CN102569842A - Preparation method of hybrid ordered mesoporous carbon coat for protecting stainless steel bipolar plate of proton exchange membrane fuel cell - Google Patents
Preparation method of hybrid ordered mesoporous carbon coat for protecting stainless steel bipolar plate of proton exchange membrane fuel cell Download PDFInfo
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Abstract
一种用于质子交换膜燃料电池不锈钢双极板防护的杂化有序介孔碳涂层的制备方法,包含以下步骤:将表面活性剂溶于无水乙醇中,搅拌,然后滴加酚醛树脂的乙醇溶液,搅拌均匀,再加入硼酸或磷酸的乙醇溶液,搅拌得到淡黄透明的溶胶-凝胶,逐滴滴加在不锈钢片上,进行滴胶和匀胶处理;接着将涂覆有溶液的不锈钢片溶剂蒸发至少8h,然后在70~120℃热聚合至少24h,在不锈钢表面形成淡黄色涂层;最后在氮气氛围碳化得到黑色的有序介孔碳涂层或碳-硼涂层或碳-磷涂层。本发明直接将杂原子掺杂到碳的前躯体中,得到均匀分布的杂原子,以维持有序的介孔结构,同时提高了304型不锈钢基体上的介孔碳涂层的电导率和疏水性,及其在硫酸溶液中的抗腐蚀性能。
A method for preparing a hybrid ordered mesoporous carbon coating for the protection of stainless steel bipolar plates in proton exchange membrane fuel cells, comprising the following steps: dissolving a surfactant in absolute ethanol, stirring, and then adding dropwise a phenolic resin ethanol solution, stir evenly, then add boric acid or phosphoric acid ethanol solution, stir to obtain a light yellow transparent sol-gel, drop by drop on the stainless steel sheet, and carry out dripping and homogenizing treatment; then the solution coated The solvent of the stainless steel sheet is evaporated for at least 8 hours, and then thermally polymerized at 70-120°C for at least 24 hours to form a light yellow coating on the surface of the stainless steel; finally carbonized in a nitrogen atmosphere to obtain a black ordered mesoporous carbon coating or carbon-boron coating or carbon - Phosphorus coating. In the present invention, heteroatoms are directly doped into the precursor of carbon to obtain uniformly distributed heteroatoms to maintain an ordered mesoporous structure, and at the same time improve the conductivity and hydrophobicity of the mesoporous carbon coating on the 304 type stainless steel substrate properties, and its corrosion resistance in sulfuric acid solution.
Description
技术领域 technical field
本发明涉及一种用于质子交换膜燃料电池不锈钢双极板防护的杂化有序介孔碳涂层的制备方法,属不锈钢双极板防护涂层制备技术领域。 The invention relates to a method for preparing a hybrid ordered mesoporous carbon coating used for the protection of stainless steel bipolar plates of proton exchange membrane fuel cells, belonging to the technical field of preparation of protective coatings for stainless steel bipolar plates.
背景技术 Background technique
双极板是质子交换膜燃料电池的重要组成部分,占总重量的将近80%及总费用的50%。能够作为双极板的材料必须具有高电导率、高耐蚀性、良好的机械强度、低透气性和价格低廉等特点。近年来,最新研究表明由于不锈钢在机械强度、耐蚀性、硬度、表面抛光和清洁等方面的优势,已成为金属双极板的最佳选择。但是,不锈钢作为双极板依然存在的一些问题,主要难题是在腐蚀介质中长期工作后,金属双极板会在表面形成了一层钝化膜,防止金属进一步腐蚀,但这层钝化膜却使得表面接触电阻增大,而且随着工作时间的增长,钝化层会越来越厚。另一个问题是,在弱酸性的条件下存在SO4 2−,Cl−,F−等离子,使得不锈钢在使用中会被腐蚀和溶解,以至于污染膜电极。金属的钝化和溶解行为无疑会使部分电能转化为热能耗散而影响燃料电池的总效率。各种涂层被用作保护金属双极板,例如碳涂层和金属涂层。碳膜涂覆的不锈钢由于价格低廉、体积小,被认为是用作质子膜燃料电池的双极板的良好材料。许多研究表明,当在钝化膜已经完全除去的金属双极板上覆盖碳涂层时,界面接触电阻明显减少[Tomokazu Fukutsuka, Takayuki Yamaguchi, Shin-Ichi Miyano, Yoshiaki Matsuo, Yosohiro Sugie, Zempachi Ogumi, Journal of Power Sources 174 (2007) 199–205]。 The bipolar plate is an important part of the proton exchange membrane fuel cell, accounting for nearly 80% of the total weight and 50% of the total cost. Materials that can be used as bipolar plates must have the characteristics of high electrical conductivity, high corrosion resistance, good mechanical strength, low gas permeability and low price. In recent years, recent studies have shown that stainless steel has become the best choice for metallic bipolar plates due to its advantages in mechanical strength, corrosion resistance, hardness, surface finish, and cleanliness. However, there are still some problems with stainless steel as a bipolar plate. The main problem is that after working in a corrosive medium for a long time, a passivation film will be formed on the surface of the metal bipolar plate to prevent further corrosion of the metal. However, the surface contact resistance increases, and as the working time increases, the passivation layer will become thicker and thicker. Another problem is that there are SO 4 2− , Cl − , F − plasmas under weakly acidic conditions, so that the stainless steel will be corroded and dissolved during use, so as to contaminate the membrane electrode. The passivation and dissolution of metals will undoubtedly convert part of the electrical energy into heat and dissipate it, which will affect the overall efficiency of the fuel cell. Various coatings are used to protect metallic bipolar plates, such as carbon coatings and metallic coatings. Carbon-film-coated stainless steel is considered a good material for bipolar plates in proton membrane fuel cells due to its low cost and small size. Many studies have shown that when a carbon coating is applied to a metal bipolar plate from which the passivation film has been completely removed, the interfacial contact resistance is significantly reduced [Tomokazu Fukutsuka, Takayuki Yamaguchi, Shin-Ichi Miyano, Yoshiaki Matsuo, Yosohiro Sugie, Zempachi Ogumi, Journal of Power Sources 174 (2007) 199–205].
