CN102468490A - Chromium carbide/graphite composite coating on surface of stainless steel bipolar plate of all-vanadium redox flow battery - Google Patents
Chromium carbide/graphite composite coating on surface of stainless steel bipolar plate of all-vanadium redox flow battery Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 64
- 239000011248 coating agent Substances 0.000 title claims abstract description 56
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 52
- 239000010935 stainless steel Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 37
- 239000010439 graphite Substances 0.000 title claims abstract description 37
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910003470 tongbaite Inorganic materials 0.000 title claims abstract description 34
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 21
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 18
- 239000011651 chromium Substances 0.000 claims abstract description 18
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract 4
- 238000009792 diffusion process Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 27
- 238000005260 corrosion Methods 0.000 abstract description 27
- 238000009713 electroplating Methods 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 11
- 239000000843 powder Substances 0.000 abstract description 7
- 239000007787 solid Substances 0.000 abstract description 7
- 238000005240 physical vapour deposition Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 2
- 239000007789 gas Substances 0.000 abstract 2
- 238000007740 vapor deposition Methods 0.000 abstract 2
- 230000008021 deposition Effects 0.000 abstract 1
- 230000008595 infiltration Effects 0.000 abstract 1
- 238000001764 infiltration Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 46
- 229910000619 316 stainless steel Inorganic materials 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 10
- 230000007774 longterm Effects 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000007654 immersion Methods 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 7
- 238000005254 chromizing Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- 239000010963 304 stainless steel Substances 0.000 description 2
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 304 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
本发明提供了一种全钒液流电池不锈钢双极板表面耐蚀、导电的碳化铬/石墨复合涂层。该复合涂层是采用化学气相沉积方法制备，气相沉积气氛为乙炔-氢气混合气或甲烷-氢气混合气，反应温度为800-9500C。在气相沉积该复合涂层前，需先在不锈钢表面制备富铬层。富铬层的制备可采取电镀、物理气相沉积、固态粉末渗等方法。同时，在该富铬层表面沉积Ni催化层有助于石墨层的沉积，并能抑制不锈钢的氧化。本发明的特点是利用了热生长的无缺陷碳化铬层的优异耐腐蚀性能与良好的导电性能，以及石墨层的良好抗腐蚀性能及低的接触电阻，通过化学气相沉积方法同步沉积而成。该复合涂层可以为全钒液流电池不锈钢双极板提供优异的抗腐蚀性能与导电性能。The invention provides a corrosion-resistant and conductive chromium carbide/graphite composite coating on the surface of a stainless steel bipolar plate of an all-vanadium redox flow battery. The composite coating is prepared by a chemical vapor deposition method, the vapor deposition atmosphere is acetylene-hydrogen mixed gas or methane-hydrogen mixed gas, and the reaction temperature is 800-950 ° C. Before vapor deposition of the composite coating, a chromium-rich layer must be prepared on the surface of the stainless steel. The chromium-rich layer can be prepared by methods such as electroplating, physical vapor deposition, and solid powder infiltration. At the same time, depositing a Ni catalytic layer on the surface of the chromium-rich layer is helpful to the deposition of the graphite layer and can inhibit the oxidation of stainless steel. The present invention is characterized in that it utilizes the excellent corrosion resistance and good electrical conductivity of the thermally grown defect-free chromium carbide layer, and the good corrosion resistance and low contact resistance of the graphite layer, and is deposited simultaneously by chemical vapor deposition. The composite coating can provide excellent corrosion resistance and electrical conductivity for the stainless steel bipolar plate of the all-vanadium redox flow battery.
Description
技术领域 technical field
本发明涉及全钒液流储能电池技术，特别提供了一种全钒液流储能电池不锈钢双极板的表面碳化铬/石墨复合涂层，使得不锈钢双极板在电池电解液中具有良好的耐腐蚀性能，并具有低的接触电阻。 The invention relates to the technology of an all-vanadium flow energy storage battery, and in particular provides a chromium carbide/graphite composite coating on the surface of a stainless steel bipolar plate of an all-vanadium flow energy storage battery, so that the stainless steel bipolar plate has a good performance in the battery electrolyte. Excellent corrosion resistance and low contact resistance.
