CN111229271B - 催化剂材料与其形成方法 - Google Patents
催化剂材料与其形成方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 204
- 239000000463 material Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 12
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 50
- 229910052799 carbon Inorganic materials 0.000 claims description 50
- 238000004544 sputter deposition Methods 0.000 claims description 25
- 239000012159 carrier gas Substances 0.000 claims description 14
- 238000005868 electrolysis reaction Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 121
- 239000010955 niobium Substances 0.000 description 99
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 61
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 50
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 41
- 230000000694 effects Effects 0.000 description 36
- 239000012528 membrane Substances 0.000 description 33
- 229910052786 argon Inorganic materials 0.000 description 31
- 229910052757 nitrogen Inorganic materials 0.000 description 30
- 238000009792 diffusion process Methods 0.000 description 22
- 238000004458 analytical method Methods 0.000 description 21
- 229910052697 platinum Inorganic materials 0.000 description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 229910021397 glassy carbon Inorganic materials 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 17
- 229910001220 stainless steel Inorganic materials 0.000 description 17
- 239000010935 stainless steel Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- -1 halogen ions Chemical class 0.000 description 13
- 239000003011 anion exchange membrane Substances 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 239000011148 porous material Substances 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 10
- 238000005546 reactive sputtering Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000000151 deposition Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 230000002441 reversible effect Effects 0.000 description 7
- 239000012670 alkaline solution Substances 0.000 description 6
- 238000001755 magnetron sputter deposition Methods 0.000 description 6
- 229910052707 ruthenium Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910001257 Nb alloy Inorganic materials 0.000 description 4