因此,各种碳材料,如石墨,导电聚合物,类金刚石碳和有机自组装材料,被用作双极板的碳涂层而被广泛研究。Fukutsuka表示通过等离子辅助气相沉积方法[T. Fukutsuka, T. Yamaguchi, S.I. Miyano, Y. Matsuo,
Y. Sugie, Z. Ogumi, J. Power Sources 1 (2007) 199-205.]在不锈钢(304SS)表面生成碳膜,与沉积前相比具有高的导电性,而且在碳层与304SS间没有形成钝化膜,但是在质子交换膜燃料电池工作条件下,沉积碳膜的304SS呈现较强的极化现象。Chung [ C.Y. Chung, S.K. Chen, P.J. Chiu, M.H.
Chang, T.T. Hung, T.H. Ko, J. Power Sources 1 (2008) 276-281.]等系统研究了碳涂层304SS作为质子膜燃料电池双极板的腐蚀行为,发现碳膜表现出与石墨电极相似的化学稳定性,可以使304SS在质子膜燃料电池的腐蚀环境中得到保护。Feng等[Kai
Feng, Xun Cai, Hailin Sun, Zhuguo Li, Paul K. Chu, Diamond & Related Materials
19 (2010) 1354-1361. Kai Feng, Yao Shen, Hailin Sun, Dongan Liu,Quanzhang An,
Xun Cai, , Paul K. Chu, i n t e r n a t i o n a l j o u rna l o f hydrogen
energy 3 4 ( 2 0 0 9 ) 6771 – 6777] 通过非平衡磁控溅射在316L不锈钢样品表面涂覆致密、连续、无定形的碳膜,其性能优于传统的石墨双极板。此碳膜的疏水性和界面接触电阻均优于石墨,而且由于其具有好的化学惰性,明显的增强了包覆316L不锈钢的耐腐蚀性。
Therefore, various carbon materials, such as graphite, conductive polymers, diamond-like carbon, and organic self-assembled materials, have been extensively studied as carbon coatings for bipolar plates. Fukutsuka indicated that by the plasma-assisted vapor deposition method [T. Fukutsuka, T. Yamaguchi, S.I. Miyano, Y. Matsuo,
Y. Sugie, Z. Ogumi, J. Power Sources 1 (2007) 199-205.] A carbon film is formed on the surface of stainless steel (304SS), which has high conductivity compared with before deposition, and there is no carbon film between the carbon layer and 304SS A passivation film is formed, but under the working conditions of a proton exchange membrane fuel cell, the 304SS deposited with a carbon film shows a strong polarization phenomenon. Chung [C.Y. Chung, S.K. Chen, P.J. Chiu, M.H.
Chang, T.T. Hung, T.H. Ko, J. Power Sources 1 (2008) 276-281.] and others systematically studied the corrosion behavior of carbon-coated 304SS as a proton membrane fuel cell bipolar plate, and found that the carbon film exhibited similar The chemical stability of 304SS can be protected in the corrosive environment of the proton membrane fuel cell. Feng et al[Kai
Feng, Xun Cai, Hailin Sun, Zhuguo Li, Paul K. Chu, Diamond & Related Materials
19 (2010) 1354-1361. Kai Feng, Yao Shen, Hailin Sun, Dongan Liu, Quanzhang An,
Xun Cai, , Paul K. Chu, i n t e r n a t i o n a l j o u rna
一种新的方法是通过旋涂法在不锈钢基板上形成介孔碳薄膜,碳基复合膜表现出最佳的防护性能,在模拟的燃料电池环境下其相应的电位极化过程非常稳定。[T. Wang, J.P. He, D. Sun, J.H. Zhou, Y.X. Guo, X.C. Ding, S.C. Wu, J.Q. Zhao, J. Tang, Corrosion Science 53 (2011) 1498-1504.] 介孔碳薄膜虽然有很多优点,如良好的防护性能,但因为大量二氧化硅的存在,需要进一步提高电导性。许多研究表明,在碳材料中掺杂供电子或吸电子元素,例如N,P,B,可以改变碳膜的电学性能,并在碳膜表面形成附加功能基团。多数有序介孔碳材料是通过后处理掺杂其他原子,此方法很简单,但是在含量和掺杂物分布方面都不好控制,使有序介孔结构部分或彻底破坏,这在应用中是非常严重的不足。 A new method is to form a mesoporous carbon film on a stainless steel substrate by spin coating. The carbon-based composite film exhibits the best protection performance, and its corresponding potential polarization process is very stable in a simulated fuel cell environment. [T. Wang, J.P. He, D. Sun, J.H. Zhou, Y.X. Guo, X.C. Ding, S.C. Wu, J.Q. Zhao, J. Tang, Corrosion Science 53 (2011) 1498-1504.] Although mesoporous carbon films have many advantages, such as good protection performance, due to the presence of a large amount of silicon dioxide, the electrical conductivity needs to be further improved. Many studies have shown that doping electron-donating or electron-withdrawing elements in carbon materials, such as N, P, and B, can change the electrical properties of carbon films and form additional functional groups on the surface of carbon films. Most ordered mesoporous carbon materials are doped with other atoms through post-treatment. This method is very simple, but it is not easy to control the content and distribution of dopants, so that the ordered mesoporous structure is partially or completely destroyed. It is a very serious deficiency.