背景技术 Background technique
全钒液流电池是将具有不同价态的钒离子溶液分别作为正极和负极的活性物质，分别储存在各自的电解液储罐中。在对电池进行充、放电实验时，电解液通过泵的作用，由外部贮液罐分别循环流经电池的正极室和负极室，并在电极表面发生氧化和还原反应，实现对电池的充放电。与其它类化学电源相比，全钒液流电池规模大、寿命长、成本低及效率等特点，具有很强的产业化前景。 The all-vanadium redox flow battery uses vanadium ion solutions with different valence states as the active materials of the positive and negative electrodes respectively, and stores them in respective electrolyte storage tanks. When the battery is charged and discharged, the electrolyte is circulated through the positive and negative chambers of the battery by the pump through the external liquid storage tank, and oxidation and reduction reactions occur on the electrode surface to realize the charging and discharging of the battery. . Compared with other types of chemical power sources, all-vanadium redox flow batteries have the characteristics of large scale, long life, low cost and high efficiency, and have strong industrialization prospects.
钒电池的关键材料包括电池隔膜、电解液、电极及双极板。双极板的主要作用是收集电化学反应产生的电流以及分隔正负极电解液。理想的双极板应该具备几个特性：第一，非常高的导电性，导电性越高，钒电池的性能会越好；第二，非常耐腐蚀，在整个充放电过程中都不会和钒电池的强酸电解液发生反应；第三，较低的渗透率，以免钒电池正负极电解液相互渗透，降低电池效率；第四，要有一定的强度。目前研究的双极板主要包括无孔石墨双极板、碳塑双极板和金属双极板。无孔石墨双极板尽管具有良好耐蚀性与导电性，但其制备工艺复杂，成本高；碳塑双极板具有制备工艺简单，成本较低，但其电阻率明显高于金属双极板和无孔石墨双极板；金属双极板具有强度高、加工性能好、致密性高、本体电阻小等特点，但在电池强酸性环境中面临腐蚀问题，因此必须对其进行表面改性处理，这是金属双极板能否应用的关键。通常采用的处理方法有热喷、丝网印刷、物理气相沉积、化学气相沉积、离子注入、电镀、化学镀等。改性后的双极板寿命虽然得到了一定程度的提高，但仍无法满足长期使用要求。因此，必须寻求新的金属双极板表面防护涂层。 The key materials of vanadium batteries include battery separator, electrolyte, electrodes and bipolar plates. The main function of the bipolar plate is to collect the current generated by the electrochemical reaction and to separate the positive and negative electrolytes. An ideal bipolar plate should have several characteristics: first, very high conductivity, the higher the conductivity, the better the performance of the vanadium battery; The strong acid electrolyte of the vanadium battery reacts; third, low permeability, so as to prevent the positive and negative electrolytes of the vanadium battery from permeating each other and reducing the battery efficiency; fourth, it must have a certain strength. The current bipolar plates mainly include non-porous graphite bipolar plates, carbon plastic bipolar plates and metal bipolar plates. Although the non-porous graphite bipolar plate has good corrosion resistance and conductivity, its preparation process is complicated and the cost is high; the carbon plastic bipolar plate has a simple preparation process and low cost, but its resistivity is significantly higher than that of the metal bipolar plate and non-porous graphite bipolar plates; metal bipolar plates have the characteristics of high strength, good processability, high density, and low bulk resistance, but they face corrosion problems in the strongly acidic environment of the battery, so surface modification must be carried out , which is the key to the application of metal bipolar plates. Commonly used processing methods include thermal spraying, screen printing, physical vapor deposition, chemical vapor deposition, ion implantation, electroplating, and chemical plating. Although the life of the modified bipolar plate has been improved to a certain extent, it still cannot meet the long-term use requirements. Therefore, new protective coatings on the surface of metal bipolar plates must be sought.
