CN115491691A - 自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料制备方法及应用 - Google Patents
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- 229910002546 FeCo Inorganic materials 0.000 title claims abstract description 68
- 239000007772 electrode material Substances 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 10
- 239000000956 alloy Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 238000013112 stability test Methods 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000000840 electrochemical analysis Methods 0.000 claims description 5
- 230000010287 polarization Effects 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 238000003723 Smelting Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000011056 performance test Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- XZWVIKHJBNXWAT-UHFFFAOYSA-N argon;azane Chemical compound N.[Ar] XZWVIKHJBNXWAT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 3
- 229910003460 diamond Inorganic materials 0.000 claims description 3
- 239000010432 diamond Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- -1 iron-cobalt-cerium-aluminum Chemical compound 0.000 claims description 2
- 238000005121 nitriding Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 238000000137 annealing Methods 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 238000003487 electrochemical reaction Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
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- 229910021397 glassy carbon Inorganic materials 0.000 description 4
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
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- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
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Abstract
本发明涉及一种自支撑纳米多孔层片状FeCo/Ce‑O‑N复合电极材料的制备方法及其作为电解水制氢阳极析氧反应(OER)催化剂的应用。本发明以FeCoCeAl合金作为前驱体,通过化学脱合金化和退火氮化处理的方法,制备了自支撑纳米多孔层片状FeCo/Ce‑O‑N。本发明制得的自支撑纳米多孔层片状FeCo/Ce‑O‑N复合电极材料具有独特的双模式孔结构、高的导电性、快的电子和离子传输速度,快的电极表面电化学反应速度和电极内部的原子扩散速度,以及FeCo和Ce‑O‑N之间的协同作用显著提高了其析氧反应电化学性能和稳定性。
Description
技术领域
本发明涉及自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料的制备方法及其作为电解水制氢阳极析氧反应(OER)催化剂的应用。
背景技术
利用丰富的太阳能和风能资源的可再生电力进行电解水是一种极具潜力的清洁的大规模制氢能源转换技术。它利用氢气(H2)作为清洁的高密度的能源载体来满足未来全球能源需求,从而建立一个环境友好的水循环能源框架。然而,无论是碱性水电解槽还是质子交换膜水电解槽中的水电解,其能效始终较低,这主要是由于析氧反应(OER)动力学缓慢以及 OER电催化剂活性不足。目前,贵金属OER电催化剂(如RuO2和IrO2)仍然认为是最先进的催化剂,但它们的稀缺性、高成本和低耐久性严重阻碍了实际应用。为了取代贵金属基电催化剂,许多以地球上含量丰富的3d过渡金属为基础的双金属或多金属材料,如铁(Fe)、钴(Co)和镍(Ni)被广泛开发应用。然而,它们大多数只能在低电流密度(<100mA cm-2) 持续工作几十小时,无法满足实际电解槽的工业要求(需要在<300mV的低过电位下,提供>500mAcm-2的高电流密度,并持续工作数千小时)。因此,人们迫切希望为高效实用的工业电解槽开发高活性、高强度和低成本的OER电催化材料。
发明内容
本发明的目的是提供一种自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料的制备方法及其作为电解水制氢阳极析氧反应(OER)催化剂的应用。该发明以FeCoCeAl合金作为前驱体,通过化学脱合金化和退火氮化处理的方法,制备了自支撑纳米多孔层片状FeCo/Ce-O-N。
本发明涉及一种自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料的制备方法及其作为电解水制氢阳极析氧反应催化剂的应用具体步骤如下:
1)自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料的制备方法:
a、按照铁、钴、铈、铝比例,分别称取纯铁、纯钴、纯铈、纯铝,去除氧化层后,在高纯氩气气氛中通过电弧熔炼的方法进行熔炼,得到铁钴铈铝合金锭;
b、使用金刚石线切割机将得到的合金锭切割成200-550μm厚的合金片;
c、砂纸打磨去除表面氧化层后,将合金片浸没于1-6mol/L的KOH溶液中,在50-85℃下进行脱合金处理,获得自支撑纳米多孔层片状FeCo/Ce-O复合电极材料;
d、将洗涤、干燥后的自支撑纳米多孔层片状FeCo/Ce-O复合电极材料在氩氨 (Ar/NH3=90/10)气氛下用管式炉进行氮化处理,加热至400-600℃保温1-4h,热处理结束后随炉冷却至室温,自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料制备完成。
2)根据上述制备方法得到的自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料,其作为电极材料进行电化学测试,包括以下步骤:
a、将所制备的自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料直接作为工作电极,碳棒作为对电极,饱和银/氯化银电极(Ag/AgCl)作为参比电极,1mol/L的KOH溶液作为电解液,组成标准的三电极体系进行电化学测试;
b、用所述所制备的自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料作为工作电极进行析氧反应(OER)电化学性能测试时,极化曲线(LSV)扫描速率在1mV/s,电化学阻抗(EIS)测试频率范围为100kHz到10mHz;
c、用自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料作为工作电极进行电化学性能测试,进行稳定性测试,恒电位下得到电流-时间曲线;
d、所制备的电极材料自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料作为电解水阳极析氧反应催化剂具有优异的析氧反应催化性能和良好的稳定性。
本发明制得的自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料具有独特的双模式孔结构、高的导电性、快的电子和离子传输速度,快的电极表面电化学反应速度和电极内部的原子扩散速度,以及FeCo和Ce-O-N之间的协同作用显著提高了其析氧反应电化学性能和稳定性。
附图说明
图1、自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料的扫描电子显微镜(SEM)图片;
图2、自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料的EDS-mapping图片;
图3、自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料的XRD图谱;
图4、自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料的高分辨透射电子显微镜(HRTEM)图片及相应区域经傅里叶变换(FFT)得到的衍射斑点;
图5、自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料和负载在玻碳电极上的商用 RuO2催化剂的析氧反应电化学性能极化曲线;
图6、自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料和负载在玻碳电极上的商用 RuO2催化剂的Tafel斜率对比;
图7、自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料和负载在玻碳电极上的商用 RuO2催化剂的EIS电化学阻抗图谱,插图为用于拟和EIS图谱的等效电路;
图8、自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料和负载在玻碳电极上的商用 RuO2催化剂的溶液电阻(RS)和电荷转移电阻(RCT)值;
图9、自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料稳定性测试,电流密度-时间曲线;
图10、自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料1000h稳定性测试后的SEM 图片;
图11、自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料1000h稳定性测试前后的XRD图谱对比。
具体实施方式
现将本发明的实施例述于后:
实施例
本实施例中的制备过程和步骤如下:
(1)将纯度为99.98%的纯铁和纯度为99.99%的纯钴分别置于稀HCl溶液中超声清洗去除表面氧化层和杂质后,用超纯水清洗去除残留杂质;将纯度为99.95%的纯铝置于稀 NaOH溶液中超声清洗去除表面氧化层和杂质后,用超纯水清洗去除残留杂质;将清洗后的金属置于真空中干燥;干燥后,分别称取2.17g纯铁、0.76g纯钴、1.81g纯铈和5.25g纯铝(金属原子比为Fe:Co:Ce:Al=15:5:5:75);
(2)将上述四种金属一同放入高真空电弧熔炼炉中,在有氩气保护的熔炼炉中进行除氧处理;
(3)加热至金属完全熔化后,保温2h,再利用循环水冷系统冷却至室温;
(4)重复过程(3)多次,以保证获得均匀的合金锭;
(5)将完全冷却至室温的合金锭(Fe15Co5Ce5Al75)置于金刚石线切割机上,切成~400 μm厚的金属片;
(6)将金属片浸没于6mol/L的KOH溶液中,在85℃的水浴锅中加热进行脱合金处理,得到自支撑纳米多孔层片状FeCo/Ce-O复合电极材料;
(7)用超纯水清洗数次去除残留KOH后,置于真空中干燥;
(8)将干燥好的自支撑纳米多孔层片状FeCo/Ce-O复合电极材料置于管式炉中,在氩氨(Ar/NH3=90/10)气氛下以5℃/min的升温速率加热至600℃保温2h,随炉冷却至室温,得到自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料。
材料的形貌和结构表征
通过扫描电镜(SEM)表征,如图1证明了自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料是由FeCo层和Ce-O-N层交替分布的层状结构。图2的EDS-mapping表征进一步证明了元素的交替分布。
图3为自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料的XRD图谱,对比标准PDF卡片证明了自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料由固溶了Co的Fe相和掺杂了N的CeO2相构成。