- 229910000990 Ni alloy Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000005121 nitriding Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910000619 316 stainless steel Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000013077 target material Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- 230000000712 assembly Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- FCZCIXQGZOUIDN-UHFFFAOYSA-N ethyl 2-diethoxyphosphinothioyloxyacetate Chemical compound CCOC(=O)COP(=S)(OCC)OCC FCZCIXQGZOUIDN-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005324 grain boundary diffusion Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
- C01B21/0622—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with iron, cobalt or nickel
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- C01B21/0602—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with two or more other elements chosen from metals, silicon or boron
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- C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
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Abstract
催化剂材料的形成方法,包括:将M’靶材与M”靶材置于含氮气的氛围中,其中M’为Ni、Co、Fe、Mn、Cr、V、Ti、Cu、或Zn,且M”为Nb、Ta、或上述的组合;分别提供功率至M’靶材与M”靶材;以及提供离子撞击M’靶材与M”靶材,以溅镀沉积M’aM”bN2于基材上,其中0.7≤a≤1.7,0.3≤b≤1.3,且a+b=2,其中M’aM”bN2为立方晶系。
Description
【技术领域】
本公开涉及催化剂材料与其制备方法。
【背景技术】
在能源短缺的现今,寻求替代能源势在必行,而氢能为最佳的替代能源。由于环境保护的观念,使用氢气作为燃料符合环保期待,电解水是制造氢气与氧气的最简单方式。尽管利用电解水产氢具有相当多的优点,但是在大量产氢的过程却具有致命的缺点,即耗费相当多的能量导致不符成本。能量消耗多与过电位过大有关,而过电位与电极、电解液、及反应生成物有关。为提升电解水效率,电极扮演重要角色。降低活化能及增加反应的界面为电解水效率的重要因素。活化能降低是受电极表面催化的影响,其取决于电极材料本身催化特性。虽然贵金属IrO2一直是最具催化效果的电极材料之一,但其价格相当昂贵。为降低成本,必须采用其他材料取代IrO2。
综上所述,目前需要新的催化剂组成进一步提升产氢反应(HER)与产氧反应(OER)的活性,以兼顾催化剂活性与降低成本的目的。
【发明内容】
本公开一实施例提供催化剂材料,其化学结构为:M’aM”bN2,其中M’为Ni、Co、Fe、Mn、Cr、V、Ti、Cu、或Zn,M”为Nb、Ta、或上述的组合,0.7≤a≤1.7,0.3≤b≤1.3,且a+b=2,其中催化剂材料为立方晶系。
在一实施例中,M’为Ni,M”为Nb,且0.7≤a≤1.51,0.49≤b≤1.30。
本发明一实施例提供催化剂材料,其化学结构为:M’cM”dCe,其中M’为Ni、Co、Fe、Mn、Cr、V、Ti、Cu、或Zn,M”为Nb、Ta、或上述的组合,0.24≤c≤1.7,0.3≤d≤1.76,且0.38≤e≤3.61,其中催化剂材料为立方晶系或非晶。
在一实施例中,M’为Ni且M”为Nb,0.90≤c≤1.47,0.53≤d≤1.10,且0.9≤e≤1.9。
在一实施例中,M’为Ni且M”为Nb,0.74≤c≤1.63,0.37≤d≤1.26,且0.38≤e≤1.30。
在一实施例中,M’为Co且M”为Nb,0.24≤c≤1.39,0.61≤d≤1.76,且0.63≤e≤3.61。
本发明一实施例提供催化剂材料的形成方法,包括:将M’靶材与M”靶材置于含氮气的氛围中,其中M’为Ni、Co、Fe、Mn、Cr、V、Ti、Cu、或Zn,且M”为Nb、Ta、或上述的组合;分别提供功率至M’靶材与M”靶材;以及提供离子撞击M’靶材与M”靶材,以溅镀沉积M’aM”bN2于基材上,其中0.7≤a≤1.7,0.3≤b≤1.3,且a+b=2,其中M’aM”bN2为立方晶系。
在一实施例中,提供至M’靶材的功率介于10至200W之间,而提供至M”靶材的功率介于10至200W之间。
在一实施例中,含氮气的氛围压力介于1毫托(mTorr)至30毫托之间。
在一实施例中,含氮气的氛围包含载气,且氮气与载气的分压比例介于0.1至10之间。
在一实施例中,基材包括多孔导电层。