发明内容 Contents of the invention
发明内容Contents of the invention
本发明的目的是提供一种全钒液流电池不锈钢双极板的表面防护涂层。该涂层可以显著提高不锈钢在全钒液流电池环境中的耐腐蚀性能，并降低金属双极板的接触电阻。 The purpose of the present invention is to provide a surface protective coating for a stainless steel bipolar plate of an all-vanadium redox flow battery. The coating can significantly improve the corrosion resistance of stainless steel in the environment of the all-vanadium redox flow battery, and reduce the contact resistance of the metal bipolar plate.
本发明提供了一种全钒液流电池不锈钢双极板表面碳化铬/石墨复合涂层，其特征在于：复合涂层内层为致密的热扩散碳化铬层，外层为致密的石墨层。这种碳化铬与石墨层的复合可以使不锈钢双极板获得优异的耐蚀性能与低的接触电阻。 The invention provides a chromium carbide/graphite composite coating on the surface of a stainless steel bipolar plate of an all-vanadium redox flow battery, which is characterized in that the inner layer of the composite coating is a dense thermal diffusion chromium carbide layer, and the outer layer is a dense graphite layer. The combination of chromium carbide and graphite layer can make the stainless steel bipolar plate obtain excellent corrosion resistance and low contact resistance.
本发明提供的全钒液流电池不锈钢双极板表面碳化铬/石墨复合涂层，所述复合涂层采用化学气相沉积方法制备。涂层的厚度通过对反应温度、反应时间、气氛等参数控制来调节。 The invention provides a chromium carbide/graphite composite coating on the surface of a stainless steel bipolar plate of an all-vanadium redox flow battery, and the composite coating is prepared by a chemical vapor deposition method. The thickness of the coating is adjusted by controlling parameters such as reaction temperature, reaction time, and atmosphere.
本发明提供的全钒液流电池不锈钢双极板表面碳化铬/石墨复合涂层，其特征在于：所述涂层制备气氛为氢气-乙炔混合气或氢气-甲烷混合气。 The chromium carbide/graphite composite coating on the surface of the stainless steel bipolar plate of the all-vanadium redox flow battery provided by the present invention is characterized in that: the coating preparation atmosphere is hydrogen-acetylene mixed gas or hydrogen-methane mixed gas.
本发明提供的全钒液流电池不锈钢双极板表面碳化铬/石墨复合涂层，其特征在于：所述复合涂层的制备温度为800-950℃。 The chromium carbide/graphite composite coating on the surface of the stainless steel bipolar plate of the all-vanadium redox flow battery provided by the present invention is characterized in that the preparation temperature of the composite coating is 800-950°C.
本发明提供的全钒液流电池不锈钢双极板表面碳化铬/石墨复合涂层，其特征在于：所述复合涂层碳化铬内层的制备需在表层铬含量不低于30%的不锈钢上进行，需预先在不锈钢表面制备富铬层，以保证制备连续碳化铬层所需的铬源。不锈钢表面富铬层的获得可以采用固态粉末渗铬、物理气相沉积、电镀等方法获得。 The chromium carbide/graphite composite coating on the surface of the stainless steel bipolar plate of the all-vanadium redox flow battery provided by the present invention is characterized in that the chromium carbide inner layer of the composite coating needs to be prepared on stainless steel with a chromium content of not less than 30% in the surface layer To carry out, it is necessary to prepare a chromium-rich layer on the surface of stainless steel in advance to ensure the chromium source required for the preparation of a continuous chromium carbide layer. The chromium-rich layer on the surface of stainless steel can be obtained by solid powder chromizing, physical vapor deposition, electroplating and other methods.