发明内容 Contents of the invention
技术问题:为了解决上述问题,本发明的目的在于提出一种工艺简单且具有优异耐腐蚀性能的杂化有序介孔碳涂层的制备方法。 Technical problem: In order to solve the above problems, the object of the present invention is to propose a method for preparing a hybrid ordered mesoporous carbon coating with simple process and excellent corrosion resistance.
技术方案:1、一种用于质子交换膜燃料电池不锈钢双极板防护的杂化有序介孔碳涂层的制备方法,其特征在于包含以下步骤: Technical solution: 1. A method for preparing a hybrid ordered mesoporous carbon coating for protection of stainless steel bipolar plates in proton exchange membrane fuel cells, characterized in that it comprises the following steps:
(1)、将表面活性剂溶于无水乙醇中,搅拌形成透明的溶液;然后滴加酚醛树脂的乙醇溶液,搅拌,备用; (1) Dissolve the surfactant in absolute ethanol, stir to form a transparent solution; then add the ethanol solution of phenolic resin dropwise, stir, and set aside;
(2)、将0.6 mol/L HCl溶液加入到无水乙醇中,调节pH3~5,再加入硼酸或磷酸,搅拌得到溶液;备用; (2), set 0.6 Add the mol/L HCl solution into absolute ethanol, adjust the pH to 3~5, then add boric acid or phosphoric acid, and stir to obtain the solution; set aside;
(3)、将步骤(2)得到的溶液逐滴加入到步骤(1)得到的溶液中,每1g表面活性剂对应的硼酸或磷酸的加入量范围为0.02~0.16 g,搅拌使其混合均匀,得到淡黄透明的溶胶-凝胶; (3) Add the solution obtained in step (2) dropwise to the solution obtained in step (1). The amount of boric acid or phosphoric acid added per 1 g of surfactant ranges from 0.02 to 0.16 g, and stir to make it evenly mixed , to obtain light yellow transparent sol-gel;
(4)、将步骤(1)或(3)配制好的溶胶-凝胶,逐滴滴加在不锈钢片上,进行滴胶和匀胶处理; (4), add the sol-gel prepared in step (1) or (3) drop by drop on the stainless steel sheet, and perform glue dropping and uniform glue treatment;
(5)、将步骤(4)得到的涂覆有溶液的不锈钢片在25 ℃下溶剂蒸发至少8 h,然后在70~120 ℃热聚合至少24 h,在不锈钢表面形成淡黄色涂层;最后在氮气氛围碳化得到黑色的有序介孔碳-硼涂层或碳-磷涂层或碳涂层。 (5) Evaporate the solution-coated stainless steel sheet obtained in step (4) at 25°C for at least 8 hours, and then thermally polymerize at 70-120°C for at least 24 hours to form a light yellow coating on the surface of the stainless steel; finally Carbonization in nitrogen atmosphere to obtain black ordered mesoporous carbon-boron coating or carbon-phosphorus coating or carbon coating.
所述步骤(1)中表面活性剂为聚氧乙烯/聚氧丙烯/聚氧乙烯两亲嵌段共聚物F127,分子式为PEO106-PPO70-PEO106。 The surfactant in the step (1) is polyoxyethylene/polyoxypropylene/polyoxyethylene amphiphilic block copolymer F127 with a molecular formula of PEO 106 -PPO 70 -PEO 106 .
所述的步骤(1)中每1 g表面活性剂溶于15mL无水乙醇中,酚醛树脂的乙醇溶液的质量分数为20%。 In the step (1), every 1 g of surfactant is dissolved in 15 mL of absolute ethanol, and the mass fraction of the ethanol solution of phenolic resin is 20%.