图4的自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料的透射电镜(TEM)图谱分别展示了Co固溶的Fe晶格间距0.198nm和N掺杂的CeO2晶格间距0.313nm,分别对应了Fe(110)晶面(晶面间距为0.203nm)和CeO2(111)晶面(晶面间距为0.312nm)。傅里叶变换(FFT)衍射斑点进一步证明自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料由FeCo和Ce-O-N两相组成。
材料的电化学性能表征结果
将通过上述制备方法获得的自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料直接作为工作电极,碳棒作为对电极,饱和银/氯化银电极(Ag/AgCl)作为参比电极,在1mol/L的KOH电解液中,组装成标准的三电极体系进行电化学测试:
A、自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料的极化曲线(LSV)测试,扫描速率为1mV/s;
B、自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料电化学阻抗(EIS)测试,过电位为0.336V,频率范围100kHz到10mHz;
C、自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料稳定性测试,恒电位(1.54V)下进行1000h,获得电流密度-时间曲线。
通过图5的不同材料的极化曲线测试,自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料的起始电位约为186mV,低于商用RuO2催化剂的217mV。在360mV的过电位下,自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料的电流密度可以达到约3940mA cm-2,而商用RuO2催化剂只能实现约114mA cm-2的电流密度。图6表示不同材料的Tafel斜率,自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料有着最小的Tafel斜率,其值为33mV dec-1,远小于商用RuO2催化剂的93mV dec-1,表明自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料快速的反应动力学。图7展示了不同材料在过电位0.336V下的EIS电化学阻抗图谱和相应的等效电路示意图;从图8中可以看出,两种材料具有相似的溶液电阻(自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料4.4Ω、商用RuO2催化剂5.0Ω),但自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料的电荷转移电阻(2.7Ω)远小于商用RuO2催化剂的24.3 Ω,表明自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料拥有良好的电子转移性能,也表明其拥有更快的反应动力学。
图9为稳定性测试的电流密度随测试时间变化的曲线,在1.54V电压下,自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料持续工作1000h,电流密度没有明显衰减,即使在此期间有瞬间断电的突发情况出现,再次施加电压启动后,仍能达到断电前的电流密度并维持稳定。说明自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料具有优异的稳定性。图10表明,在经过1000h稳定性测试后,自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料仍维持原有的异质层状结构,说明其具有优异的结构稳定性。图11对比了自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料在1000h稳定性测试前后的XRD图谱,可以看出没有明显变化,材料仍然由固溶了Co的Fe相和掺杂了N的CeO2相构成。
该复合材料可作为电解水制氢阳极析氧反应催化剂,在工业级产氢的领域具有很好的应用前景。
Claims (2)
1.一种自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料的制备方法,具体步骤如下:
其作为电解水制氢阳极析氧反应催化剂的应用具体步骤如下:
a、按照铁、钴、铈、铝比例,分别称取纯铁、纯钴、纯铈、纯铝,去除氧化层后,在高纯氩气气氛中通过电弧熔炼的方法进行熔炼,得到铁钴铈铝合金锭;
b、使用金刚石线切割机将得到的合金锭切割成200-550μm厚的合金片;
c、砂纸打磨去除表面氧化层后,将合金片浸没于1-6mol/L的KOH溶液中,在50-85℃下进行脱合金处理,获得自支撑纳米多孔层片状FeCo/Ce-O复合电极材料;
d、将洗涤、干燥后的自支撑纳米多孔层片状FeCo/Ce-O复合电极材料在Ar/NH3=90/10的氩氨气氛下用管式炉进行氮化处理,加热至400-600℃后保温1-4h,热处理结束后随炉冷却至室温,自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料制备完成。
2.根据权利要求1所述述制备方法得到的复合电极材料,其作为电极材料进行电化学测试,包括以下步骤:
a、将所制备的自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料直接作为工作电极,碳棒作为对电极,饱和银/氯化银电极(Ag/AgCl)作为参比电极,1mol/L的KOH溶液作为电解液,组成标准的三电极体系进行电化学测试;
b、用所述所制备的自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料作为工作电极进行析氧反应OER电化学性能测试时,极化曲线LSV扫描速率在1mV/s,电化学阻抗EIS测试频率范围为100kHz~10mHz;
c、用自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料作为工作电极进行电化学性能测试,进行稳定性测试,恒电位下得到电流-时间曲线;
d、所制备的电极材料自支撑纳米多孔层片状FeCo/Ce-O-N复合电极材料作为电解水制氢阳极析氧反应催化剂具有析氧反应催化性能和稳定性,用于工业级产氢。
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