本发明一实施例提供催化剂材料的形成方法,包括:将M’靶材、M”靶材、与碳靶材置于载气氛围中,其中M’为Ni、Co、Fe、Mn、Cr、V、Ti、Cu、或Zn,且M”为Nb、Ta、或上述的组合;分别提供功率至M’靶材、M”靶材、与碳靶材;以及提供离子撞击M’靶材、M”靶材、与碳靶材,以溅镀沉积M’cM”dCe于基材上,其中0.24≤c≤1.7,0.3≤d≤1.76,且0.38≤e≤3.61,其中M’cM”dCe为立方晶系或非晶。
在一实施例中,提供至M’靶材的功率介于10至200W之间,提供至M”靶材的功率介于10至200W之间,且提供至碳靶材的功率介于10至200W之间。
在一实施例中,载气氛围的压力介于1毫托至30毫托之间。
在一实施例中,基材包括多孔导电层。
【附图说明】
图1为一实施例中,膜电极组的示意图。
图2为一实施例中,Ru催化剂与NixRuy催化剂的OER曲线。
图3为一实施例中,Ru2N2催化剂NixRuyN2催化剂的OER曲线。
图4为一实施例中,Ru催化剂与NixRuy催化剂的HER曲线。
图5为一实施例中,Ru催化剂与NixRuyN2催化剂的HER曲线。
图6为一实施例中,Ni2N2催化剂与MnxRuyN2催化剂的OER曲线。
图7为一实施例中,Ni2N2催化剂与MnxRuyN2催化剂的HER曲线。
图8为一实施例中,NiaNbbN2催化剂的OER曲线。
图9为一实施例中,NicNbdCe催化剂与Nb0.6556C1.3444催化剂的OER曲线。
图10为一实施例中,NicNbdCe催化剂与Nb0.6556C1.3444催化剂的OER曲线。
图11为一实施例中,CocNbdCe催化剂与Nb0.6556C1.3444催化剂的OER曲线。
图12为一实施例中,CocNbdCe催化剂与Nb0.6556C1.3444催化剂的OER曲线。
图13为一实施例中,CocNbdCe催化剂与Nb0.6556C1.3444催化剂的OER曲线。
图14为一实施例中,CocNbdCe催化剂与Nb0.6556C1.3444催化剂的OER曲线。
图15为一实施例中,CocNbdCe催化剂与Nb0.6556C1.3444催化剂的OER曲线。
图16至图19为实施例中,膜电极组的电流-电压曲线。
图20为一实施例中,膜电极组长时间操作后的电流图。
【附图标记说明】
11 阳极;
11A、15A 气液扩散层;
11B、15B 催化剂层;
13 阴离子交换膜;
15 阴极;
100 膜电极组。
【具体实施方式】
本公开一实施例提供催化剂材料,其化学结构为:M’aM”bN2,其中M’为Ni、Co、Fe、Mn、Cr、V、Ti、Cu、或Zn,M”为Nb、Ta、或上述的组合,0.7≤a≤1.7,0.3≤b≤1.3,且a+b=2,其中催化剂材料为立方晶系。在一实施例中,a介于约0.3128至1.5082之间,例如:a为1.0296-1.3182或1.3182-1.5082,而b介于约0.4918至1.6872之间,例如:b为0.4918-0.6818或0.6818-0.9702。在一实施例中,M’为Ni,M”为Nb,0.7≤a≤1.51,且0.49≤b≤1.30。若a过小(即b过大),则活性不佳。若a过大(即b过小),则活性与稳定性不佳。
本发明一实施例提供催化剂材料,其化学结构为:M’cM”dCe,其中M’为Ni、Co、Fe、Mn、Cr、V、Ti、Cu、或Zn,M”为Nb、Ta、或上述的组合,0.24≤c≤1.7,0.3≤d≤1.76,且0.38≤e≤3.61,其中催化剂材料为立方晶系或非晶。在一实施例中,M’为Ni且M”为Nb,0.90≤c≤1.47,0.53≤d≤1.10,且0.9≤e≤1.9。在一实施例中,M’为Ni且M”为Nb,0.74≤c≤1.63,0.37≤d≤1.26,且0.38≤e≤1.30。在一些实施例中,M’为Co且M”为Nb,0.24≤c≤1.39,0.61≤d≤1.76,且0.63≤e≤3.61。若c过小(即d过大),则活性不佳。若c过大(即d过小),则活性与稳定性不佳。若e过小,则活性不佳。若e过大,则活性与稳定性不佳。
本发明一实施例提供催化剂材料的形成方法,包括:将M’靶材与M”靶材置于含氮气的氛围中,其中M’为Ni、Co、Fe、Mn、Cr、V、Ti、Cu、或Zn,且M”为Nb、Ta、或上述的组合。分别提供功率至M’靶材与M”靶材;以及提供离子撞击M’靶材与M”靶材,以溅镀沉积M’aM”bN2于基材上,其中其中0.7≤a≤1.7,0.3≤b≤1.3,且a+b=2,其中M’aM”bN2为立方晶系。在一实施例中,含氮气的氛围压力介于1毫托至30毫托之间。若含氮气的氛围压力过低,则无法进行有效氮化反应。若含氮气的氛围压力过高,则无法进行有效氮化反应。在一实施例中,含氮气的氛围包含载气如氦气、氩气、其他合适的惰性气体(钝气)、或上述的组合,且氮气与载气的分压比例介于0.1-10之间。若氮气的分压比例过低,则无法进行有效氮化反应。若氮气的分压比例过高,则无法进行有效氮化反应。上述方法分别提供功率至M’靶材与M”靶材。举例来说,提供至M’靶材的功率介于10-200W之间。若提供至M’靶材的功率过低,则催化剂材料中的M’比例过低。若提供至M’靶材的功率过高,则催化剂材料中的M’比例过高。另一方面,提供至M”靶材的功率介于10-200W之间。若提供至M”靶材的功率过低,则催化剂材料中的M”比例过低。若提供至M”靶材的功率过高,则催化剂材料中的M”比例过高。上述功率可为直流电功率或射频功率。
上述方法亦提供离子撞击M’靶材与M”靶材,以溅镀沉积M’aM”bN2于基材上。举例来说,可等离子体(电浆)激发氮气与载气以形成离子,并使离子撞击靶材。在一实施例中,基材包括多孔导电层,比如多孔的金属网(如不锈钢网、钛网、镍网、镍合金网、铌合金网、铜网、或铝网)。多孔导电层的孔径取决于M’aM”bN2的用途。举例来说,若具其上有M’aM”bN2的多孔导电层作为电解碱性水溶液的阳极(用于OER),则多孔导电层的孔径介于40微米至150微米之间。
