CN113881960A - 一种电解海水制氢用低成本钛基二氧化锰复合阳极制备方法 - Google Patents
一种电解海水制氢用低成本钛基二氧化锰复合阳极制备方法 Download PDFInfo
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 239000013535 sea water Substances 0.000 title claims abstract description 28
- 239000001257 hydrogen Substances 0.000 title claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000010936 titanium Substances 0.000 title claims description 119
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 43
- 229910052719 titanium Inorganic materials 0.000 title claims description 39
- 238000002360 preparation method Methods 0.000 title claims description 30
- 238000005868 electrolysis reaction Methods 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000010410 layer Substances 0.000 claims abstract description 44
- 238000005507 spraying Methods 0.000 claims abstract description 33
- 239000011572 manganese Substances 0.000 claims abstract description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001301 oxygen Substances 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 238000004070 electrodeposition Methods 0.000 claims abstract description 15
- 239000002344 surface layer Substances 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000010891 electric arc Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
- LWOJVCRSXHGDIJ-UHFFFAOYSA-N manganese;oxomolybdenum Chemical compound [Mn].[Mo]=O LWOJVCRSXHGDIJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 238000007751 thermal spraying Methods 0.000 claims description 4
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910015667 MoO4 Inorganic materials 0.000 claims description 2
- 239000010419 fine particle Substances 0.000 claims description 2
- 239000002932 luster Substances 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000005488 sandblasting Methods 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims 1
- 239000000725 suspension Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 abstract description 4
