CN111926309B - 一种金属氧化物电极用钛基的防钝化涂层及其制备方法 - Google Patents
一种金属氧化物电极用钛基的防钝化涂层及其制备方法 Download PDFInfo
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- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 4
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- QORWLRPWMJEJKP-UHFFFAOYSA-N butan-1-olate;tantalum(5+) Chemical compound [Ta+5].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] QORWLRPWMJEJKP-UHFFFAOYSA-N 0.000 claims description 3
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- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种金属氧化物电极用钛基的防钝化涂层，由过渡层和功能涂层构成，所述的过渡层为导电性TiO2膜层，所述的功能涂层为SnO2基复合涂层，其化学组成为：钛基防护成分SnO2、改性剂，按摩尔百分比总量为100％计，其中钛基防护成分SnO2的摩尔分数不少于90％，余为改性剂，所述改性剂为高价贱金属氧化物、贵金属氧化物中的一种，本发明得到的涂层具有低成本、沉积可控、成分均匀，结构致密，高稳定性和对环境友好的特点，易于实现涂层成分的设计，工艺简单，适合规模化生产，解决了现有技术存在的成本高、Sn沉积不易控制且稳定性差的问题。
Description
技术领域：
本发明涉及一种金属氧化物电极用钛基的防钝化涂层及其制备方法。
背景技术：
金属氧化物电极是一种在阀型基体上涂敷金属氧化物而成的电极，在电解、电镀、铝箔化成和阴极保护等领域具有广泛的应用。通常金属氧化物电极选用纯钛为电极的基体材料。研究表明，金属氧化物电极的失效部分归因于钛基体表面发生钝化而形成不导电的氧化钛薄膜。为了延迟钛基钝化和延长氧化物电极使用寿命，一般在钛基体、活性氧化物涂层之间引入耐腐蚀性好、导电性好和电化学活性低的涂(镀)层，如贵金属镀层等中间层。目前比较典型的涂镀层有Pt镀层和SnO2-Sb2O3涂层。陶自春等(陶自春等，铂中间层的制备对铱钽涂层钛阳极性能的性能.材料科学与工程，2004,22(2):240)报道了采用电镀、刷镀和磁控溅射等3种工艺制备Pt镀层。研究结果表明，Pt镀层抗氧化性能好，含Pt镀层的铱钽氧化物阳极寿命较长，但Pt价格昂贵，制作成本高，限制了电极应用。SnO2-Sb2O3涂层(宋秀丽等，钛基氧化物阳极中间层的研究进展，电化学，2013，19(4):313)一般采用无机氯化物热分解法制备，这种涂层价格低廉，具有耐蚀性但涂层中的Sn沉积不易控制且稳定性差。
发明内容：
本发明的目的是提供一种金属氧化物电极用钛基的防钝化涂层及其制备方法，具有低成本、沉积可控、高稳定性和对环境友好的特点，解决了现有技术存在的成本高、Sn沉积不易控制且稳定性差的问题。
本发明是通过以下技术方案予以实现的：
一种金属氧化物电极用钛基的防钝化涂层，由过渡层和功能涂层构成，所述的过渡层为导电性TiO2膜层，所述的功能涂层为SnO2基复合涂层，其化学组成为：钛基防护成分SnO2、改性剂，按摩尔百分比总量为100％计，其中钛基防护成分SnO2的摩尔分数不少于90％，余为改性剂，所述改性剂为高价贱金属氧化物、贵金属氧化物中的一种。
所述的高价贱金属氧化物为Ta2O5、Nb2O5。
所述的贵金属氧化物为RuO2、IrO2。
所述的功能涂层厚度为0.5～5μm。
二氧化锡SnO2价格低廉，无明显毒性。二氧化锡在酸性环境中耐蚀性好，具有搪瓷性，与TiO2膜层附着强度高，可为钛基提供有效保护。
改性剂的含量低，附加成本低，在酸性环境中较稳定，其作用是改善氧化物涂层的导电性能，同时提高涂层的化学稳定性。
上述的功能涂层小于0.5μm，不能有效保护钛基，厚度大于5μm则降低了与钛基的结合力，因此涂层理想的厚度为0.5～5μm。
