CN112195435A - 一种类核壳结构Al@(TiB2+Ti4O7)-PbO2阳极板及其制备方法 - Google Patents
一种类核壳结构Al@(TiB2+Ti4O7)-PbO2阳极板及其制备方法 Download PDFInfo
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Abstract
本发明公开一种类核壳结构Al@(TiB2+Ti4O7)‑PbO2阳极板及其制备方法,属于湿法冶金和电化学冶金技术领域。本发明所述Al@(TiB2+Ti4O7)‑PbO2阳极板主要包括Al金属板载体,TiB2+Ti4O7陶瓷中间过渡层和PbO2活性催化层。本发明所述方法,首先制备TiB2+Ti4O7混合陶瓷粉末;然后在经表面粗化刻蚀后的Al板上先预喷涂NiAl系打底层,紧接着喷涂TiB2+Ti4O7陶瓷中间过渡层,以制备Al@(TiB2+Ti4O7)类核壳结构电极基体;最后采用电沉积法,在其表面电沉积PbO2活性催化层。本发明所制备的阳极板具有催化活性高、成本低廉、使用寿命长、适应性广等优点。
Description
技术领域
本发明涉及一种类核壳结构Al@(TiB2+Ti4O7)-PbO2阳极板及其制备方法,属于湿法冶金和电化学冶金技术领域。
背景技术
有色金属己成为决定一个国家经济、科学技术、国防建设等发展的重要物质基础,也是提升国家综合实力和保障国家安全的关键战略性资源。而在现今的有色金属行业中,随着金属矿石品质的不断降低,湿法冶金正以其独特的优势成为有色金属提取的主要方式之一,而湿法冶金自身也存在着对能源、环境和资源的大量消耗,因此它备受人们所重视。就目前而言,大约有20-30种金属的工业化大规模提炼以及生产均是以湿法冶金的电化学过程为主,而作为湿法冶金工业电化学体系中“心脏”器官的电极材料,其选择和制备一直是实现工业化生产的瓶颈问题所在。
在当前湿法冶金和电化学工业中常用的阳极材料主要有Pb合金电极、Ti基金属氧化物涂层电极以及石墨电极等,其中Pb-Ag合金电极和Ti基涂层电极的应用最为广泛。Pb-Ag合金电极被广泛用于硫酸及硫酸盐介质、中性介质和铬酸盐介质等环境中,在湿法冶金领域一直占有非常重要的地位。但不可否认由于Pb阳极质量大、强度低、内阻高,特别是表面靠电解过程这一自然方式形成的氧化膜催化层疏松、多孔,易于脱落;Ti基涂层电极具有尺寸稳定、耐腐蚀、重量轻和高强度的优点,在氯碱行业中应用广泛,具有良好的前景和发展方向。但是Ti电极的内阻较大,导致其电解能耗较大,而且Ti电极主要以铱、钌、钽等稀贵金属氧化物作为活性催化涂层原料,原料成本较贵,涂层在硫酸电解过程中易脱落失效。
Al因其良好的导电性,以及具有即使在电沉积过程中被浸蚀也不会毒化电解液、污染阴极析出产品等优点,而受到研究者们的广泛关注。然而,所有的研究均未能解决在长期电沉积过程中新生态氧原子和酸液沿着涂层孔隙扩散到基体表面形成氧化物绝缘层或基体被浸蚀使阳极失效的问题。因此,如何进一步的提升新型电极的性能,就需从如何降低涂层电极基体的电阻率,同时保护低电阻率的基体在电沉积过程中不被浸蚀的问题入手。