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 12
- 229910000510 noble metal Inorganic materials 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000011229 interlayer Substances 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
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- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- JFBJUMZWZDHTIF-UHFFFAOYSA-N chlorine chlorite Inorganic materials ClOCl=O JFBJUMZWZDHTIF-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- -1 hydrogen Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
一种电解海水制氢用低成本钛基二氧化锰复合阳极制备方法，在钛基材表面电弧热喷涂制备出(Ti+Zr)N中间层，而后在其上阳极电沉积制备(Mn1‑xMox)O2+x‑WC活性层，获得Ti/(Ti+Zr)N/(Mn1‑xMox)O2+x‑WC形稳阳极。本发明利用(Ti+Zr)N取代IrO2中间层，且选用纳米尺度的碳化钨对掺Mo的二氧化锰氧化物活性层进行复合协同，有效利用了中间层优异的导电性，以及耐酸、碱、盐的抗腐蚀性，并经电弧喷涂制备使得表面粗化，比表面积明显增多，有助于活性表层具有更多的活性位点；产品表面裂纹宽度显著缩小，活性层细化、致密，且厚度增大，在实际工况下的析氧效率电解可达到99.9％。
Description
技术领域
本发明属于电催化形稳阳极材料制备技术领域，特别涉及一种电解海水制氢用低成本钛基二氧化锰复合阳极制备方法。
背景技术
氢能因具有燃烧热值高、来源丰富、运输和存储方便、反应产物绿色无污染的优点，被认为是未来最有潜力的能源载体和传统化石能源的最佳替代品。电解水制氢具有产氢纯度高等优势，被寄予厚望，而采用海水电解则避免了水纯化等额外成本，还可以直接利用广泛存在的海水或苦咸水进行制氢，因此，电解海水氢能开发更是被优先考虑。但实现海水电解制氢生产，既要求阳极不能释放有毒的氯气，还要求其必须具备高效率和长寿命的析氧反应特性。
然而，大量的研究事实已经证实几乎所有可用阳极材料在电解海水过程中都会优先产生氯气，目前已知，只有锰的氧化物可以在海水电解阳极反应中优先产生氧气，而尽管它的析氧效率仍不足以避免氯气的析出，但钛基MnO2涂层阳极依然成为海水环境中最有发展前景的阳极材料。
为了更好地做到工程应用，目前通常选择在钛基体与MnO2涂层之间添加一层贵金属氧化物(IrO2性能最佳)中间层，来阻挡活性氧的侵蚀从而防止钛基体表面生成绝缘的TiO2薄膜，利用其优异的导电和稳定性等特性。但贵金属氧化物除了制备工艺(热刷涂多次刷涂+热解)复杂以外，还存在储量稀少、价格高昂等多方面问题，从而极大地限制了它在实际工程上的应用。此外，对于表层MnO2活性层为了增强其导电性、析氧抑氯催化活性，通常还会通过掺杂Mo、W、Fe、V等元素以增强其析氧效率和避免氯气产生，但元素掺杂使得MnO2涂层导电性和活性增强的效果仍有限。
发明内容
为了克服上述的电解海水制氢用钛基二氧化锰涂层电极制备技术中存在的IrO2中间层成本高昂，制备工艺复杂以及仅通过元素掺杂并不能明显改变涂层导电性和催化活性的弊端，本发明的目的在于提供一种电解海水制氢用低成本钛基二氧化锰复合阳极制备方法，采用大气气氛下电弧喷涂导电(Ti+Zr)N中间层代替贵金属氧化物IrO2热解层，电弧喷涂制备技术操作简便，易于操控，施涂迅速，工作效率高，制备成本显著降低；并鉴于既然少量的Mo等元素掺杂到MnO2涂层中能够提升析氧效率，考虑W的催化活性与Mn接近，且其较Mo具有更高的催化活性，选择具有类Pt等特性(碳化钨WC具有六方晶体结构，有类似于贵金属铂的电子表面结构，对氧反应显示出良好的催化性能，它自身具有优异的高硬度，耐腐蚀)的WC进行复合，以期协同Mo掺杂来实现对析氧催化活性和析氧效率的显著提升。本发明通过在钛基材上通过电弧喷涂TiN中间层，表面再电沉积制备WC复合的掺Mo二氧化锰涂层，最终得到Ti/(Ti+Zr)N/(Mn1-xMox)O2+x-WC阳极。这一形稳阳极具有高的析氧效率，良好的抑氯特性，电极耐久性好。