所述的步骤(4)中,滴胶速度为400~800 rpm,滴胶时间10~20 s,匀胶速度选择为1500~3000 rpm,匀胶时间45~60 s,重复滴胶和匀胶过程5次。 In the step (4), the dispensing speed is 400~800 rpm, the glue dispensing time is 10-20 s, the speed of dispensing glue is selected as 1500-3000 rpm, the dispensing time is 45-60 s, and the dispensing and dispensing process is repeated 5 times.
所述的步骤(5)中碳化在通有氮气气流的气氛管式炉中进行,350 ℃下保温3~5 h,目标温度下400~700 ℃下保温2 h,升温速率严格控制在1 ℃/min The carbonization in the step (5) is carried out in an atmosphere tube furnace with a nitrogen gas flow, at 350°C for 3-5 hours, at the target temperature of 400-700°C for 2 hours, and the heating rate is strictly controlled at 1°C /min
步骤(1)中酚醛树脂的乙醇溶液(酚醛树脂质量分数20%),具体制备方法是:首先,在烧杯中称取6.1 g苯酚,缓慢升温至40~42
℃使其熔化;然后向烧杯内缓慢滴加1.3 g的NaOH(质量分数20%)水溶液,同时磁力搅拌10 min,使溶液均匀;接着,逐滴加入10.5
g甲醛溶液(质量分数37%),并升温至70~75
℃,剧烈搅拌60 min使苯酚和甲醛发生聚合反应;反应结束后将溶液自然冷却至室温,然后用0.6
mol/L的HCl溶液将烧杯中溶液的pH值调节为中性(7.0);将调好pH值的溶液置于真空干燥箱中,在45 ℃下挥发水分,期间可以看到有白色的NaCl晶体析出;最后,将烧杯中的酚醛树脂部分溶解于无水乙醇中,并配成质量分数为20%的酚醛树脂乙醇溶液,备用。
The ethanol solution of phenolic resin in step (1) (phenolic
有益效果:本发明直接将杂原子掺杂到碳的前躯体中,得到均匀分布的杂原子,以维持有序的介孔结构,同时了提高不锈钢基体上的介孔碳涂层的电导率和疏水性,以及其在硫酸溶液中的抗腐蚀性能。 Beneficial effects: the present invention directly dopes heteroatoms into carbon precursors to obtain evenly distributed heteroatoms to maintain an ordered mesoporous structure, and at the same time improve the electrical conductivity and Hydrophobicity, and its corrosion resistance in sulfuric acid solution.
附图说明 Description of drawings
图1是有序介孔CB-x-500涂层XRD图谱, Figure 1 is the XRD pattern of the ordered mesoporous CB-x-500 coating,
其中图1a是有序介孔CB-x-500涂层的小角XRD图谱,从图谱可知随着硼酸用量增加,在0.8o位置小角XRD衍射峰逐渐降低,意味着CB-x-500涂层有序度的降低,说明硼酸的添加量在0.2-0.8更有利于有序介孔结构的保持; Figure 1a is the small-angle XRD pattern of the ordered mesoporous CB-x-500 coating. It can be seen from the pattern that as the amount of boric acid increases, the small-angle XRD diffraction peak at the position of 0.8 o gradually decreases, which means that the CB-x-500 coating has The order degree decreases, indicating that the addition of boric acid in the range of 0.2-0.8 is more conducive to the maintenance of the ordered mesoporous structure;
图1b是CB-x-500涂层大角XRD图谱; Figure 1b is the large-angle XRD pattern of CB-x-500 coating;
图2是有序介孔CB-0.08-y涂层的XRD图谱, Figure 2 is the XRD pattern of the ordered mesoporous CB-0.08-y coating,
其中:图2a是有序介孔CB-0.08-y涂层的小角XRD图谱,图2b是有序介孔CB-0.08-y涂层的大角XRD图谱;从图2a中可以看出涂层的有序度都保持的完好; Among them: Figure 2a is the small-angle XRD spectrum of the ordered mesoporous CB-0.08-y coating, and Figure 2b is the large-angle XRD spectrum of the ordered mesoporous CB-0.08-y coating; it can be seen from Figure 2a that the coating Order is maintained intact;
图3是有序介孔CP-0.06-500涂层的XRD图谱, Figure 3 is the XRD spectrum of the ordered mesoporous CP-0.06-500 coating,
其中:图3a是有序介孔CP-0.06-500涂层的小角XRD图谱,图3b是有序介孔CP-0.06-500涂层的大角XRD图谱; Among them: Figure 3a is the small-angle XRD spectrum of the ordered mesoporous CP-0.06-500 coating, and Figure 3b is the large-angle XRD spectrum of the ordered mesoporous CP-0.06-500 coating;
图4是有序介孔CB-x-500涂层的TEM图: (a,b) CB-0-500; (c,d) CB-0.02-500; (e,f) CB-0.04-500; (g,h) CB-0.08-500; (i,j) CB-0.16-500;其中图4h中的插图是CB-0.08-500电子衍射图,说明该涂层主要是无定形碳为主; Figure 4 is the TEM image of the ordered mesoporous CB-x-500 coating: (a,b) CB-0-500; (c,d) CB-0.02-500; (e,f) CB-0.04-500 ; (g,h) CB-0.08-500; (i,j) CB-0.16-500; where the inset in Figure 4h is the CB-0.08-500 electron diffraction pattern, indicating that the coating is mainly amorphous carbon;