本发明一实施例提供催化剂材料的形成方法,包括:将M’靶材、M”靶材、与碳靶材置于载气氛围中,其中M’为Ni、Co、Fe、Mn、Cr、V、Ti、Cu、或Zn,且M”为Nb、Ta、或上述的组合。分别提供功率至M’靶材、M”靶材、与碳靶材;以及提供离子撞击M’靶材、M”靶材、与碳靶材,以溅镀沉积M’cM”dCe于基材上,其中0.24≤c≤1.7,0.3≤d≤1.76,且0.38≤e≤3.61,其中M’cM”dCe为立方晶系或非晶。在一实施例中,载气氛围的压力介于1毫托至30毫托之间。若载气氛围压力过低,则无法形成有效结晶。若载气氛围压力过高,则无法形成有效结晶。在一实施例中,载气可为氦气、氩气、其他合适的惰性气体、或上述的组合。上述方法分别提供功率至M’靶材、M”靶材、与碳靶材。举例来说,提供至M’靶材的功率介于10至200W之间。若提供至M’靶材的功率过低,则催化剂材料中的M’比例过低。若提供至M’靶材的功率过高,则催化剂材料中的M’比例过高。提供至M”靶材的功率介于10至200W之间。若提供至M”靶材的功率过低,则催化剂材料中的M”比例过低。若提供至M”靶材的功率过高,则催化剂材料中的M”比例过高。另一方面,提供至碳靶材的功率介于10至200W之间。若提供至碳靶材的功率过低,则催化剂材料中的碳比例过低。若提供至碳靶材的功率过高,则催化剂材料中的碳比例过高。上述功率可为直流电功率或射频功率。
上述方法亦提供离子撞击M’靶材、M”靶材、与碳靶材,以溅镀沉积M’cM”dCe于基材上。举例来说,可等离子体激发氮气以形成离子,并使离子撞击靶材。在一实施例中,基材包括多孔导电层,比如多孔的金属网(如不锈钢网、钛网、镍网、镍合金网、铌合金网、铜网、或铝网)。多孔导电层的孔径取决于M’cM”dCe的用途。举例来说,若其上具有M’cM”dCe的多孔导电层作为电解碱性水溶液的阳极(用于OER),则多孔导电层的孔径介于40微米至150微米之间。
在一实施例中,上述催化剂材料可用于电解产氢的膜电极组。如图1所示,膜电极组100包括阳极11、阴极15、与阴离子交换膜13,且阴离子交换膜夹设于阳极11与阴极15之间。阳极11包括催化剂层11B于气液扩散层11A上,而阴极15包括催化剂层15B于气液扩散层15A上。此外,阴离子交换膜13夹设于阳极11的催化剂层11B与阴极15的催化剂层15B之间。催化剂层11B的化学结构为M’aM”bN2或M’cM”dCe,而M’、M”、a、b、c、d、与e的定义同前述,在此不重复。
在一实施例中,阴离子交换膜13可为含卤素离子的咪唑高分子或其他合适材料。举例来说,阴离子交换膜13可为购自Fumatech的FAS或购自Dioxide materials的X37-50。由于膜电极组100用于电解碱性水溶液产氢,因此采用阴离子交换膜13而非其他离子交换膜。
在一实施例中,气液扩散层11A与气液扩散层15A各自包括多孔导电层。举例来说,气液扩散层11A可为多孔的金属网(如不锈钢网、钛网、镍网、镍合金网、铌合金网、铜网、或铝网)。另一方面,气液扩散层15A可为多孔的金属网(如不锈钢网、钛网、镍网、镍合金网、铌合金网、铜网、或铝网)或多孔碳材(如碳纸或碳布)。在一实施例中,气液扩散层11A的孔径介于40微米至150微米之间。若气液扩散层11A的孔径过小,则增加传质阻抗。若气液扩散层11A的孔径过大,则丧失活性面积。在一实施例中,气液扩散层15A的孔径介于0.5微米至5微米之间。若气液扩散层15A的孔径过小,则增加传质阻抗。若气液扩散层15A的孔径过大,则丧失活性面积。
在其他实施例中,阳极11的气液扩散层11A与阴极15的气液扩散层15A的孔径不同及/或组成不同,或者阳极11的催化剂层11B与阴极15的催化剂层15B的元素组成或元素比例不同,应视需求而定。举例来说,催化剂层11B的化学结构为M’aM”bN2或M’cM”dCe,而催化剂层15B的化学结构为MxRuyN2或MxRuy,其中M为Ni、Co、Fe、Mn、Cr、V、Ti、Cu、或Zn,0<x<1.3,0.7<y<2,x+y=2,MxRuyN2为立方晶系或非晶,且MxRuy为立方晶系。在此实施例中,气液扩散层11A可为多孔金属网,而气液扩散层11B可为多孔碳纸,以进一步增加膜电极组在电解中的耐久性。在另一实施例中,催化剂层11B的化学结构为M’aM”bN2或M’cM”dCe,而阴极15可为市售电极。
上述膜电极组可用于电解产氢。举例来说,可将膜电极组浸置于碱性水溶液中。举例来说,碱性水溶液可为NaOH、KOH、其他合适的碱类、或上述的组合的水溶液。在一实施例中,碱性水溶液的pH值大于14且小于15。若碱性水溶液的pH值过低,则导电度不佳。若碱性水溶液的pH值过高,则溶液黏度过高。上述方法亦施加电位至阳极与阴极以电解碱性水溶液,使阴极产生氢气,并使阳极产生氧气。
综上所述,本公开实施例的催化剂符合电解碱性水溶液产氢的需求。在OER部分,催化剂可解决现有催化剂的催化效果不佳、导电性不良、抗氧化耐蚀性低等问题。催化剂需具备高导电能力和高OER的电化学活性。本公开实施例的催化剂在扩散观点中,在低温下的晶界扩散系数远大于体扩散系数。由于催化剂中添加的杂质原子M’可填充于晶界,可阻隔原子经由晶界扩散,以改善其效能。催化剂的快速扩散路径如晶界等,可被某些材料填充,以阻止相邻的材料原子经由晶界或其它缺陷扩散。藉由插入晶界缝隙的氮原子或碳原子,可大量减少原子经由晶界扩散的机会。综上所述,采用氮原子与碳原子可增加抗氧化性及材料稳定性。由于氮化物或碳化物的导电佳且兼顾活性与成本,以M”的氮化物或碳化物(与Pt活性相近)结合M’可得到高导电度与电化学活性的催化剂。