为了实现上述目的，本发明采用的技术方案是：
一种电解海水制氢用低成本钛基二氧化锰复合阳极制备方法，首先在预处理好的钛基材表面利用电弧热喷涂制备出良好导电、耐蚀的(Ti+Zr)N中间层，而后在(Ti+Zr)N中间层上表面利用阳极复合电沉积制备WC复合的锰钼氧化物活性表层，最终得到析氧效率高，可长久使用的Ti/(Ti+Zr)N/(Mn1-xMox)O2+x-WC形稳涂层阳极，其中x为摩尔数，其值取0.1～0.2。
进一步地，所述钛基材的预处理是碱洗除油、草酸刻蚀和喷砂处理，使得表面形成凹凸不平的麻面层，呈灰色，失去金属光泽，获得无油污和氧化皮的洁净表面。
进一步地，所述电弧热喷涂采用两丝同送方式，所选取的喷涂丝材，一根为纯锆丝，另一根为纯钛丝，在大气环境中喷涂丝材穿过喷涂喷嘴中心，在围绕喷嘴和气罩形成的环形火焰中，金属丝的尖端被连续地被加热到其熔点。然后，通过气罩的压缩空气将其雾化，成喷射粒子，依靠空气流加速喷射到基体上，从而熔融的粒子冷却到塑性或半熔化状态，在雾化过程中与空气中氮气、氧气快速反应，形成金属锆和钛的氮/氧化物，熔覆沉积在预处理过的钛基体表面。
进一步地，可设定喷涂功率30-40kW，电弧电压5-35V，喷涂距离100-250mm，压缩空气压力0.3-1.0MPa，喷涂时间10-30s，喷涂过程中借助高温高速焰流，通过喷涂丝材与空气中氮气、氧气反应形成具有良好导电性，耐酸、碱、盐，且与钛基底结合紧密的(Ti+Zr)N中间层。
进一步地，所述纯锆丝和纯钛丝的直径为1.5-2.5mm。
进一步地，所述(Ti+Zr)N中间层厚度为30-200μm。
进一步地，为获得良好结合在制备中间层前首先对预处理后的钛基材进行电弧喷涂预热，温度控制为70-150℃。
电弧喷涂制备(Ti+Zr)N中间层的过程中，喷涂距离过长则离子到达基体时的温度及速率均会过低，颗粒沉积不上去，且粒子被氧化程度提高；过短则粒子在焰流中停留时间过短，未能充分加热和加速，因此，一般选择距离在10-20cm。
进一步地，所述复合电沉积制备WC复合的锰钼氧化物活性表层，是以Ti/(Ti+Zr)N为阳极，两块等面积的不锈钢板为阴极，置于含MnSO4、Na2MoO4、纳米级WC微粒及H2SO4的混合溶液中进行电沉积制备。之后将所制备的阳极用蒸馏水冲洗干净，热风吹干，得到表面致密、均匀、稳定性和活性均良好的Ti/(Ti+Zr)N/(Mn-Mo)Ox-WC形稳阳极材料。
进一步地，所述混合溶液中MnSO4浓度为0.2-0.3mol/L，Na2MoO4浓度为0.02-0.04mol/L，纳米级WC颗粒添加量为5-30g/L，用H2SO4调节溶液pH至0.5，电沉积温度为70-90℃，电沉积时间为20-60min，电流密度为400-800A·m-2。
进一步地，在将阳极和阴极置于混合溶液之前，将阳极除油洁净，并经10-20％HNO3溶液中浸蚀2-3min。
进一步地，所述电沉积制备过程中保持对混合溶液进行机械搅拌，确保WC颗粒悬浮，搅拌速率控制在200-600rpm。
与目前公认的电解海水制氢用Ti/IrO2/(Mn1-xMox)O2+x阳极制备技术相比，本发明对钛基体利用电弧喷涂技术制备出(Ti+Zr)N中间层，然后利用阳极沉积技术制备出Ti/(Ti+Zr)N/(Mn1-xMox)O2+x-WC阳极。本发明利用(Ti+Zr)N取代贵金属氧化物IrO2中间层，且选用理化性质优异的纳米尺度的碳化钨对掺Mo的二氧化锰氧化物活性层((Mn1-xMox)O2+x)进行复合协同，有效地利用了(Ti+Zr)N中间层优异的导电性，以及耐酸、碱、盐的抗腐蚀性，并经过电弧喷涂制备使得表面粗化，比表面积明显增多，有助于活性表层具有更多的活性位点。电弧喷涂(Ti+Zr)N中间层制备大大地简化了以涂刷法制备IrO2中间层的繁琐环节，并有效地降低了以贵重金属Ir、Ru氧化物等作为中间体的成本，加之，电弧喷涂工艺操作方便，电弧喷涂是两丝同时送进，喷涂效率高，运行费用少，成本低。同时，将纳米WC复合技术与元素掺杂相结合引入到钛基二氧化锰改性阳极的制备中，可明显解决阳极催化活性低、稳定性差等问题。经WC复合的Ti/TiN/(Mn1-xMox)O2+x阳极，表面裂纹宽度显著缩小，活性层细化、致密，且厚度增大，从而使得Ti/(Ti+Zr)N/(Mn1-xMox)O2+x-WC阳极在实际工况下的析氧效率电解可达到99.9％，经200h使用后才出现下降，显现出良好的取代应用前景。
附图说明
图1是本发明电弧喷涂(Ti+Zr)N中间层制备示意图。
图2是本发明制备的(Ti+Zr)N中间层结构图示。