图5是有序介孔CB-0.08-y涂层的TEM图: (a,b) CB-0.08-400; (c,d) CB-0.08-500; (e,f) CB-0.08-600; (g,h) CB-0.08-700; Figure 5 is the TEM image of the ordered mesoporous CB-0.08-y coating: (a,b) CB-0.08-400; (c,d) CB-0.08-500; (e,f) CB-0.08-600; (g, h) CB-0.08-700;
图6是有序CB-x-500涂层的N2吸脱附等温曲线和孔径分布曲线, Fig. 6 is the N2 adsorption-desorption isotherm curve and pore size distribution curve of the ordered CB-x-500 coating,
其中:图6a是CB-x-500涂层的N2吸脱附等温曲线,图6b是CB-x-500涂层的孔径分布曲线; Among them: Figure 6a is the N adsorption-desorption isotherm curve of CB-x-500 coating, and Figure 6b is the pore size distribution curve of CB-x-500 coating;
图7是有序CB-0.08-y涂层的N2吸脱附等温曲线和孔径分布曲线, Figure 7 is the N2 adsorption-desorption isotherms and pore size distribution curves of the ordered CB-0.08-y coating,
其中:图7a是CB-0.08-y涂层的N2吸脱附等温曲线,图7b是CB-0.08-y涂层的孔径分布曲线; Among them: Figure 7a is the N adsorption - desorption isotherm curve of CB-0.08-y coating, and Figure 7b is the pore size distribution curve of CB-0.08-y coating;
图8是有序CB-x-500涂层在0.5 M H2SO4体系下的Tafel曲线;从图中计算出来的电化学数据列于表2中,从表中可以看出硼酸的添加量在0.02~0.08 g之间涂层的腐蚀防护比较好; Figure 8 is the Tafel curve of the ordered CB-x-500 coating in the 0.5 MH 2 SO 4 system; the electrochemical data calculated from the figure are listed in Table 2, and it can be seen from the table that the amount of boric acid added is The corrosion protection of the coating between 0.02 and 0.08 g is better;
图9是有序CB-0.08-y涂层在0.5 M H2SO4体系下的Tafel曲线。从图中计算出来的电化学数据列于表2中,从表中可以看出热处理温度在400~600 ℃之间涂层的腐蚀防护比较好。 Fig. 9 is the Tafel curve of ordered CB-0.08-y coating under 0.5 MH 2 SO 4 system. The electrochemical data calculated from the figure are listed in Table 2. It can be seen from the table that the corrosion protection of the coating is better when the heat treatment temperature is between 400 and 600 °C.
具体实施方式 Detailed ways
以下实施例获得的涂层的命名方式是:以CB-x-y的形式标记掺硼的碳涂层产物,其中x表示加入硼酸的质量(g),y表示最终热处理温度,以CP-x-y的形式标记掺磷的碳涂层产物,其中x表示加入磷酸的质量(g),y表示最终热处理温度,则各实施例中样品命名如下表: The naming method of the coating obtained in the following examples is: the boron-doped carbon coating product is marked in the form of CB-xy, where x indicates the mass (g) of boric acid added, and y indicates the final heat treatment temperature, in the form of CP-xy Mark the phosphorus-doped carbon coating product, where x represents the mass (g) of phosphoric acid added, and y represents the final heat treatment temperature, and the samples in each embodiment are named in the following table:
实施例1: Example 1:
(1)将1 g聚氧乙烯/聚氧丙烯/聚氧乙烯两亲嵌段共聚物F127(购自Sigma-Aldrich公司)溶于15.0 ml无水乙醇中,搅拌1 h形成透明的溶液A;同时将1.8 ml的的HCl溶液(0.6
mol/L)加入到5 ml无水乙醇中,调节pH在3~5范围内,再缓慢加入0.02 g硼酸,磁力搅拌得到溶液B;缓慢滴加5 g酚醛树脂的乙醇溶液(酚醛树脂质量分数20%)于溶液A中,搅拌10 min;然后逐滴将溶液B加于溶液A中,搅拌1 h使其混合均匀,从而得到淡黄透明的碳-硼溶液;
(1) Dissolve 1 g of polyoxyethylene/polyoxypropylene/polyoxyethylene amphiphilic block copolymer F127 (purchased from Sigma-Aldrich) in 15.0 ml of absolute ethanol, and stir for 1 h to form a transparent solution A; At the same time, 1.8 ml of HCl solution (0.6
mol/L) into 5 ml of absolute ethanol, adjust the pH in the range of 3 to 5, then slowly add 0.02 g of boric acid, and magnetically stir to obtain solution B; slowly add 5 g of ethanol solution of phenolic resin dropwise (mass fraction of
(2)将在台式匀胶机上将之前配制好的碳-硼溶胶-凝胶,逐滴滴加在不锈钢片上,滴胶速度选择为500 rpm,滴胶时间10 s,匀胶速度选择为1500 rpm/s,匀胶时间60 s,重复滴胶和匀胶过程5次;
(2) Add the previously prepared carbon-boron sol-gel drop by drop on the stainless steel sheet on the desktop glue homogenizer. rpm/s, glue homogenization time 60 s, repeat the process of dispensing glue and