本发明所述的防钝化涂层制备方法包括以下步骤：
①用5％～10％(质量分数)的草酸溶液在85～95℃下蚀刻钛材2～4h，水洗后室温下凉干；
②钛基在空气气氛、400～450℃下进行预氧化5～15min得到过渡层；
③将涂液均匀涂覆在过渡层上；以涂液金属摩尔百分比总量为100％计，所述的涂液配方为：Sn有机前驱体摩尔分数不少于90％，余为改性剂前驱体，溶剂为乙醇和正丁醇，涂液中金属离子浓度为0.1～0.4mol/L；涂液浓度大，涂覆次数少；浓度小，涂覆次数多，操作中灵活使用；
④在100～120℃下固化10～15min；
⑤在450～520℃下热氧化分解10～15min；
⑥在450～520℃下热处理1h。
通常置于大气环境中的钛基表面覆有一层疏松的氧化钛，这种氧化物膜层会影响钛基与后续涂覆涂层的结合力。草酸的作用是去除钛基表面的氧化钛膜层，以得到清洁的基体。
预氧化是在钛基表面预制导电性的氧化钛薄层，构成一层过渡层，目的是提高钛基与SnO2基复合涂层间的结合力。预氧化时，钛基表面保持空气流动。时间超过15min，则易于生成绝缘的膜层，优选预氧化时间5～15min。
所述的Sn有机前驱体为烷氧基锡、醋酸锡。与锡氯化物相比，有机前驱体的沸点较高，挥发减少，锡沉积率得以提高。
所述的改性剂前驱体为高价贱金属、贵金属前驱体中的一种；高价贱金属前驱体选自氯化钽、五正丁氧基钽、氟铌酸、草酸铌中的任一种，优选五正丁氧基钽、草酸铌。
贵金属前驱体为氯化钌、三氯化铱、氯铱酸中的任一种，优选氯化钌、氯铱酸。
涂覆可以采用刷涂、浸涂和喷涂方式。选用刷涂时，用力适度，纵向和横向刷涂交替进行，以保证涂层的均匀性。采用浸涂时，提拉速度为1～50μm/s。采用喷涂时，进气压力0.2～0.5MPa，喷涂距离20～30cm。考虑到操作易于自动化、涂层均匀性和一致性，优选喷涂方式。
上述的固化是在热力的作用下去除有机溶剂，将前驱物附着在钛基过渡层表面。当温度高于120℃时，溶剂挥发过快，会影响涂层的结合力，一般选择100～120℃进行干燥固化。
热氧化分解是将前驱体转变为金属氧化物。当温度低于450℃时，金属前驱体氧化分解不彻底。当高于520℃时，钛材会发生严重氧化，因此理想的热氧化分解温度为450～520℃，优选480～500℃。
热处理是消除复合涂层中的内应力，提高钛基、过渡层与功能涂层间的结合力。温度高于520℃时，钛材会发生严重氧化，因此理想的热处理温度为450～520℃。
本发明的有益效果如下：
本发明得到的涂层具有低成本、沉积可控、成分均匀，结构致密，高稳定性和对环境友好的特点，易于实现涂层成分的设计，工艺简单，适合规模化生产，解决了现有技术存在的成本高、Sn沉积不易控制且稳定性差的问题。
附图说明：
图1-4分别是实施例1-4制得的防钝化涂层的扫描电镜图。
具体实施方式：
以下是对本发明的进一步说明，而不是对本发明的限制。
实施例1：
选用纯钛片TA2为基体，用10％(质量分数)的草酸90℃下蚀刻3h，水洗后室温下晾干，接着在400℃下预氧化10min，得到氧化钛过渡层。按锡钽金属摩尔比9：1，将烷氧基锡和五氯化钽溶于体积比为1：1的乙醇-正丁醇混合溶剂中，得到总金属摩尔浓度为0.20mol/L的涂液。每次用软毛刷均匀涂刷在氧化钛过渡层上，接着在110℃下干燥固化10min，然后在480℃下热氧化分解10min，反复进行直到将涂液刷完。最后，在500℃下热处理1h，制得Ti/TiO2/SnO2-Ta2O5涂层。
扫描电镜测试表明，如图1所示，该防钝化涂层结构致密，裂缝少而小。能谱分析表明，锡沉积率为99％。
对比例1：
参考实施例1，不同之处在于，用5％～10％(质量分数)的草酸溶液在85～95℃下蚀刻钛材2～4h，水洗后室温下凉干后没经过预氧化得到氧化钛过渡层，直接将涂液涂刷在清洁的钛基上得到Ti/SnO2-Ta2O5涂层。
对比例2：
参考实施例1，不同之处在于，用5％～10％(质量分数)的草酸溶液在85～95℃下蚀刻钛材2～4h，水洗后室温下凉干后没经过预氧化得到氧化钛过渡层，直接将涂液涂刷在清洁的钛基上，且五氯化钽用三氯化锑代替得到Ti/SnO2-Sb2O3涂层。