为了让本公开的上述和其他目的、特征、和优点能更明显易懂,下文特举多个实施例配合所附图示,作详细说明如下:
实施例
制备例1
采用反应磁控溅镀机台,在玻璃碳电极(5mm OD×4mm H)上沉积Pt催化剂。将Pt靶材置入溅镀机台中,施加功率至Pt靶材,并将氩气(流速为20sccm)通入机台,且机台内的压力为30毫托。以氩离子撞击Pt靶材,在室温下进行溅镀5至6分钟,以在玻璃碳电极上形成膜厚约100nm的Pt催化剂,催化剂披覆量为0.042mg。
制备例2
采用反应磁控溅镀机台,在玻璃碳电极(5mm OD×4mm H)上分别沉积不同元素比例的NixRuy催化剂。将Ni靶材与Ru靶材置入溅镀机台中,调整施加至Ni靶材的功率(10至200W之间)与Ru靶材的功率(10至200W之间),并将氩气(流速为20sccm)通入机台,且机台内的压力为20毫托。以氩离子撞击Ni靶材与Ru靶材,在室温下进行反应式溅镀5至6分钟,以在玻璃碳电极上形成膜厚约100nm的NixRuy催化剂,催化剂披覆量为0.024mg。由EDS分析NixRuy催化剂,x介于约0.065至0.85之间,而y介于约1.935至1.15之间。由SEM分析NixRuy催化剂,其表面形貌为粒状。由X射线衍射分析(XRD)分析NixRuy催化剂,其为立方晶系。另一方面,可只将Ru靶材置入溅镀机台中,以类似参数在玻璃碳电极上形成膜厚约100nm的Ru催化剂,催化剂披覆量为0.024mg。
制备例3
采用反应磁控溅镀机台,在玻璃碳电极(5mm OD×4mm H)上分别沉积不同元素比例的NixRuyN2催化剂。将Ni靶材与Ru靶材置入溅镀机台中,调整施加至Ni靶材的功率(10至200W之间)与Ru靶材的功率(10至200W之间),并将氮气与氩气(流速为20sccm)通入机台,氮气/(氩气+氮气)=50%,且机台内的压力为20毫托。以氩离子撞击Ni靶材与Ru靶材,在室温下进行反应式溅镀5至6分钟,以形成膜厚约100nm的NixRuyN2催化剂于玻璃碳电极上,催化剂披覆量为0.024mg。由EDS分析NixRuyN2催化剂,x介于约0.069至1.086之间,而y介于约1.931至0.914之间。由SEM分析NixRuyN2催化剂,其表面形貌为三角锥与四角锥。由XRD分析NixRuyN2催化剂,其为立方晶系或非晶。另一方面,可只将Ru靶材置入溅镀机台中,以类似参数在玻璃碳电极上形成膜厚约100nm的Ru2N2催化剂,催化剂披覆量为0.024mg。
实施例1
将上述Pt、Ru、Ru2N2、NixRuy、与NixRuyN2催化剂,进行OER电化学活性测试如下。在0.1MKOH溶液中,分别取Pt、Ru、Ru2N2、NixRuy、与NixRuyN2催化剂形成其上的玻璃碳电极作为工作电极。取Hg/HgO作为参考电极,并取铂作为辅助电极。扫描电压范围:-0.8~1V,扫描速度为50mV/s,扫描次数为10次。接着进行OER的CV测量,扫描电压范围:-0.8~0.1V,扫描速度为10mV/s,且扫描次数为5次。上述OER结果如图2(Ru与NixRuy)与图3(Ru2N2与NixRuyN2)所示,横轴为相对于可逆氢电极(Reversible hydrogen electrode,RHE)的电位(V),纵轴为电流密度(J,mA/cm2)。如图2所示,纯Ru催化剂层无OER活性,而添加Ni的Ru催化剂活性明显提升。如图3所示,Ru2N2催化剂活性远高于Ru催化剂活性,而添加适量Ni的Ru2N2催化剂(即NixRuyN2催化剂)的活性可大幅提升。举例来说,NixRuyN2的x介于0.4至1.1之间时,可具有较佳效果。部分催化剂的比较如表1所示:
表1
由表1可知,OER中的Ni0.29Ru1.71与Ni0.46Ru1.53N2催化剂的电流密度,均高于铂膜催化剂的电流密度。不过NixRuy无抗氧化能力,因此不适于应用于OER。换言之,Ni0.46Ru1.53N2比铂膜催化剂更适用于OER。
实施例2
将上述Pt、Ru、NixRuy、与NixRuyN2催化剂,进行HER电化学活性测试如下。在0.1MKOH溶液中,分别取其上形成Pt、Ru、Ru2N2、NixRuy、与NixRuyN2催化剂的玻璃碳电极作为工作电极。取Hg/HgO作为参考电极,并取铂作为辅助电极。在HER测量部分,工作电极的转速为1600rpm,扫描电压范围:0~1V,扫描速度为10mV/s,扫描次数为3次。上述HER结果如图4(Ru与NixRuy)与图5(Ru与NixRuyN2)所示,横轴为相对于可逆氢电极(RHE)的电位(V),纵轴为电流密度(J,mA/cm2)。如图4所示,添加Ni的Ru催化剂(即NixRuy)活性明显高于Ru催化剂。部分催化剂的比较如表2所示:
表2
由上述可知,HER中的Ni0.06Ru1.93与Ni1.2Ru0.8N2催化剂的电流密度,均高于铂膜催化剂的电流密度。换言之,Ni0.06Ru1.93与Ni1.2Ru0.8N2催化剂均比铂膜催化剂更适用于HER。
制备例4
采用反应磁控溅镀机台,在玻璃碳电极(5mm OD×4mm H)上分别沉积不同元素比例的MnxRuyN2催化剂。将Mn靶材与Ru靶材置入溅镀机台中,调整施加至Mn靶材的功率(10至200W之间)与Ru靶材的功率(10至200W之间),并将氮气与氩气(流速为20sccm)通入机台,氮气/(氩气+氮气)=50%,且机台内的压力为20毫托。以氩离子撞击Mn靶材与Ru靶材,在室温下进行反应式溅镀5至6分钟,以在玻璃碳电极上形成膜厚约100nm的MnxRuyN2催化剂,催化剂披覆量为0.024mg。由EDS分析MnxRuyN2催化剂,x介于约0.01至0.8之间,而y介于约1.2至1.99之间。