专利申请“一种铝基复合陶瓷涂层电极板及其制备方法”公开了Al/TiB2+Ti4O7基体电极的制备方法,电极虽具有良好的导电性和耐腐蚀性,但由于该方法所制备的原始粉末只是通过简单的混料机混粉制备,所以成分均匀性和粉末流动性仍有待提高,且最外层无PbO2活性催化层,因此其析氧电位偏高;专利“一种镍电积用铝基复合阳极及其制备方法”(周生刚,罗开亮,徐阳…)公开了Al/TiB2/PbO2电极的制备方法,该电极具有槽电压低,电流效率高等优点,但是由于Al金属基体和TiB2陶瓷自身固有的差异如热膨胀系数差异过大等原因,电极界面处容易造成开裂,从而涂层和活性催化层易脱落失效,同时该电极没有添加高导电材料如Ti4O7等,所以其电阻较高。
发明内容
本发明的目的在于弥补现有技术的不足,采用质量轻、导电好、价格低廉的阀型金属Al为“核”、用与之润湿性好、耐蚀强、具有一定催化活性的 TiB2与 Ti4O7混合金属陶瓷粉包覆层为“壳”,以此获得Al@(TiB2+Ti4O7)类核壳结构电极基体,最后在其表面采用电沉积工艺制备PbO2活性催化层,以获得Al@(TiB2+Ti4O7)-PbO2阳极板。
本发明通过以下技术方案实现:
一种类核壳结构Al@(TiB2+Ti4O7)-PbO2阳极板,所述Al@(TiB2+Ti4O7)-PbO2阳极板主要包括Al金属板载体,TiB2+Ti4O7陶瓷中间过渡层和PbO2活性催化层。
本发明的另一目的在于提供所述Al@(TiB2+Ti4O7)-PbO2阳极板的制备方法,具体包括以下步骤:
(1)Al金属板预处理:对Al金属板表面进行打磨,超声清洗后用蒸馏水清洗表面,干燥后进行喷砂处理。
(2)TiB2+Ti4O7混合陶瓷粉末的制备:采用喷雾造粒的方法对团聚烧结型TiB2+Ti4O7混合粉末进行球化造粒处理,以提高粉末流动性和改善其成分均匀性。
(3)喷涂TiB2+Ti4O7混合陶瓷中间层:在步骤(1)预处理过的Al金属板表面采用大气等离子喷涂的方式喷涂步骤(2)造粒处理过的TiB2+Ti4O7混合陶瓷粉末;具体过程为:首先对Al金属板进行200-300℃预热处理,然后先预喷涂NiAl系打底层,以改善因Al和TiB2、Ti4O7金属陶瓷间热力学性质差异过大所引起的涂层开裂等缺陷;紧接着在Ar、H2的气氛作用下,通过等离子焰流对混合粉末进行加热,使其呈熔融或半熔融态沉积在Al金属板上,以得到Al@(TiB2+Ti4O7)类核壳结构电极基体。
(4)电沉积PbO2活性催化层:将步骤(3)所制得的Al@(TiB2+Ti4O7)电极基体置于电沉积液中作为阳极,以石墨作为阴极,在直流电源的作用下进行电沉积工艺,以制备Al@(TiB2+Ti4O7)-PbO2阳极板。
优选的,本发明步骤(1)所述Al金属板为1060纯铝或6061铝合金,尺寸为200mm×200mm×6mm。
优选的,本发明Al金属板预处理的具体过程为:首先对Al金属板表面的打磨,再在5-15wt.%的NaOH碱性溶液中超声清洗10-20min,然后用蒸馏水清洗表面,干燥后进行喷砂处理,喷砂所需的刚玉砂的粒径为40-80目,Al金属板表面粗糙度为1-4。
优选的,本发明步骤(2)中所述喷雾造粒的具体过程为:将TiB2和Ti4O7粉末按90wt.%TiB2+10wt.%Ti4O7的比例混合,同时加入去离子水,在行星球磨机中球磨,然后再将聚乙烯醇加入浆料中继续球磨,以制备复合粉体浆料供喷雾造粒使用,最后,采用喷雾干燥机进行喷雾造粒,在喷雾造粒过程中,其喷雾造粒参数具体为:干燥温度为150-240℃,粘接剂含量为0.3-1.5wt.%,固相含量为40-60wt.%,其余为水,雾化盘转速为9000r/min-10800r/min;喷雾造粒处理后,混合粉末的松装密度明显提高,粉末呈球形或类球形。