为了便于对照，在0.5mol/L硫酸溶液中测试了对比例1得到的Ti/SnO2-Ta2O5涂层、对比例2得到的Ti/SnO2-Sb2O3涂层、实施例1得到Ti/TiO2/SnO2-Ta2O5涂层的开路电位。测试结果如下：对比例1得到的Ti/SnO2-Ta2O5涂层的开路电位为0.42V，Ti/SnO2-Sb2O3涂层的开路电位为0.36V(VsSCE)，Ti/TiO2/SnO2-Ta2O5涂层的开路电位为0.55V。由此判断，实施例1得到Ti/TiO2/SnO2-Ta2O5涂层的化学稳定性较高。
用φ12mm的圆形轴分别将Ti/SnO2-Ta2O5涂层样品和Ti/TiO2/SnO2-Ta2O5涂层样品弯曲至平行，发现前者弯曲处有少量剥离脱落。由此判断，实施例1预氧化在钛基表面预制导电性的氧化钛薄层较对比例1提高钛基与SnO2基复合涂层间的结合力。
实施例2
选用纯钛网TA2为基体，用8％(质量分数)的草酸85℃蚀刻4h，水洗后室温下晾干，接着在450℃下预氧化12min，得到氧化钛过渡层。按锡铌金属摩尔比9.5：0.5，将醋酸锡和草酸铌溶于体积比为1：1的乙醇-正丁醇混合溶剂中，得到总金属摩尔浓度为0.25mol/L的涂液。将带有氧化钛过渡层的钛基浸入涂液中，以20μm/s速率提拉，室温下静置5min，接着在120℃下干燥固化12min，然后在500℃下热氧化分解10min，反复进行5次。最后，在500℃下热处理1h，制得Ti/TiO2/SnO2-Nb2O5涂层。
扫描电镜测试表明，如图2所示，该防钝化涂层结构致密，裂缝少而小。
实施例3
选用纯钛片TA2为基体，用10％(质量分数)的草酸90℃下蚀刻3h，水洗后室温下晾干，接着在420℃下预氧化10min，得到氧化钛过渡层。按锡钌金属摩尔比9：1，将烷氧基锡和氯化钌溶于体积比为1：1的乙醇-正丁醇混合溶剂中，得到总金属摩尔浓度为0.30mol/L的涂液。每次用软毛刷均匀涂刷在氧化钛过渡层上，接着在110℃下干燥固化10min，然后在450℃下热氧化分解10min，反复进行直到将涂液刷完。最后，在480℃下热处理1h，制得Ti/TiO2/SnO2-RuO2涂层。
扫描电镜测试表明，如图3所示，该防钝化涂层结构致密，裂缝少而小。在0.5mol/L硫酸溶液中的开路电位OCP测试结果：Ti/TiO2/SnO2-RuO2为0.65V。
实施例4
选用纯钛片TA2为基体，用10％(质量分数)的草酸95℃下蚀刻3h，水洗后室温下晾干，接着在450℃下预氧化15min，得到氧化钛过渡层。按锡铱金属摩尔比9.2：0.8，将烷氧基锡和氯铱酸溶于体积比为1：1的乙醇-正丁醇混合溶剂中，得到总金属摩尔浓度为0.20mol/L的涂液。喷涂时，进气压力0.4MPa，喷涂距离25cm。接着在110℃下干燥固化10min，然后在480℃下热氧化分解15min，反复进行直到复合涂层厚度为5μm。最后，在480℃下热处理1h，制得Ti/TiO2/SnO2-IrO2涂层。
扫描电镜测试表明，如图4所示，该防钝化涂层裂缝少而小，结构致密。在0.5mol/L硫酸溶液中的开路电位OCP测试结果：Ti/TiO2/SnO2-IrO2涂层为0.55V。
Claims (7)
1.一种金属氧化物电极用钛基的防钝化涂层，其特征在于，由过渡层和功能涂层构成，所述的过渡层附着在钛基表面，为导电性TiO2膜层，所述的功能涂层为SnO2基复合涂层，其化学组成为：钛基防护成分SnO2、改性剂，按摩尔百分比总量为100％计，其中钛基防护成分SnO2的摩尔分数不少于90％，余为改性剂，所述改性剂为高价贱金属氧化物、贵金属氧化物中的一种；所述的高价贱金属氧化物为Ta2O5、Nb2O5中的任一种；所述的贵金属氧化物为RuO2、IrO2；所述的功能涂层的厚度为0.5～5μm。
2.权利要求1所述的金属氧化物电极用钛基的防钝化涂层的制备方法，其特征在于，包括以下步骤：
①用质量分数为5％～10％的草酸溶液在85～95℃下蚀刻钛材2～4h，水洗后室温下凉干；
②步骤①得到的钛基在空气气氛、400～450℃下进行预氧化5～15min得到过渡层；
③将涂液均匀涂覆在过渡层上；以涂液金属摩尔百分比总量为100％计，所述的涂液配方为：Sn有机前驱体摩尔分数不少于90％，余为改性剂前驱体，溶剂为乙醇和正丁醇，涂液中金属离子浓度为0.1～0.4mol/L；
④在100～120℃下固化10～15min；