实施例3
将上述MnxRuyN2催化剂,进行OER电化学活性测试如下。在0.1MKOH溶液中,取其上形成MnxRuyN2催化剂的玻璃碳电极作为工作电极。取Hg/HgO作为参考电极,工作电极的转速为1600rpm,并取铂作为辅助电极。扫描电压范围:-0.8~1V,扫描速度为50mV/s,扫描次数为10次。接着进行OER的CV测量,扫描电压范围:-0.8~0.1V,扫描速度为10mV/s,且扫描次数为5次。上述OER结果如图6(Ni2N2与MnxRuyN2)所示,横轴为相对于可逆氢电极(RHE)的电位(V),纵轴为电流密度(J,mA/cm2)。如图6所示,添加适量Mn的Ru2N2催化剂(即MnxRuyN2催化剂)的活性可大幅提升。举例来说,MnxRuyN2的x介于0.3至0.7之间时,可具有较佳效果。部分催化剂的比较如表3所示:
表3
由表3可知,OER中的Mn0.323Ru1.677N2催化剂的电流密度高于铂膜催化剂的电流密度。换言之,Mn0.323Ru1.677N2比铂膜催化剂更适用于OER。
实施例4
将MnxRuyN2催化剂进行HER电化学活性测试如下。在0.1MKOH溶液中,取其上形成MnxRuyN2催化剂的玻璃碳电极作为工作电极。取Hg/HgO作为参考电极,并取铂作为辅助电极。在HER测量部分,工作电极的转速为1600rpm,扫描电压范围:0~1V,扫描速度为10mV/s,扫描次数为3次。上述HER结果如图7所示,横轴为相对于可逆氢电极(RHE)的电位(V),纵轴为电流密度(J,mA/cm2)。部分催化剂的比较如表4所示:
表4
由上述可知,HER中的Mn0.079Ru1.92N2催化剂的电流密度高于铂膜催化剂的电流密度。换言之,Mn0.079Ru1.92N2催化剂均比铂膜催化剂更适用于HER。
制备例5
采用反应磁控溅镀机台,在玻璃碳电极(5mm OD×4mm H)上分别沉积不同元素比例的NiaNbbN2催化剂。将Ni靶材与Nb靶材置入溅镀机台中,调整施加至Ni靶材的功率(10至200W之间)与Nb靶材的功率(10至200W之间),并将氮气与氩气(流速为10sccm)通入机台,氮气/(氩气+氮气)=50%,且机台内的压力为5毫托。以氩离子撞击Ni靶材与Nb靶材,在室温下进行反应式溅镀5至6分钟,以在玻璃碳电极上形成膜厚约100nm的NiaNbbN2催化剂,催化剂披覆量为0.017mg。由EDS分析NiaNbbN2催化剂,a介于约0.3128至1.5082之间,例如,a为1.0296-1.3182或1.3182-1.5082,而b介于约0.4918至1.6872之间,例如:b为0.4918-0.6818或0.6818-0.9702。由XRD分析NiaNbbN2催化剂,其为立方晶系。
制备例6
采用反应磁控溅镀机台,在玻璃碳电极(5mm OD×4mm H)上分别沉积不同元素比例的NicNbdCe催化剂。将Ni靶材、Nb靶材、与碳靶材置入溅镀机台中,调整施加至Ni靶材的功率(10至200W之间)、Nb靶材的功率(10至200W之间)与碳靶材的功率(10至200W之间),并将氩气(10sccm)通入机台,且机台内的压力为5毫托。以氩离子撞击Ni靶材、Nb靶材、与碳靶材,在室温下进行反应式溅镀5至6分钟,以在玻璃碳电极上形成膜厚约100nm的NicNbdCe催化剂,催化剂披覆量为0.017mg。由EDS分析NicNbdCe催化剂,c介于约0.58至1.47之间,d介于约0.53至1.42之间,而e介于约0.92至2.47之间。由XRD分析NicNbdCe催化剂,其为立方晶系或非晶。另一方面,可只将Nb靶材与碳靶材置入溅镀机台中,以类似参数在玻璃碳电极上形成膜厚约100nm的Nb0.6556C1.3444催化剂,催化剂披覆量为0.017mg。
制备例7
采用反应磁控溅镀机台,在玻璃碳电极(5mm OD×4mm H)上分别沉积不同元素比例的NicNbdCe催化剂。将Ni靶材、Nb靶材、与碳靶材置入溅镀机台中,调整施加至Ni靶材的功率(10至200W之间)、Nb靶材的功率(10至200W之间)与碳靶材的功率(10至200W之间),并将氩气(10sccm)通入机台,且机台内的压力为5毫托。以氩离子撞击Ni靶材、Nb靶材、与碳靶材,在室温下进行反应式溅镀5至6分钟,以在玻璃碳电极上形成膜厚约100nm的NicNbdCe催化剂,催化剂披覆量为0.017mg。由EDS分析NicNbdCe催化剂,c介于约0.74至1.63之间,d介于约0.37至1.26之间,而e介于约0.38至1.30之间。由XRD分析NicNbdCe催化剂,其为立方晶系或非晶。
实施例5
将上述Pt、NiaNbbN2、NicNbdCe、与Nb0.6556C1.3444催化剂,进行OER电化学活性测试如下。在0.1MKOH溶液中,分别取其上形成Pt、NiaNbbN2、NicNbdCe、与Nb0.6556C1.3444催化剂的玻璃碳电极作为工作电极。取Hg/HgO作为参考电极,工作电极的转速为1600rpm,并取铂作为辅助电极。扫描电压范围:-0.8~1V,扫描速度为50mV/s,扫描次数为10次。接着进行OER的CV测量,扫描电压范围:-0.8~0.1V,扫描速度为10mV/s,且扫描次数为5次。上述OER结果如图8(NiaNbbN2)、图9(NicNbdCe与Nb0.6556C1.3444)、与图10(NicNbdCe与Nb0.6556C1.3444)所示,横轴为相对于可逆氢电极(RHE)的电位(V),纵轴为电流密度(J,mA/cm2)。如图8所示,添加适量Ni的Nb2N2催化剂(即NiaNbbN2)活性明显提升。如图9与10所示,添加适量Ni的NbC催化剂(即NicNbdCe催化剂)的活性可大幅提升。部分催化剂的比较如表5所示:
表5
由表5可知,OER中的Ni1.5Nb0.5N2与Ni1.62Nb0.37C0.39催化剂的电流密度,均高于铂膜催化剂的电流密度。换言之,Ni1.5Nb0.5N2与Ni1.62Nb0.37C0.39比铂膜催化剂更适用于OER。
制备例8
采用反应磁控溅镀机台,在玻璃碳电极(5mm OD×4mm H)上分别沉积不同元素比例的CocNbdCe催化剂。将Co靶材、Nb靶材、与碳靶材置入溅镀机台中,调整施加至Co靶材的功率(30-100W之间)、Nb靶材的功率(35W)与碳靶材的功率(100W),并将氩气(10sccm)通入机台,且机台内的压力为5毫托。以氩离子撞击Co靶材、Nb靶材、与碳靶材,在室温下进行反应式溅镀10至15分钟,以在玻璃碳电极上形成膜厚约100nm的CocNbdCe催化剂,催化剂披覆量为0.017mg。由EDS分析CocNbdCe催化剂,c介于约0.24至1.39之间,d介于约0.61至1.76之间,而e介于约0.63至3.61之间。由XRD分析CocNbdCe催化剂,其为立方晶系或非晶。
实施例6
将上述CocNbdCe与Nb0.6556C1.3444催化剂,进行OER电化学活性测试如下。在0.1MKOH溶液中,分别取其上形成CocNbdCe与Nb0.6556C1.3444催化剂的玻璃碳电极作为工作电极。取Hg/HgO作为参考电极,工作电极的转速为1600rpm,并取铂作为辅助电极。扫描电压范围:-0.8~1V,扫描速度为50mV/s,扫描次数为10次。接着进行OER的CV测量,扫描电压范围:-0.8~0.1V,扫描速度为10mV/s,且扫描次数为5次。上述OER结果如图11至图15(CocNbdCe与Nb0.6556C1.3444)所示,横轴为相对于可逆氢电极(RHE)的电位(V),纵轴为电流密度(J,mA/cm2)。如图11至图15所示,添加适量Co的NbdCe催化剂(即CocNbdCe)活性明显提升。
制备例9
采用反应磁控溅镀机台,在不锈钢网(316不锈钢,200mesh 50mm×50mm)上沉积Ni1.5Nb0.5N2催化剂。将Ni靶材与Nb靶材置入溅镀机台中,调整施加至Ni靶材的功率(10-200W)与Nb靶材的功率(10-200W),并将氮气与氩气(流速为10sccm)通入机台,氮气/(氩气+氮气)=50%,且机台内的压力为5毫托。以氩离子撞击Ni靶材与Nb靶材,在室温下进行反应式溅镀8分钟,以形成膜厚约300nm的Ni1.5Nb0.5N2催化剂(由EDS确认)于不锈钢网上,单位面积的催化剂披覆量为0.17mg/cm2。由XRD分析Ni1.5Nb0.5N2催化剂,其为立方晶系。
实施例7
取市售的PtC(HISPEC 13100,Johnson Matthey)涂布于H23C8(Freudenberg)碳纸上作为HER的阴极,阴极催化剂的单位面积披覆量控制为1.8mg/cm2。取制备例9的Ni1.5Nb0.5N2-不锈钢网作为OER的阳极,并将阴离子交换膜X37-50(购自DioxideMaterials)夹设于阴极与阳极的催化剂层之间,以形成膜电极组。将膜电极组浸置于2M的KOH溶液中,进行电化学活性测试如下。扫描电压范围:1.3~2.2V,扫描速度为50mV/s。上述膜电极组的电流-电压曲线如图16所示,在2V时可产生10.2A的电流,整个测试系统的阻抗为27mΩ。上述膜电极组的每分钟衰变率为0.001%。
制备例10
采用反应磁控溅镀机台,在不锈钢网(316不锈钢,200mesh 50mm×50mm)上沉积Ni1.62Nb0.37C0.39催化剂。将Ni靶材、Nb靶材、与碳靶材置入溅镀机台中,调整施加至Ni靶材的功率(10-200W)、Nb靶材的功率(10-200W)、与碳靶材的功率(10-200W),并将氩气(流速为10sccm)通入机台,且机台内的压力为5毫托。以氩离子撞击Ni靶材、Nb靶材、与碳靶材,在室温下进行反应式溅镀8分钟,以在不锈钢网上形成膜厚约300nm的Ni1.62Nb0.37C0.39催化剂(由EDS确认),单位面积的催化剂披覆量为0.17mg/cm2。由XRD分析Ni1.62Nb0.37C0.39催化剂,其为立方晶系或非晶。
实施例8
取市售的PtC(HISPEC 13100,Johnson Matthey)涂布于H23C8(Freudenberg)碳纸上作为HER的阴极,阴极催化剂的单位面积披覆量控制为1.8mg/cm2,制备例10的Ni1.62Nb0.37C0.39-不锈钢网作为OER的阳极,并将阴离子交换膜X37-50(购自DioxideMaterials)夹设于阴极与阳极的催化剂层之间,以形成膜电极组。将膜电极组浸置于2M的KOH溶液中,进行电化学活性测试如下。扫描电压范围:1.3~2.2V,扫描速度为50mV/s。上述膜电极组的电流-电压曲线如图17所示,在2V时可产生10.2A的电流,整个测试系统的阻抗为33mΩ。上述膜电极组的每分钟衰变率为0.02%。
比较例1
取市售的PtC(HISPEC 13100,Johnson Matthey)涂布于H23C8(Freudenberg)碳纸上作为HER的阴极,阴极催化剂的单位面积披覆量控制为1.8mg/cm2,市售的DSA不溶性阳极(IrO2/RuO2-Ti mesh,佳荣能源科技股份有限公司)作为OER的阳极,并将阴离子交换膜X37-50(购自Dioxide Materials)夹设于阴极与阳极的催化剂层之间,以形成膜电极组。将膜电极组浸置于2M的KOH溶液中,进行电化学活性测试如下。扫描电压范围:1.3~2.2V,扫描速度为50mV/s。上述膜电极组的电流-电压曲线如图18所示,在2V时可产生10.6A,整个测试系统的阻抗为40mΩ。上述膜电极组的每分钟衰变率为0.0087%。