图3是本发明制备的(Ti+Zr)N中间层表面扫描电镜图。
图4是本发明制备的(Ti+Zr)N中间层剖面的扫描电镜图。
图5是本发明制备的(Ti+Zr)N中间层X射线衍射谱图。
图6是本发明方法制备的阳极表层X射线衍射谱图。
图7是本发明方法制备的阳极在90℃，pH 12的3.5wt％NaCl溶液中电解时析氧效率随时间的演化行为对比。
具体实施方式
下面结合附图和实施例详细说明本发明的实施方式。
实施例1
首先采用经过打磨、碱洗、酸洗的钛板为基体，然后采用电弧喷涂技术制备(Ti+Zr)N中间层，最后再以Ti/(Ti+Zr)N电极材料为阳极，等面积大小的不锈钢为阴极，阳极电氧化制备出(Mn1-xMox)O2+x-WC活性层，从而获得Ti/(Ti+Zr)N/(Mn1-xMox)O2+x-WC电极。
(Ti+Zr)N中间层的制备如图1所示，采用两丝同送方式，喷涂丝材分别为纯锆丝和纯钛丝，在大气环境中喷涂丝材穿过喷涂喷嘴中心，在围绕喷嘴和气罩形成的环形火焰中，金属丝的尖端被连续地被加热到其熔点。然后，通过气罩的压缩空气将其雾化，成喷射粒子，依靠空气流加速喷射到基体上，从而熔融的粒子冷却到塑性或半熔化状态，在雾化过程中与空气中氮气、氧气快速反应，形成金属锆和钛的氮/氧化物，熔覆沉积在预处理过的钛基体表面。
本实施例中(Ti+Zr)N中间层制备工艺参数：钛、锆丝直径：1.8mm；预热温度80℃；喷涂功率36kW；工作电压30V；喷涂距离10cm。
(Mn1-xMox)O2+x-WC活性层阳极电沉积条件如下：沉积液配方为0.2mol/L MnSO4、0.03/L Na2MoO4·2H2O和10g/L纳米级WC，电流密度600A·m-2，温度80℃，沉积时间30min，电磁搅拌，用H2SO4调节溶液pH至0.5。将制备的Ti/(Ti+Zr)N/(Mn1-xMox)O2+x-WC电极用蒸馏水冲洗干净，冷风吹干，得到表面致密、均匀的形稳阳极。对电极结构进行观察，经过电弧喷涂(Ti+Zr)N中间层的Ti/(Ti+Zr)N基体相较于钛基体表面粗糙度更大，相应比表面积更多，制备的活性层具有更多的活性位点。
Ti/(Ti+Zr)N/(Mn1-xMox)O2+x-WC阳极相较于无WC复合的Ti/TiN/(Mn1-xMox)O2+x阳极，表面裂纹宽度显著缩小，活性层均匀且致密，且厚度增加，如图2、图3和图4所示。
对(Ti+Zr)N中间层表面进行XRD分析，如图5所示，可见所制备的(Ti+Zr)N中间层是以TiN和ZrN互溶体为主相的多相组成物，由于较高熔点的锆较于钛具有更高的氧亲和性，因此，中间层组成中呈现为较多锆氧化物的杂相。
对Ti/(Ti+Zr)N/(Mn1-xMox)O2+x和Ti/(Ti+Zr)N/(Mn1-xMox)O2+x-WC阳极表面进行XRD分析，如图6所示，可见所获得的涂层都是以γ-MnO2为主相(JCPDS No.30-0820)涂层，这与电沉积二氧化锰的一般晶体学特征保持一致。当涂层中引入纳米级碳化钨(JCPDS No.20-1316)颗粒进行复合后，受到WC衍射峰的影响，MnO2衍射峰(2θ为37.120、42.401、56.027、75.022和78.921)出现一定程度向右偏移的特征。同时，2θ角为62.027°处也显示出明显属于WC衍射的峰。
实施例2
电极长期的耐用性是通过以1000A·m-2的恒定电流密度在90℃和pH为12的3.5wt％NaCl溶液中持续电解来进行评估。在实际的海水电解中，阳极室和阴极室将被分开以避免氢气和氧气的混合。由于H+和OH-的产生，阳极电解液的pH值迅速降低，阴极电解的pH值则迅速升高。如果允许H+和OH-离子混合，它们会结合产生水分子，中和电解液的酸碱性。因此，实际电解过程中会定期将碱性的阴极电解液引入阳极室，在阳极室电解至pH值为7左右，再将电解液返回阴极电解液罐。因此，使用pH值为12的3.5wt％NaCl溶液来检查电极的耐用性。纯钛(>99.98％)电极用作电解过程中的对电极。析氧效率的测定是通过在300ml3.5wt％NaCl溶液中以1000A·m-2的恒定电流密度电解，直到通过300库仑电荷。释放氧气的含量是通过电解消耗的总电荷与电解过程中形成氯的电荷之间的差值来估算的，通过碘量法(GB 19106-2003)测定电解液中氯和次氯酸盐的生成量。