⑤在450～520℃下热氧化分解10～15min；
⑥在450～520℃下热处理1h。
3.根据权利要求2所述的金属氧化物电极用钛基的防钝化涂层的制备方法，其特征在于，所述的Sn有机前驱体为烷氧基锡、醋酸锡中的一种；所述的改性剂前驱体为高价贱金属、贵金属前驱体中的一种。
4.根据权利要求3所述的金属氧化物电极用钛基的防钝化涂层的制备方法，其特征在于，高价贱金属前驱体选自氯化钽、五正丁氧基钽、氟铌酸、草酸铌中的任一种。
5.根据权利要求3所述的金属氧化物电极用钛基的防钝化涂层的制备方法，其特征在于，贵金属前驱体为氯化钌、三氯化铱、氯铱酸中的任一种。
6.根据权利要求2所述的金属氧化物电极用钛基的防钝化涂层的制备方法，其特征在于，涂覆采用刷涂、浸涂和喷涂方式中任一种；选用刷涂时，纵向和横向刷涂交替进行；采用浸涂时，提拉速度为1～50μm/s；采用喷涂时，进气压力0.2～0.5MPa，喷涂距离20～30cm。
7.根据权利要求2所述的金属氧化物电极用钛基的防钝化涂层的制备方法，其特征在于，热氧化分解温度为480～500℃。
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Application publication date: 20201113 Assignee: Guangzhou shunyao Energy Technology Co.,Ltd. Assignor: Institute of resource utilization and rare earth development, Guangdong Academy of Sciences Contract record no.: X2024980006118 Denomination of invention: A titanium based anti passivation coating for metal oxide electrodes and its preparation method Granted publication date: 20220422 License type: Common License Record date: 20240523 Application publication date: 20201113 Assignee: Guangzhou Zhuoyue Power Technology Co.,Ltd. Assignor: Institute of resource utilization and rare earth development, Guangdong Academy of Sciences Contract record no.: X2024980006061 Denomination of invention: A titanium based anti passivation coating for metal oxide electrodes and its preparation method Granted publication date: 20220422 License type: Common License Record date: 20240522 Application publication date: 20201113 Assignee: GUANGZHOU ZHUOYUE POWER NEW ENERGY Co.,Ltd. Assignor: Institute of resource utilization and rare earth development, Guangdong Academy of Sciences Contract record no.: X2024980006026 Denomination of invention: A titanium based anti passivation coating for metal oxide electrodes and its preparation method Granted publication date: 20220422 License type: Common License Record date: 20240522 |