(3)将涂覆有溶液的不锈钢片转移到烘箱中,在25 ℃下溶剂蒸发8 h,然后在70~120 ℃热聚合24 h,在不锈钢表面形成淡黄色涂层; (3) The stainless steel sheet coated with the solution was transferred to an oven, the solvent was evaporated at 25 °C for 8 h, and then thermally polymerized at 70-120 °C for 24 h to form a light yellow coating on the surface of the stainless steel;
(4)将涂覆有涂层的不锈钢片放入瓷舟,准备碳化。碳化在通有氮气气流的气氛管式炉中进行,350 ℃下保温3 h,目标温度下500 ℃下保温2 h,升温速率严格控制在1 ℃/min; (4) Put the coated stainless steel sheet into the porcelain boat and prepare for carbonization. The carbonization was carried out in an atmosphere tube furnace with a nitrogen gas flow. The temperature was kept at 350 °C for 3 h, and at the target temperature of 500 °C for 2 h. The heating rate was strictly controlled at 1 °C/min;
获得CB-0.02-500涂层, B元素在碳化过程中高度分散在碳矩阵中,这就保证了涂层的有序介孔结构不被破坏(见图1和图4(c,d)),具体结构数据见表1。在0.5 M H2SO4中进行Tafel测试的数据见表2,从表2中可以看出,与未涂覆涂层的304型不锈钢相比,涂覆有CB-0.02-500涂层的自腐蚀电位正移约500 mV,腐蚀电流密度下降了一个数量级。 The CB-0.02-500 coating is obtained, and the B element is highly dispersed in the carbon matrix during the carbonization process, which ensures that the ordered mesoporous structure of the coating is not destroyed (see Figure 1 and Figure 4(c,d)) , see Table 1 for specific structural data. The data of the Tafel test in 0.5 MH2SO4 are shown in Table 2. From Table 2, it can be seen that compared with the uncoated Type 304 stainless steel, the self-corrosion The potential shifted positively by about 500 mV, and the corrosion current density decreased by an order of magnitude.
实施例2: Example 2:
本实施例除了硼酸加入量为0.04 g,其余内容均同实施例1。 In this embodiment, except that the addition of boric acid is 0.04 g, all the other contents are the same as in Example 1.
获得CB-0.04-500涂层,B元素在碳化过程中高度分散在碳矩阵中,这就保证了涂层的有序介孔结构不被破坏(见图1和图4(e,f)),具体结构数据见表1。在0.5 M H2SO4中进行Tafel测试的数据见表2,从表2中可以看出,与未涂覆涂层的304型不锈钢相比,涂覆有CB-0.04-500涂层的自腐蚀电位正移约500 mV,腐蚀电流密度下降了一个数量级。 The CB-0.04-500 coating is obtained, and the B element is highly dispersed in the carbon matrix during the carbonization process, which ensures that the ordered mesoporous structure of the coating is not destroyed (see Figure 1 and Figure 4(e,f)) , see Table 1 for specific structural data. The data of the Tafel test in 0.5 MH2SO4 are shown in Table 2. From Table 2, it can be seen that compared with the uncoated Type 304 stainless steel, the self-corrosion The potential shifted positively by about 500 mV, and the corrosion current density decreased by an order of magnitude.
实施例3: Example 3:
本实施例除了硼酸加入量为0.08 g,其余内容均同实施例1。 In this embodiment, except that the addition of boric acid is 0.08 g, all the other contents are the same as in Example 1.
获得CB-0.08-500涂层,B元素在碳化过程中高度分散在碳矩阵中,这就保证了涂层的有序介孔结构不被破坏(见图1和图4(g,h)),具体结构数据见表1。在0.5 M H2SO4中进行Tafel测试的数据见表2,从表2中可以看出,与未涂覆涂层的304型不锈钢相比,涂覆有CB-0.08-500涂层的自腐蚀电位正移约500 mV,腐蚀电流密度下降了一个数量级。 The CB-0.08-500 coating is obtained, and the B element is highly dispersed in the carbon matrix during the carbonization process, which ensures that the ordered mesoporous structure of the coating is not destroyed (see Figure 1 and Figure 4(g,h)) , see Table 1 for specific structural data. The data of the Tafel test in 0.5 MH2SO4 are shown in Table 2. From Table 2, it can be seen that compared with the uncoated Type 304 stainless steel, the self-corrosion The potential shifted positively by about 500 mV, and the corrosion current density decreased by an order of magnitude.
实施例4: Example 4:
本实施例除了硼酸加入量为0.16 g,其余内容均同实施例1。 In this embodiment, except that the addition of boric acid is 0.16 g, all the other contents are the same as in Example 1.