优选的,本发明步骤(2)所述TiB2、Ti4O7原始粉末均由团聚烧结法制备,其原始粉末粒径为1-3μm,喷雾造粒后粉末粒径为15-45μm。
优选的,本发明步骤(3)所述NiAl系打底层的厚度为20-50μm;在大气等离子喷涂过程中,其喷涂参数具体为,喷涂功率32-42kW,送粉速率为2-4rpm,喷涂距离10-14cm,Ar流量为100-120SCF/h,H2流量为15-18SCF/h,喷涂路径为环形间歇式。
优选的,本发明步骤(4)所述在电沉积PbO2活性层过程中,其电沉积参数具体为,电流密度为0.01-0.05A/cm2,电沉积温度为30-60℃,电沉积时间为2-6h,电沉积液pH为1-2。
除特别说明外,本发明所有百分比都为质量百分比。
本发明制备所得到的Al@(TiB2+Ti4O7)-PbO2阳极板具有催化活性高、成本低廉、使用寿命长、适应性广等优点,其使用方法和外形尺寸完全满足传统铅电极和钛电极的工况要求,可用作有色金属电解用新型电极板。
本发明的有益效果:
(1)本发明首先采用大气等离子喷涂技术在经表面粗化刻蚀后的Al板上沉积TiB2+Ti4O7混合金属陶瓷,制备出Al@(TiB2+Ti4O7)类核壳结构电极基体;其中,Al内核作为电极的集流载体和导电骨架,壳层TiB2+Ti4O7既是Al内核的防腐保护层和电子传输层,又是最外活性涂层的连结强化中间过渡层,利用TiB2的高导电性、耐蚀性和与Al的润湿性,以及Ti4O7的自身的高催化性、耐蚀性和与PbO2较好的结合性,构筑成一个既能有效保护Al基体,又能高效传输电子和活性转换的过渡中间核壳体;最后采用电沉积法,在其表面电沉积PbO2活性催化层,制备一种催化活性高、成本低廉、使用寿命长、适应性广的节能新型复合功能电极。
(2)本发明在大气等离子喷涂工艺中,首先对TiB2+Ti4O7混合陶瓷粉末进行喷雾造粒处理,有效改善了混合粉末自身的流动性以及成分均匀性等问题,使其有效提高喷涂效率;此外,由于金属基体与陶瓷之间固有的热膨胀等性能差异较大,通过在Al基体上预喷涂NiAl系打底层,可以有效缓解涂层开裂等问题,使其金属/陶瓷界面结合更为牢固,从而能有效提高Al基体耐腐蚀性能。
(3)和现有阳极板结构设计相比,本设计采用新型“类核-壳结构”电极结构设计思路,以期通过性能互补得到性能更为优异的电极材料;具体的,Al 导电好质量轻,但不耐腐蚀;TiB2耐蚀强、导电好,但属硬脆相、难成形;Ti4O7析氧电位低、耐蚀性强;PbO2催化活性高,但析氧电位高;为此,通过将三者进行有效调配,以引起不同组份之间的电子交换,从而引发协同作用,使电极性能得到进一步改善。尽管当前耐酸型金属氧化物涂层电极材料的研究已成为国内外关注的热点项目,但是采用类核壳结构金属陶瓷包覆铝基的氧化物涂层材料的研究还未见报道。
附图说明
图1是造粒前后TiB2+Ti4O7混合粉末的SEM图。
图2是造粒后TiB2+Ti4O7混合粉末的XRD图。
图3是Al@(TiB2+Ti4O7)类核壳结构电极基体截面SEM图。
图4是电沉积PbO2活性催化层表面SEM图。
图5是不同阳极 LSV曲线对比图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步详细说明,但本发明的保护范围并不限于所述内容,在本领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下作出各种变化。