本发明提供的全钒液流电池不锈钢双极板表面碳化铬/石墨复合涂层，所述复合涂层中的石墨外层可在Ni催化层的作用下更好地生长，因此在不锈钢表面富铬层的表面预先沉积一层厚度不超过1微米的Ni催化层。Ni催化层的制备可以采用电镀、物理气相沉积等方法。 The chromium carbide/graphite composite coating on the surface of the stainless steel bipolar plate of the all-vanadium redox flow battery provided by the present invention, the graphite outer layer in the composite coating can grow better under the action of the Ni catalyst layer, so rich The surface of the chromium layer is pre-deposited with a Ni catalytic layer with a thickness not exceeding 1 micron. The Ni catalytic layer can be prepared by methods such as electroplating and physical vapor deposition.
本发明提供的全钒液流电池不锈钢双极板表面碳化铬/石墨复合涂层,可施加在各种类型不锈钢（如304、316L、310型不锈钢）表面。复合涂层越厚，可以对不锈钢提供更长时间的保护。 The chromium carbide/graphite composite coating on the surface of the stainless steel bipolar plate of the all-vanadium redox flow battery provided by the present invention can be applied on the surface of various types of stainless steel (such as 304, 316L, and 310 stainless steel). The thicker the composite coating, the longer it will protect the stainless steel. the
以在316L不锈钢表面施加碳化铬/石墨复合涂层为例，该涂层能显著提高不锈钢在25℃2.5 mol/L的H2SO4水溶液中的腐蚀电位，降低腐蚀电流。涂层在长期浸泡过程中未发生破坏。不锈钢的电阻率为0.3Ω·cm。 Taking the application of chromium carbide/graphite composite coating on the surface of 316L stainless steel as an example, the coating can significantly increase the corrosion potential of stainless steel in 2.5 mol/L H 2 SO 4 aqueous solution at 25 °C and reduce the corrosion current. The coating was not damaged during long-term immersion. The resistivity of stainless steel is 0.3Ω·cm.
the
具体实施方式 Detailed ways
实施例1 Example 1
采用化学气相沉积方法在316不锈钢双极板表面制备碳化铬/石墨复合涂层。首先采用固态粉末渗铬法在316不锈钢表面制备富铬层，进一步采用电镀法在不锈钢表面沉积厚度为1微米的金属Ni层。在9000C，H2-4%C2H2混合气氛中反应2小时，可以获得外层厚度为2.5微米，内层厚度为10微米的碳化铬/石墨复合涂层。涂层能显著提高不锈钢在25℃, 2.5 mol/L H2SO4水溶液中的腐蚀电位，降低腐蚀电流。涂层在长期浸泡过程中未发生破坏。不锈钢的电阻率为0.3Ω·cm。 Chromium carbide/graphite composite coatings were prepared on the surface of 316 stainless steel bipolar plates by chemical vapor deposition. First, a chromium-rich layer was prepared on the surface of 316 stainless steel by solid powder chromizing method, and a metal Ni layer with a thickness of 1 micron was deposited on the surface of stainless steel by electroplating. React at 900 ℃ for 2 hours in a H 2 -4% C 2 H 2 mixed atmosphere, and a chromium carbide/graphite composite coating with an outer layer thickness of 2.5 microns and an inner layer thickness of 10 microns can be obtained. The coating can significantly increase the corrosion potential and reduce the corrosion current of stainless steel in 25℃, 2.5 mol/L H 2 SO 4 aqueous solution. The coating was not damaged during long-term immersion. The resistivity of stainless steel is 0.3Ω·cm.