在实际工况下将本发明的Ti/(Ti+Zr)N/(Mn1-xMox)O2+x-WC和Ti/(Ti+Zr)N/(Mn1- xMox)O2+x电极与公认的电解海水用Ti/IrO2/(Mn1-xMox)O2+x析氧阳极进行对比测试，参考图7，从三种电极的电解析氧效率随时间变化的对比试验中可以看出，电弧喷涂(Ti+Zr)N中间层的Ti/(Ti+Zr)N/(Mn1-xMox)O2+x-WC和Ti/(Ti+Zr)N/(Mn1-xMox)O2+x阳极在电解初始阶段与含有贵金属氧化物中间层的Ti/IrO2/(Mn-Mo)Ox阳极的析氧效率都接近100％。其中，表层复合碳化钨的Ti/(Ti+Zr)N/(Mn1-xMox)O2+x-WC阳极表现出最优异的性能，电解初始阶段析氧效率可达到99.9％，在电解200h后电极性能才开始显著下降，表现为析氧性能的显著降低。而未掺杂WC的Ti/(Ti+Zr)N/(Mn1-xMox)O2+x和Ti/IrO2/(Mn1-xMox)O2+x阳极在电解较短时间100h内析氧性能持续退化，其中Ti/(Ti+Zr)N/(Mn1-xMox)O2+x阳极在100h析氧性能仅为15.9％，可见采用本发明方法制备的Ti/(Ti+Zr)N/(Mn1-xMox)O2+x-WC电极在实际工况中应用效果很好，通过电弧喷涂制备的中间层可在短期内达到与贵金属氧化物中间层同样的效果。
以上对本发明实施所提供的一种电解海水制氢用低成本钛基二氧化锰复合阳极制备方法进行了详细介绍，文中应用了具体实施例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的方法及其核心思想；而对于本领域的一般技术人员，依据本发明的思想，在具体实范围施方式及应用上均会有改变之处，故本说明书内容不应理解为对本发明的限制。
Claims (10)
1.一种电解海水制氢用低成本钛基二氧化锰复合阳极制备方法，其特征在于，首先在预处理好的钛基材表面利用电弧热喷涂制备出(Ti+Zr)N中间层，而后在(Ti+Zr)N中间层上表面利用阳极复合电沉积制备WC复合的锰钼氧化物活性表层，最终得到Ti/(Ti+Zr)N/(Mn1-xMox)O2+x-WC形稳涂层阳极，其中x为摩尔数，其值取0.1～0.2。
2.根据权利要求1所述电解海水制氢用低成本钛基二氧化锰复合阳极制备方法，其特征在于，所述钛基材的预处理是碱洗除油、草酸刻蚀和喷砂处理，使得表面形成凹凸不平的麻面层，呈灰色，失去金属光泽，获得无油污和氧化皮的洁净表面。
3.根据权利要求1所述电解海水制氢用低成本钛基二氧化锰复合阳极制备方法，其特征在于，所述电弧热喷涂采用两丝同送方式，所选取的喷涂丝材，一根为纯锆丝，另一根为纯钛丝，在大气环境中喷涂丝材穿过喷涂喷嘴中心，设定喷涂功率30-40kW，电弧电压5-35V，喷涂距离100-250mm，压缩空气压力0.3-1.0MPa，喷涂过程中借助高温高速焰流，通过喷涂丝材与空气中氮气、氧气反应形成(Ti+Zr)N中间层。
4.根据权利要求3所述电解海水制氢用低成本钛基二氧化锰复合阳极制备方法，其特征在于，在制备中间层前首先对预处理后的钛基材进行电弧喷涂预热，温度控制为70-150℃。
5.根据权利要求1或3或4所述电解海水制氢用低成本钛基二氧化锰复合阳极制备方法，其特征在于，所述(Ti+Zr)N中间层厚度为30-200μm。
6.根据权利要求1所述电解海水制氢用低成本钛基二氧化锰复合阳极制备方法，其特征在于，所述复合电沉积制备WC复合的锰钼氧化物活性表层，是是以Ti/(Ti+Zr)N为阳极，两块等面积的不锈钢板为阴极，置于含MnSO4、Na2MoO4、纳米级WC微粒及H2SO4的混合溶液中进行电沉积制备。
7.根据权利要求1所述电解海水制氢用低成本钛基二氧化锰复合阳极制备方法，其特征在于，所述混合溶液中MnSO4浓度为0.2-0.3mol/L，Na2MoO4浓度为0.02-0.04mol/L，纳米级WC颗粒添加量为5-30g/L，用H2SO4调节溶液pH至0.5，电沉积温度为70-90℃，电沉积时间为20-60min，电流密度为400-800A·m-2。
8.根据权利要求6或7所述电解海水制氢用低成本钛基二氧化锰复合阳极制备方法，其特征在于，完成沉积后，将所制备的阳极用蒸馏水冲洗干净，热风吹干，得到表面致密、均匀的Ti/(Ti+Zr)N/(Mn1-xMox)O2+x-WC形稳阳极材料。
9.根据权利要求6所述电解海水制氢用低成本钛基二氧化锰复合阳极制备方法，其特征在于，在将阳极和阴极置于混合溶液之前，将阳极除油洁净，并经10-20％HNO3溶液中浸蚀2-3min。
10.根据权利要求6所述电解海水制氢用低成本钛基二氧化锰复合阳极制备方法，其特征在于，所述电沉积制备过程中保持对混合溶液进行机械搅拌，确保WC颗粒悬浮，搅拌速率控制在200-600rpm。
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