实施例1
一种类核壳结构Al@(TiB2+Ti4O7)-PbO2阳极板,主要包括Al金属板载体,TiB2+Ti4O7陶瓷中间过渡层和PbO2活性催化层,所用Al金属板为6061铝合金,尺寸为200mm×200mm×6mm,具体制备过程包括以下步骤:
(1)用钢丝刷对Al金属板表面进行打磨处理,再在10wt.%的NaOH碱性溶液中超声清洗10min,蒸馏水清洗表面,干燥箱干燥后进行喷砂处理,以获得表面粗化的Al金属板。
(2)采用喷雾造粒的方法对团聚烧结型TiB2+Ti4O7混合粉末(90wt.%TiB2+10wt.%Ti4O7)进行球化造粒处理,具体的工艺参数为,干燥温度为180℃,粘接剂含量为0.6wt.%,固相含量为40wt.%,雾化盘转速为 9050r/min,造粒前后TiB2+Ti4O7混合粉末的SEM图如图1所示;从图1可知,喷雾造粒处理前,粉末呈不规则形状,且两种粉末混合均匀程度较低;喷雾造粒处理后,混合粉末呈球形或类球形,从而粉末流动性明显提高,有助于送粉;结合图2XRD可知,造粒处理后,原始粉末主要相仍为TiB2相和Ti4O7相,造粒未引入其它杂质相,喷雾造粒后粉末粒径约为15-45μm。
(3)在步骤(1)预处理过的Al金属板表面采用大气等离子喷涂的方式喷涂步骤(2)造粒处理过的TiB2+Ti4O7混合陶瓷粉末;具体的,首先用等离子枪对Al金属板表面进行200℃预热处理,然后先预喷涂NiAl系打底层,打底层厚度约为20-50μm;紧接着在Ar、H2的气氛作用下,将混合粉末送入混合器,设定喷涂路径和具体的工艺参数,喷涂功率36kW,送粉速率为2rpm,喷涂距离12cm,Ar流量为100SCF/h,H2流量为15SCF/h,喷涂路径为环形间歇式;在等离子焰流的加热作用下,混合粉末呈熔融或半熔融态沉积在Al金属板上,以得到Al@(TiB2+Ti4O7)类核壳结构电极基体;图3为Al@(TiB2+Ti4O7)类核壳结构电极基体截面SEM图,从图3分析可知,涂层呈典型的层状结构,涂层空隙较少。此外,NiAl系打底层有效改善了金属/陶瓷界面间的结合问题,界面出无明显裂纹,部分区域呈冶金式结合。
(4)将步骤(3)所制得的Al@(TiB2+Ti4O7)电极基体置于电沉积液中作为阳极,以石墨作为阴极,在直流电源的作用下进行电沉积工艺,以制备Al@(TiB2+Ti4O7)-PbO2阳极板;具体的,电流密度为0.02A/cm2,电沉积温度为30℃,电沉积时间为2h,电沉积液pH为1;PbO2活性催化层表面SEM图如图4所示。从图4分析可知,催化层表面PbO2颗粒由四面体颗粒堆积而成,颗粒间的缝隙较小,颗粒尺寸较为均匀。
实施例2
一种类核壳结构Al@(TiB2+Ti4O7)-PbO2阳极板,主要包括Al金属板载体,TiB2+Ti4O7陶瓷中间过渡层和PbO2活性催化层,所用Al金属板为1060纯铝,尺寸为200mm×200mm×6mm,具体制备过程包括以下步骤::
(1)用钢丝刷对Al金属板表面进行打磨处理,再在5wt.%的NaOH碱性溶液中超声清洗20min,蒸馏水清洗表面,干燥箱干燥后进行喷砂处理,以获得表面粗化的Al金属板。
(2)采用喷雾造粒的方法对团聚烧结型TiB2+Ti4O7混合粉末(90wt.%TiB2+10wt.%Ti4O7)进行球化造粒处理,具体的工艺参数为,干燥温度为200℃,粘接剂含量为1wt.%,固相含量为50wt.%,雾化盘转速为 9000r/min。