实施例2 Example 2
采用化学气相沉积方法在316不锈钢双极板表面制备碳化铬/石墨复合涂层。首先采用固态粉末渗铬法在316不锈钢表面制备富铬层，进一步采用电镀法在不锈钢表面沉积厚度为1微米的金属Ni层。在9500C，H2-4%C2H2混合气氛中反应2小时，可以获得外层厚度为3微米，内层厚度为14微米的碳化铬/石墨复合涂层。涂层能显著提高不锈钢在25℃, 2.5 mol/L H2SO4水溶液中的腐蚀电位，降低腐蚀电流。涂层在长期浸泡过程中未发生破坏。不锈钢的电阻率为0.33Ω·cm。 Chromium carbide/graphite composite coatings were prepared on the surface of 316 stainless steel bipolar plates by chemical vapor deposition. First, a chromium-rich layer was prepared on the surface of 316 stainless steel by solid powder chromizing method, and a metal Ni layer with a thickness of 1 micron was deposited on the surface of stainless steel by electroplating. React at 950 0 C for 2 hours in a H 2 -4% C 2 H 2 mixed atmosphere to obtain a chromium carbide/graphite composite coating with an outer layer thickness of 3 microns and an inner layer thickness of 14 microns. The coating can significantly increase the corrosion potential and reduce the corrosion current of stainless steel in 25℃, 2.5 mol/L H 2 SO 4 aqueous solution. The coating was not damaged during long-term immersion. The resistivity of stainless steel is 0.33Ω·cm.
the
实施例3 Example 3
采用化学气相沉积方法在316不锈钢双极板表面制备碳化铬/石墨复合涂层。首先采用固态粉末渗铬法在316不锈钢表面制备富铬层，进一步采用电镀法在不锈钢表面沉积厚度为1微米的金属Ni层。在9000C，H2-8%C2H2混合气氛中反应2小时，可以获得外层厚度约为2.8微米，内层厚度为13微米的碳化铬/石墨复合涂层。涂层能显著提高不锈钢在25℃, 2.5 mol/L H2SO4水溶液中的腐蚀电位，降低腐蚀电流。涂层在长期浸泡过程中未发生破坏。不锈钢的电阻率为0.32Ω·cm。 Chromium carbide/graphite composite coatings were prepared on the surface of 316 stainless steel bipolar plates by chemical vapor deposition. First, a chromium-rich layer was prepared on the surface of 316 stainless steel by solid powder chromizing method, and a metal Ni layer with a thickness of 1 micron was deposited on the surface of stainless steel by electroplating. React at 900 ℃ for 2 hours in a H 2 -8% C 2 H 2 mixed atmosphere, and a chromium carbide/graphite composite coating with an outer layer thickness of about 2.8 microns and an inner layer thickness of 13 microns can be obtained. The coating can significantly increase the corrosion potential and reduce the corrosion current of stainless steel in 25℃, 2.5 mol/L H 2 SO 4 aqueous solution. The coating was not damaged during long-term immersion. The resistivity of stainless steel is 0.32Ω·cm.
the
实施例4 Example 4
采用化学气相沉积方法在316不锈钢双极板表面制备碳化铬/石墨复合涂层。首先采用固态粉末渗铬法在316不锈钢表面制备富铬层，进一步采用电镀法在不锈钢表面沉积厚度为1微米的金属Ni层。在9000C，H2-4%C2H2混合气氛中反应3小时，可以获得外层厚度约为4微米，内层厚度为17微米的碳化铬/石墨复合涂层。涂层能显著提高不锈钢在25℃, 2.5 mol/L H2SO4水溶液中的腐蚀电位，降低腐蚀电流。涂层在长期浸泡过程中未发生破坏。不锈钢的电阻率为0.35Ω·cm。 Chromium carbide/graphite composite coatings were prepared on the surface of 316 stainless steel bipolar plates by chemical vapor deposition. First, a chromium-rich layer was prepared on the surface of 316 stainless steel by solid powder chromizing method, and a metal Ni layer with a thickness of 1 micron was deposited on the surface of stainless steel by electroplating. React at 900 ℃ for 3 hours in a mixed atmosphere of H 2 -4%C 2 H 2 , and a chromium carbide/graphite composite coating with an outer layer thickness of about 4 microns and an inner layer thickness of 17 microns can be obtained. The coating can significantly increase the corrosion potential and reduce the corrosion current of stainless steel in 25℃, 2.5 mol/L H 2 SO 4 aqueous solution. The coating was not damaged during long-term immersion. The resistivity of stainless steel is 0.35Ω·cm.
