, from EIS data the formation of a film that interferes with copper electrodeposition can be inferred. At higher cathodic overpotentials, when copper electrodeposition is under mass transport control, the cathode coverage by a PEG-copper chloride-mediated film becomes either partially or completely detached as the concentration of chloride ions at the negatively charged copper surface diminishes. The copper cathode grain topography at the μm scale depends on the cathodic overpotential, plating solution composition and average current density. Available data about the solution constituents and their adsorption on copper make it possible to propose a likely complex mechanism to understand copper electrodeposition from these media, including the accelerating effect of MPSA and the dynamics of PEG-copper chloride complex adsorbate interfering with the surface mobility of depositing copper ad-ions/ad-atoms.     

The influence of some parameters on the surface roughness of thin copper foils using statistical analysis

The influence of nucleation potential, nucleation time, growth potential and substrate roughness on the surface roughness of thin copper foils deposited electrolytically on titanium substrates from a 83 g dm^–3 Cu²⁺ and 140 g dm^–3 H₂SO₄ solution at a temperature of 65 °C, using 2k⁴ factorial design, was studied. A mathematical model to determine the average surface roughness, a quality parameter of thin copper foils, was established. Statistical adjustment of the model enables its use in accurate prediction (error lower than 5%) of the average surface roughness of thin copper foils. The initial steps of copper nucleation and growth are particularly important for the quality of thin (18 m) copper foils, because during its manufacture, a rapid and homogeneous covering of the entire surface of the electrode becomes fundamental in order to obtain foils with a low surface roughness and a low degree of pinholes per unit area. Mechanisms for copper nucleation on titanium, based on the Thirsk and Harrison model for different experimental conditions, were determined with the aid of potentiostatic current transients. It was shown that the roughness of the thin copper foils is a function of not only the growth process, but also the nucleation process and that the lowest surface roughness is related to a pre-nucleation step at –0.590 V for 10 ms on a titanium substrate polished with 600-grit paper.     

火电厂铜合金凝汽器氯离子腐蚀及缓蚀剂研究综述

目前我国火力发电厂凝汽器材质以铜合金为主,而氯离子对铜合金凝汽器的腐蚀是火电厂循环冷却水系统的主要腐蚀性因素,直接关系到生产的安全运行.作者首先针对铜合金材质氯离子腐蚀评价方法及腐蚀机理进行了综述,然后对该类缓蚀剂的研究进展进行了系统归纳,涉及BTA及其衍生物以及MBT的论述,亦包括了其他唑类及非唑类缓蚀剂情况,同时对部分缓蚀剂的腐蚀控制机理进行了描述,旨在对铜合金材质氯离子的腐蚀及控制的现状及发展方向有一个系统的把握.     

减摩抗磨类新型润滑油添加剂的研究进展

减摩抗磨类润滑油添加剂能提高基础润滑油的摩擦学性能使其在润滑领域具有广阔的应用前景,但是商用润滑油添加剂大多含有P、S等有害元素,因此,寻找更加环保、经济的润滑油添加剂具有重要意义。本文根据润滑油添加剂结构种类和润滑机理的不同,以及国内外各种润滑油添加剂在润滑方面的相关成果,综述了近年来纳米颗粒(纳米单质及其复合颗粒、纳米氧化物、纳米硫化物、纳米氮化物)、含氮杂环化合物及其衍生物、硼酸酯及其衍生物、离子液体等添加剂的合成方法以及在减摩抗磨方面的应用,并对其发展状况和减摩抗磨机理进行了探究。指出了其润滑机理主要为吸附膜机理、摩擦反应膜机理和滚珠机理。最后对其存在的问题进行分析,提出了当前润滑领域研究的热点和方向依然是复合添加剂的制备和机理探究。     

Synthesis and practicability of novel additives for copper electroplating with semiconductor packaging

Connection reliability between Large Scale Integrated circuit (LSI) and electronic devices is increasingly important with the miniaturization of electronic devices. For the formation of fine conductors on wiring in electronic devices, copper electroplating is generally applied and is controlled with various organic additives. In this study, for the purpose of developing additives capable of working on a finer conductive copper circuit, we focused our attention on the synthesis of organic additives with inhibition action for the plating. Generally, poly(ethylene glycol) (PEG) was used as an inhibitor. We synthesized the PEG derivatives, which were α‐(2‐chloroethyl)‐ω‐chloropoly(oxyethylene) (PEG‐Cl) and α‐(2‐sulfoethyl)‐ω‐sulfopoly(oxyethylene)disodium, and evaluated them for their Via‐filling properties. Good filling properties were achieved by the addition of these synthesized materials to a normal copper‐plating bath. Furthermore, with PEG‐Cl, good filling properties were achieved without chlorine ions, which were usually added to the bath. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 837–840, 2005