(3)采用等离子喷涂法在表面粗化的Al金属板上沉积TiB2+Ti4O7混合陶瓷涂层。具体的,将表面粗化的Al金属板固定在工作架上,用等离子枪对Al金属板表面进行200℃预热处理,将喷雾造粒处理后的TiB2+Ti4O7混合粉末送入送粉器中,喷涂功率为40kW,送粉速率为3rpm,喷涂距离12cm,Ar流量为120SCF/h,H2流量为15SCF/h;检查设定参数无误和送粉器送粉均匀连续后,点击电脑上预先编程好的喷涂路径(环形间歇式)开始热喷涂工序。
(4)采用电沉积工艺进行PbO2活性催化层的制备;其中,阴阳极尺寸相同,极间距为2cm,电解液循环流动;电沉积参数为,电流密度为0.04A/cm2,电沉积温度为40℃,电沉积时间为2h,电沉积液pH为2。本实施例制备得到的催化层表面PbO2颗粒由四面体颗粒堆积而成,颗粒间的缝隙较小,颗粒尺寸较为均匀。
实施例3
一种类核壳结构Al@(TiB2+Ti4O7)-PbO2阳极板,主要包括Al金属板载体,TiB2+Ti4O7陶瓷中间过渡层和PbO2活性催化层,所用Al金属板为1060纯铝,尺寸为200mm×200mm×6mm,具体制备过程包括以下步骤:
(1)用钢丝刷对Al金属板表面进行打磨处理,再在10wt.%的NaOH碱性溶液中超声清洗15min,蒸馏水清洗表面,干燥箱干燥后进行喷砂处理,以获得表面粗化的Al金属板。
(2)采用喷雾造粒的方法对团聚烧结型TiB2+Ti4O7混合粉末(90wt.%TiB2+10wt.%Ti4O7)进行球化造粒处理,具体的工艺参数为,干燥温度为240℃,粘接剂含量为1.5wt.%,固相含量为60wt.%,雾化盘转速为 10800r/min。
(3)采用等离子喷涂法在表面粗化的Al金属板上沉积TiB2+Ti4O7混合陶瓷涂层;具体的,将表面粗化的Al金属板固定在工作架上,用等离子枪对Al金属板表面进行200℃预热处理,将喷雾造粒处理后的TiB2+Ti4O7混合粉末送入送粉器中,喷涂功率为42kW,送粉速率为4rpm,喷涂距离14cm,Ar流量为110SCF/h,H2流量为18SCF/h;检查设定参数无误和送粉器送粉均匀连续后,点击电脑上预先编程好的喷涂路径(环形间歇式)开始热喷涂工序。
(4)采用电沉积工艺进行PbO2活性催化层的制备;其中,阴阳极尺寸相同,极间距为2cm,电解液循环流动;电沉积参数为,电流密度为0.04A/cm2,电沉积温度为40℃,电沉积时间为2h,电沉积液pH为2。本实施例制备得到的催化层表面PbO2颗粒由四面体颗粒堆积而成,颗粒间的缝隙较小,颗粒尺寸较为均匀。
图5为不同阳极 LSV曲线对比图。从图5分析可知,不同实施例所制备的Al@(TiB2+Ti4O7)-PbO2阳极的极化电位相比Pb基合金电极和Ti基PbO2电极的电极电位均负移,从而该方法说明所制备的电极催化活性较高,实施例3制备的Al@(TiB2+Ti4O7)-PbO2阳极的电催化活性相比其它两个实施例所制备的电极的催化活性更高。
Claims (8)
1.一种类核壳结构Al@(TiB2+Ti4O7)-PbO2阳极板,其特征在于:所述Al@(TiB2+Ti4O7)-PbO2阳极板主要包括Al金属板载体,TiB2+Ti4O7陶瓷中间过渡层和PbO2活性催化层。
2.权利要求1所述类核壳结构Al@(TiB2+Ti4O7)-PbO2阳极板的制备方法,其特征在于,具体包括以下步骤:
(1)Al金属板预处理:对Al金属板表面进行打磨,超声清洗后用蒸馏水清洗表面,干燥后进行喷砂处理;
(2)TiB2+Ti4O7混合陶瓷粉末的制备:采用喷雾造粒的方法对TiB2+Ti4O7混合粉末进行球化造粒处理,所用的粘结剂为聚乙烯醇;
(3)喷涂TiB2+Ti4O7混合陶瓷中间层:在步骤(1)预处理过的Al金属板表面采用等离子喷涂的方式喷涂步骤(2)造粒处理过的TiB2+Ti4O7混合陶瓷粉末,首先对Al金属板进行200-300℃预热处理,然后先预喷涂NiAl系打底层,紧接着在Ar、H2的气氛作用下,通过等离子焰流对TiB2+Ti4O7混合粉末进行加热,使其呈熔融或半熔融态沉积在Al金属板上,以得到Al@(TiB2+Ti4O7)类核壳结构电极基体;
(4)电沉积PbO2活性催化层:将步骤(3)所制得的Al@(TiB2+Ti4O7)电极基体置于电沉积液中作为阳极,以石墨作为阴极,在直流电源的作用下进行电沉积工艺,以制备Al@(TiB2+Ti4O7)-PbO2阳极板。
3.根据权利要求2所述类核壳结构Al@(TiB2+Ti4O7)-PbO2阳极板的制备方法,其特征在于:Al金属板预处理的具体过程为:首先对Al金属板表面的打磨,再在5-15wt.%的NaOH碱性溶液中超声清洗10-20min,然后用蒸馏水清洗表面,干燥后进行喷砂处理,喷砂所需的刚玉砂的粒径为40-80目,Al金属板表面粗糙度为1-4。
4.根据权利要求3所述类核壳结构Al@(TiB2+Ti4O7)-PbO2阳极板的制备方法,其特征在于:步骤(1)所述Al金属板为1060纯铝或6061铝合金,尺寸为200mm×200mm×6mm。
5.根据权利要求2所述类核壳结构Al@(TiB2+Ti4O7)-PbO2阳极板的制备方法,其特征在于:步骤(2)中所述喷雾造粒的具体过程为:将TiB2和Ti4O7粉末按90wt.%TiB2+10wt.%Ti4O7的比例混合,同时加入去离子水,在行星球磨机中球磨,然后再将聚乙烯醇加入浆料中继续球磨,以制备复合粉体浆料供喷雾造粒使用,最后,采用喷雾干燥机进行喷雾造粒,在喷雾造粒过程中,其喷雾造粒参数具体为:干燥温度为150-240℃,粘接剂含量为0.3-1.5wt.%,固相含量为40-60wt.%,其余为水,雾化盘转速为9000r/min-10800 r/min。
6.根据权利要求5所述类核壳结构Al@(TiB2+Ti4O7)-PbO2阳极板的制备方法,其特征在于:所述TiB2、Ti4O7原始粉末均由团聚烧结法制备,其原始粉末粒径为1-3μm,喷雾造粒后粉末粒径为15-45μm。
7.根据权利要求2所述类核壳结构Al@(TiB2+Ti4O7)-PbO2阳极板的制备方法,其特征在于:步骤(3)所述NiAl系打底层的厚度为20-50μm;在大气等离子喷涂过程中,其喷涂参数具体为:喷涂功率32-42kW,送粉速率为2-4rpm,喷涂距离10-14cm,Ar流量为100-120SCF/h,H2流量为15-18SCF/h,喷涂路径为环形间歇式。
8.根据权利要求2所述类核壳结构Al@(TiB2+Ti4O7)-PbO2阳极板的制备方法,其特征在于:步骤(4)所述在电沉积PbO2活性层的过程中,其电沉积参数具体为,电流密度为0.01-0.05A/cm2,电沉积温度为30-60℃,电沉积时间为2-6h,电沉积液pH为1-2。
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