the
实施例5 Example 5
采用化学气相沉积方法在304不锈钢双极板表面制备碳化铬/石墨复合涂层。首先采用固态粉末渗铬法在304不锈钢表面制备富铬层，进一步采用电镀法在不锈钢表面沉积厚度为1微米的金属Ni层。在9000C，H2-4%C2H2混合气氛中反应2小时，可以获得外层厚度为2微米，内层厚度为12微米的碳化铬/石墨复合涂层。涂层能显著提高不锈钢在25℃, 2.5 mol/L H2SO4水溶液中的腐蚀电位，降低腐蚀电流。涂层在长期浸泡过程中未发生破坏。不锈钢的电阻率为0.3Ω·cm。 Chromium carbide/graphite composite coatings were prepared on the surface of 304 stainless steel bipolar plates by chemical vapor deposition. First, a chromium-rich layer was prepared on the surface of 304 stainless steel by solid powder chromizing method, and a metal Ni layer with a thickness of 1 micron was deposited on the surface of stainless steel by electroplating. React at 900 ℃ for 2 hours in a mixed atmosphere of H 2 -4%C 2 H 2 , and a chromium carbide/graphite composite coating with an outer layer thickness of 2 microns and an inner layer thickness of 12 microns can be obtained. The coating can significantly increase the corrosion potential and reduce the corrosion current of stainless steel in 25℃, 2.5 mol/L H 2 SO 4 aqueous solution. The coating was not damaged during long-term immersion. The resistivity of stainless steel is 0.3Ω·cm.
the
实施例6 Example 6
采用化学气相沉积方法在316不锈钢双极板表面制备碳化铬/石墨复合涂层。首先采用电镀法在316不锈钢表面制备厚度为8微米的铬层，进一步采用电镀法在不锈钢表面沉积厚度为1微米的金属Ni层。在9000C，H2-4%C2H2混合气氛中反应2小时，可以获得外层厚度约为2.3微米，内层厚度为9微米的碳化铬/石墨复合涂层。涂层能显著提高不锈钢在25℃, 2.5 mol/L H2SO4水溶液中的腐蚀电位，降低腐蚀电流。涂层在长期浸泡过程中未发生破坏。不锈钢的电阻率为0.28Ω·cm。 Chromium carbide/graphite composite coatings were prepared on the surface of 316 stainless steel bipolar plates by chemical vapor deposition. First, a chromium layer with a thickness of 8 microns was prepared on the surface of 316 stainless steel by electroplating, and a metal Ni layer with a thickness of 1 micron was deposited on the surface of stainless steel by electroplating. React at 900 ℃ for 2 hours in a H 2 -4% C 2 H 2 mixed atmosphere, and a chromium carbide/graphite composite coating with an outer layer thickness of about 2.3 microns and an inner layer thickness of 9 microns can be obtained. The coating can significantly increase the corrosion potential and reduce the corrosion current of stainless steel in 25℃, 2.5 mol/L H 2 SO 4 aqueous solution. The coating was not damaged during long-term immersion. The resistivity of stainless steel is 0.28Ω·cm.