实施例7、实施例8、与比较例1的膜电极组比较如表6所示:
表6
由表6可知,实施例的Ni1.5Nb0.5N2催化剂与Ni1.62Nb0.37C0.39催化剂的活性,远高于市售的阳极催化剂的活性。
制备例11
采用反应磁控溅镀机台,在不锈钢网(316不锈钢,200mesh,50mm×50mm)上沉积Ni0.75Ru1.25N2催化剂。将Ni靶材与Ru靶材置入溅镀机台中,调整施加至Ni靶材的功率(150W)与Ru靶材的功率(100W),并将氮气与氩气通入机台,氮气/(氩气+氮气)=50%,且机台内的压力为5毫托。以氩离子撞击Ni靶材与Ru靶材,在室温下进行反应式溅镀8分钟,以在不锈钢网上形成膜厚约300nm的Ni0.75Ru1.25N2催化剂(由EDS确认),单位面积的催化剂披覆量为0.17mg/cm2。由SEM分析Ni0.75Ru1.25N2催化剂,其表面形貌为三角锥与四角锥。由XRD分析Ni0.75Ru1.25N2催化剂,其为立方晶系或非晶。
实施例9
取制备例11的Ni0.75Ru1.25N2-不锈钢网作为HER的阴极,制备例9的Ni1.5Nb0.5N2-不锈钢网作为OER的阳极,并将阴离子交换膜X37-50(购自Dioxide Materials)夹设于阴极与阳极的催化剂层之间,以形成膜电极组。将膜电极组浸置于2M的KOH溶液中,进行电化学活性测试如下。扫描电压范围:1.3~2.2V,扫描速度为50mV/s。上述膜电极组在1.87V时可产生10.5A的电流,整个测试系统的阻抗为12mΩ。上述膜电极组的每分钟衰变率为0.0057%。
制备例12
采用反应磁控溅镀机台,在碳纸H23C8(freudenberg,50mm×50mm)上沉积Ni0.75Ru1.25N2催化剂。将Ni靶材与Ru靶材置入溅镀机台中,调整施加至Ni靶材的功率(150W)与Ru靶材的功率(100W),并将氮气与氩气通入机台,氮气/(氩气+氮气)=50%,且机台内的压力为5毫托。以氩离子撞击Ni靶材与Ru靶材,在室温下进行反应式溅镀8分钟,以在碳纸H23C8上形成膜厚约300nm的Ni0.75Ru1.25N2催化剂(由EDS确认),单位面积的催化剂披覆量为0.17mg/cm2。由SEM分析Ni0.75Ru1.25N2催化剂,其表面形貌为三角锥与四角锥。由XRD分析Ni0.75Ru1.25N2催化剂,其为立方晶系或非晶。
实施例10
取制备例12的Ni0.75Ru1.25N2-碳纸作为HER的阴极,制备例9的Ni1.5Nb0.5N2-不锈钢网作为OER的阳极,并将阴离子交换膜X37-50(购自Dioxide Materials)夹设于阴极与阳极的催化剂层之间,以形成膜电极组。将膜电极组浸置于2M的KOH溶液中,进行电化学活性测试如下。扫描电压范围:1.3~2.2V,扫描速度为50mV/s。上述膜电极组的电流-电压曲线如图19所示,在1.96V时可产生10.5A的电流,整个测试系统的阻抗为17mΩ。上述膜电极组的每分钟衰变率为0.000035%。控制膜电极组的电位为2V并持续操作48小时,其电流稳定如图20所示。换言之,Ni0.75Ru1.25N2-碳纸可抵抗还原反应,Ni1.5Nb0.5N2-不锈钢网可抵抗氧化反应,且Ni0.75Ru1.25N2-碳纸与Ni1.5Nb0.5N2-不锈钢网均可抵抗碱腐蚀。
实施例7、实施例9、与实施例10的膜电极组比较如表7所示:
表7
由表7可知,阴极的催化剂层采用Ni0.75Ru1.25N2催化剂可大幅提高催化剂活性。此外,阴极的Ni0.75Ru1.25N2催化剂形成于碳纸上时,可进一步改善膜电极组的耐久性。
虽然本公开已以数个实施例揭露如上,然其并非用以限定本公开,任何本技术领域中的技术人员,在不脱离本公开的精神和范围内,应可作任意的更改与润饰,因此本公开的保护范围应以所附权利要求所界定的范围为准。
Claims (7)
1.M’cM”dCe催化剂材料在多孔导电层上作为用于OER的电解碱性水溶液的阳极的用途,
其中M’为Ni、Co、Fe、Mn、Cr、V、Ti、Cu、或Zn,
M”为Nb、Ta、或上述的组合,
0.24≤c≤1.7,0.3≤d≤1.76,且0.38≤e≤3.61,
其中该M’cM”dCe催化剂材料为立方晶系。
2.如权利要求1所述的用途,其中M’为Ni且M”为Nb,0.90≤c≤1.47,0.53≤d≤1.10,且0.9≤e≤1.9。
3.如权利要求1所述的用途,其中M’为Ni且M”为Nb,0.74≤c≤1.63,0.37≤d≤1.26,且0.38≤e≤1.30。
4.如权利要求1所述的用途,其中M’为Co且M”为Nb,0.24≤c≤1.39,0.61≤d≤1.76,且0.63≤e≤3.61。
5.如权利要求1所述的用途,其中所述M’cM”dCe催化剂材料的形成方法包括:
将M’靶材、M”靶材、与碳靶材置于载气氛围中,其中M’为Ni、Co、Fe、Mn、Cr、V、Ti、Cu、或Zn,且M”为Nb、Ta、或上述的组合;
分别提供功率至该M’靶材、该M”靶材、与该碳靶材;以及
提供离子撞击M’靶材、该M”靶材、与该碳靶材,以溅镀沉积M’cM”dCe催化剂材料于多孔导电层上。
6.如权利要求5所述的用途,其中提供至该M’靶材的功率为10至200W,提供至该M”靶材的功率为10至200W,且提供至该碳靶材的功率为10至200W。
7.如权利要求5所述的用途,其中该载气氛围的压力为1毫托至30毫托。
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