获得CB-0.16-500涂层,B元素在碳化过程中高度分散在碳矩阵中,这就保证了涂层的有序介孔结构不被破坏(见图1和图4(i,j)),具体结构数据见表1。在0.5 M H2SO4中进行Tafel测试的数据见表2,从表2中可以看出,与未涂覆涂层的304型不锈钢相比,涂覆有CB-0.16-500涂层的自腐蚀电位正移约500 mV,腐蚀电流密度下降了一倍。 The CB-0.16-500 coating is obtained, and the B element is highly dispersed in the carbon matrix during the carbonization process, which ensures that the ordered mesoporous structure of the coating is not destroyed (see Figure 1 and Figure 4(i,j)) , see Table 1 for specific structural data. The data of the Tafel test in 0.5 MH2SO4 are shown in Table 2. From Table 2, it can be seen that compared with the uncoated Type 304 stainless steel, the self-corrosion The potential shifted positively by about 500 mV, and the corrosion current density doubled.
实施例5: Example 5:
本实施例除了目标温度为400 ℃下保温2 h,其余内容均同实施例3。 In this example, except that the target temperature is kept at 400°C for 2 hours, the rest of the content is the same as in Example 3.
获得CB-0.08-400涂层,B元素在碳化过程中高度分散在碳矩阵中,这就保证了涂层的有序介孔结构不被破坏(见图1和图5(a,b)),具体结构数据见表1。在0.5 M H2SO4中进行Tafel测试的数据见表2,从表2中可以看出,与未涂覆涂层的304型不锈钢相比,涂覆有CB-0.08-400涂层的自腐蚀电位正移约500 mV腐蚀电流密度下降了一个数量级。 The CB-0.08-400 coating is obtained, and the B element is highly dispersed in the carbon matrix during the carbonization process, which ensures that the ordered mesoporous structure of the coating is not destroyed (see Figure 1 and Figure 5(a,b)) , see Table 1 for specific structural data. The data of the Tafel test in 0.5 MH2SO4 are shown in Table 2. From Table 2, it can be seen that compared with the uncoated Type 304 stainless steel, the self-corrosion Positive shift of about 500 mV corrosion current density decreased by an order of magnitude.
实施例6: Embodiment 6:
本实施例除了目标温度为600 ℃下保温2 h,其余内容均同实施例3。 In this example, except that the target temperature is 600 °C for 2 hours, the rest of the content is the same as that of Example 3.
获得CB-0.08-600涂层, B元素在碳化过程中高度分散在碳矩阵中,这就保证了涂层的有序介孔结构不被破坏(见图1和图5(e,f)),具体结构数据见表1。在0.5 M H2SO4中进行Tafel测试的数据见表2,从表2中可以看出,与未涂覆涂层的304型不锈钢相比,涂覆有CB-0.08-600涂层的自腐蚀电位正移约500 mV,腐蚀电流密度下降了一个数量级。 The CB-0.08-600 coating is obtained, and the B element is highly dispersed in the carbon matrix during the carbonization process, which ensures that the ordered mesoporous structure of the coating is not destroyed (see Figure 1 and Figure 5(e,f)) , see Table 1 for specific structural data. The data of the Tafel test in 0.5 MH2SO4 are shown in Table 2. From Table 2, it can be seen that compared with the uncoated Type 304 stainless steel, the self-corrosion The potential shifted positively by about 500 mV, and the corrosion current density decreased by an order of magnitude.
实施例7: Embodiment 7:
本实施例除了目标温度为700 ℃下保温2 h,其余内容均同实施例3。 In this example, except that the target temperature is 700 °C for 2 hours, the rest of the content is the same as that of Example 3.
获得CB-0.08-700涂层,B元素在碳化过程中高度分散在碳矩阵中,这就保证了涂层的有序介孔结构不被破坏(见图1和图5(g,h)),具体结构数据见表1。在0.5 M H2SO4中进行Tafel测试的数据见表2,从表2中可以看出,与未涂覆涂层的304型不锈钢相比,涂覆有CB-0.08-700涂层的自腐蚀电位正移约300 mV,腐蚀电流密度下降了一倍。 The CB-0.08-700 coating is obtained, and the B element is highly dispersed in the carbon matrix during the carbonization process, which ensures that the ordered mesoporous structure of the coating is not destroyed (see Figure 1 and Figure 5(g,h)) , see Table 1 for specific structural data. The data of the Tafel test in 0.5 MH2SO4 are shown in Table 2. From Table 2, it can be seen that compared with the uncoated Type 304 stainless steel, the self-corrosion The potential shifted positively by about 300 mV, and the corrosion current density doubled.