the
实施例7 Example 7
采用化学气相沉积方法在316不锈钢双极板表面制备碳化铬/石墨复合涂层。首先采用物理气相沉积法在316不锈钢表面制备厚度为5微米的铬层，进一步采用电镀法在不锈钢表面沉积厚度为1微米的金属Ni层。在9000C，H2-4%C2H2混合气氛中反应2小时，可以获得外层厚度约为2.4微米，内层厚度为6微米的碳化铬/石墨复合涂层。涂层能显著提高不锈钢在25℃, 2.5 mol/L H2SO4水溶液中的腐蚀电位，降低腐蚀电流。涂层在长期浸泡过程中未发生破坏。不锈钢的电阻率为0.29Ω·cm。 Chromium carbide/graphite composite coatings were prepared on the surface of 316 stainless steel bipolar plates by chemical vapor deposition. First, a chromium layer with a thickness of 5 microns was prepared on the surface of 316 stainless steel by physical vapor deposition, and a metal Ni layer with a thickness of 1 micron was deposited on the surface of stainless steel by electroplating. React at 900 ℃ for 2 hours in a H 2 -4% C 2 H 2 mixed atmosphere, and a chromium carbide/graphite composite coating with an outer layer thickness of about 2.4 microns and an inner layer thickness of 6 microns can be obtained. The coating can significantly increase the corrosion potential and reduce the corrosion current of stainless steel in 25℃, 2.5 mol/L H 2 SO 4 aqueous solution. The coating was not damaged during long-term immersion. The resistivity of stainless steel is 0.29Ω·cm.
the
实施例8 Example 8
采用化学气相沉积方法在316不锈钢双极板表面制备碳化铬/石墨复合涂层。首先采用物理气相沉积法在316不锈钢表面制备厚度为5微米的铬层，进一步采用电镀法在不锈钢表面沉积厚度为0.5微米的金属Ni层。在9000C，H2-4%C2H2混合气氛中反应2小时，可以获得外层厚度约为2微米，内层厚度为6微米的碳化铬/石墨复合涂层。涂层能显著提高不锈钢在25℃, 2.5 mol/L H2SO4水溶液中的腐蚀电位，降低腐蚀电流。涂层在长期浸泡过程中未发生破坏。不锈钢的电阻率为0.3Ω·cm。 Chromium carbide/graphite composite coatings were prepared on the surface of 316 stainless steel bipolar plates by chemical vapor deposition. First, a chromium layer with a thickness of 5 microns was prepared on the surface of 316 stainless steel by physical vapor deposition, and a metal Ni layer with a thickness of 0.5 microns was deposited on the surface of stainless steel by electroplating. React at 900 ℃ for 2 hours in a H 2 -4% C 2 H 2 mixed atmosphere, and a chromium carbide/graphite composite coating with an outer layer thickness of about 2 microns and an inner layer thickness of 6 microns can be obtained. The coating can significantly increase the corrosion potential and reduce the corrosion current of stainless steel in 25℃, 2.5 mol/L H 2 SO 4 aqueous solution. The coating was not damaged during long-term immersion. The resistivity of stainless steel is 0.3Ω·cm.
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| CN102723499A (en) * | 2012-06-07 | 2012-10-10 | 上海交通大学 | Metal bipolar plate of fuel cell with surface plating layers and preparation method thereof |
| CN102800871A (en) * | 2012-08-14 | 2012-11-28 | 上海交通大学 | Fuel cell metal bipolar plate carbon chromium gradient coating and preparation method |
| CN102851667A (en) * | 2012-09-08 | 2013-01-02 | 陕西长岭电子科技有限责任公司 | Treatment method of anode shell inner surface of sodium-sulfur battery |
| CN103633336A (en) * | 2012-08-29 | 2014-03-12 | 中国科学院大连化学物理研究所 | Bipolar plate for liquid flow energy storage battery and preparation method |
| CN104617317A (en) * | 2015-02-04 | 2015-05-13 | 大连融科储能技术发展有限公司 | A method for surface treatment of a bipolar plate for a flow battery and the resulting bipolar plate |
| US20150147620A1 (en) * | 2013-11-22 | 2015-05-28 | Samsung Electronics Co., Ltd. | Redox flow battery |
| CN105531862A (en) * | 2013-09-12 | 2016-04-27 | 住友电气工业株式会社 | Battery cell stacks and redox flow batteries |
| CN108336371A (en) * | 2018-02-05 | 2018-07-27 | 大连融科储能技术发展有限公司 | A bipolar plate for an all-vanadium redox flow battery |
| CN108637166A (en) * | 2018-05-16 | 2018-10-12 | 安徽三环水泵有限责任公司 | A kind of preparation method of slurry pump impeller |
| CN109478656A (en) * | 2016-06-10 | 2019-03-15 | 帝国创新有限公司 | Corrosion-inhibiting coating |
| CN109524682A (en) * | 2018-11-12 | 2019-03-26 | 临沂市产品质量监督检验所 | A kind of metal compound bipolar plate used for all-vanadium redox flow battery and preparation method thereof |
| CN113265638A (en) * | 2021-07-20 | 2021-08-17 | 中国科学院宁波材料技术与工程研究所 | High-conductivity corrosion-resistant graphite-like carbon protective multilayer composite coating and preparation method and application thereof |
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| CN102723499B (en) * | 2012-06-07 | 2014-08-06 | 上海交通大学 | Metal bipolar plate of fuel cell with surface plating layers and preparation method thereof |
| CN102723499A (en) * | 2012-06-07 | 2012-10-10 | 上海交通大学 | Metal bipolar plate of fuel cell with surface plating layers and preparation method thereof |
| CN102800871B (en) * | 2012-08-14 | 2015-07-08 | 上海交通大学 | Fuel cell metal bipolar plate carbon chromium gradient coating and preparation method |
| CN102800871A (en) * | 2012-08-14 | 2012-11-28 | 上海交通大学 | Fuel cell metal bipolar plate carbon chromium gradient coating and preparation method |
| CN103633336A (en) * | 2012-08-29 | 2014-03-12 | 中国科学院大连化学物理研究所 | Bipolar plate for liquid flow energy storage battery and preparation method |
| CN102851667A (en) * | 2012-09-08 | 2013-01-02 | 陕西长岭电子科技有限责任公司 | Treatment method of anode shell inner surface of sodium-sulfur battery |
| CN105531862A (en) * | 2013-09-12 | 2016-04-27 | 住友电气工业株式会社 | Battery cell stacks and redox flow batteries |
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| CN104617317A (en) * | 2015-02-04 | 2015-05-13 | 大连融科储能技术发展有限公司 | A method for surface treatment of a bipolar plate for a flow battery and the resulting bipolar plate |
| CN109478656A (en) * | 2016-06-10 | 2019-03-15 | 帝国创新有限公司 | Corrosion-inhibiting coating |
| CN109478656B (en) * | 2016-06-10 | 2023-08-29 | Ip2Ipo创新有限公司 | Corrosion resistant coating |
| CN108336371A (en) * | 2018-02-05 | 2018-07-27 | 大连融科储能技术发展有限公司 | A bipolar plate for an all-vanadium redox flow battery |
| CN108637166A (en) * | 2018-05-16 | 2018-10-12 | 安徽三环水泵有限责任公司 | A kind of preparation method of slurry pump impeller |
| CN108637166B (en) * | 2018-05-16 | 2020-02-11 | 安徽三环水泵有限责任公司 | Preparation method of slurry pump impeller |
| CN109524682A (en) * | 2018-11-12 | 2019-03-26 | 临沂市产品质量监督检验所 | A kind of metal compound bipolar plate used for all-vanadium redox flow battery and preparation method thereof |
| CN113265638A (en) * | 2021-07-20 | 2021-08-17 | 中国科学院宁波材料技术与工程研究所 | High-conductivity corrosion-resistant graphite-like carbon protective multilayer composite coating and preparation method and application thereof |
| CN113265638B (en) * | 2021-07-20 | 2021-09-14 | 中国科学院宁波材料技术与工程研究所 | High-conductivity corrosion-resistant graphite-like carbon protective multilayer composite coating and preparation method and application thereof |
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