实施例8: Embodiment 8:
(1)将1 g表面活性剂F127溶于20.0 ml无水乙醇中,搅拌1 h形成透明的溶液A;缓慢滴加5 g酚醛树脂的乙醇溶液(酚醛树脂质量分数20%)于溶液A中,搅拌得到淡黄透明的碳溶液;
(1) Dissolve 1 g of surfactant F127 in 20.0 ml of absolute ethanol, stir for 1 h to form a transparent solution A; slowly add 5 g of ethanol solution of phenolic resin (mass fraction of
(2)将在台式匀胶机上将之前配制好的碳溶胶-凝胶,逐滴滴加在不锈钢片上,滴胶速度选择为800 rpm/s,滴胶时间20 s,匀胶速度选择为3000 rpm/s,匀胶时间45s,重复滴胶和匀胶过程5次;
(2) Add the previously prepared carbon sol-gel drop by drop on the stainless steel sheet on the desktop glue homogenizer, the glue dropping speed is selected as 800 rpm/s, the glue dropping time is 20 s, and the glue uniform speed is selected as 3000 rpm/s, glue homogenization time 45s, repeat the glue dropping and
(3)将涂覆有溶液的不锈钢片转移到烘箱中,在25 ℃下溶剂蒸发8 h,然后在70~120 ℃热聚合24 h,在不锈钢表面形成淡黄色涂层; (3) The stainless steel sheet coated with the solution was transferred to an oven, the solvent was evaporated at 25 °C for 8 h, and then thermally polymerized at 70-120 °C for 24 h to form a light yellow coating on the surface of the stainless steel;
(4)将涂覆有涂层的不锈钢片放入瓷舟,准备碳化。碳化在通有氮气气流的气氛管式炉中进行,350 ℃下保温5 h,目标温度下500 ℃下保温2 h,升温速率严格控制在1 ℃/min; (4) Put the coated stainless steel sheet into the porcelain boat and prepare for carbonization. The carbonization was carried out in an atmosphere tube furnace with a nitrogen gas flow, held at 350 °C for 5 h, and at the target temperature of 500 °C for 2 h, and the heating rate was strictly controlled at 1 °C/min;
获得CB-0-500涂层具有高度有序的介孔结构(见图1和图4(a,b)),具体结构数据见表1。在0.5 M H2SO4中进行Tafel测试的数据见表2,从表2中可以看出,与未涂覆涂层的304型不锈钢相比,涂覆有CB-0-500涂层的自腐蚀电位正移约300 mV,腐蚀电流密度下降了一个数量级。 The obtained CB-0-500 coating has a highly ordered mesoporous structure (see Figure 1 and Figure 4(a,b)), and the specific structural data are shown in Table 1. The data of the Tafel test in 0.5 MH2SO4 are shown in Table 2. From Table 2, it can be seen that compared with the uncoated Type 304 stainless steel, the self-corrosion The potential shifted positively by about 300 mV, and the corrosion current density decreased by an order of magnitude.
实施例9: Embodiment 9:
本实施例除了步骤(1)中添加物由磷酸代替硼酸,添加量为0.06g外,其余内容均同实施例1。 In this embodiment, except that the additive in step (1) replaces boric acid by phosphoric acid, and the addition amount is 0.06g, all the other contents are the same as in Example 1.
获得的CP-0.06-500涂层具有高度有序的介孔结构(见图3),具体结构数据见表1。在0.5 M H2SO4中进行Tafel测试的数据见表2,从表2中可以看出,与未涂覆涂层的304型不锈钢相比,涂覆有CP-0.06-500涂层的自腐蚀电位正移约550 mV,腐蚀电流密度下降了一倍。 The obtained CP-0.06-500 coating has a highly ordered mesoporous structure (see Figure 3), and the specific structural data are shown in Table 1. The data of the Tafel test in 0.5 MH2SO4 are shown in Table 2. From Table 2, it can be seen that compared with the uncoated Type 304 stainless steel, the self-corrosion The potential is shifted positively by about 550 mV, and the corrosion current density is doubled.
表1是由N2吸脱附等温曲线计算得到的有序介孔CB和CP涂层的孔结构参数 Table 1 Pore structure parameters of ordered mesoporous CB and CP coatings calculated from N2 adsorption-desorption isotherms
从表1中,可以看到添加B或P后的有序介孔碳涂层具有较大的比表面积,在400~700 m2/g之间,且介孔比例都较高,都在78%以上,且结合图6b和图7b可以知道CB涂层的孔径分布非常集中。 From Table 1, it can be seen that the ordered mesoporous carbon coating after adding B or P has a large specific surface area, between 400 and 700 m 2 /g, and the mesopore ratio is relatively high, both at 78 % or more, and combined with Figure 6b and Figure 7b, it can be seen that the pore size distribution of the CB coating is very concentrated.
表2 是样品的电导率,接触角,以及在0.5 M H2SO4中进行Tafel测试的自腐蚀电位和自腐蚀电流密度 Table 2 is the electrical conductivity, contact angle, and self-corrosion potential and self-corrosion current density of the Tafel test in 0.5 MH 2 SO 4
从表2中,可以看到添加B或P后的有序介孔碳涂层的电导率和接触角都相应增大,且添加量越大,电导率和接触角增加的越多。但通过腐蚀防护性能表征可以推出硼酸的添加量应该在0.02~0.08 g之间,热处理温度最好是在400~600 ℃之间。 From Table 2, it can be seen that the conductivity and contact angle of the ordered mesoporous carbon coatings increase correspondingly after adding B or P, and the greater the addition amount, the more the conductivity and contact angle increase. However, through the characterization of corrosion protection performance, it can be deduced that the amount of boric acid added should be 0.02~0.08 g, the heat treatment temperature is preferably between 400 and 600 °C.
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