CN111495407A - 一种制备Co/MnO/氮掺杂碳复合电催化剂的方法 - Google Patents
一种制备Co/MnO/氮掺杂碳复合电催化剂的方法 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 16
- 239000010411 electrocatalyst Substances 0.000 title claims description 16
- 239000010941 cobalt Substances 0.000 claims abstract description 22
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 22
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- 238000000137 annealing Methods 0.000 claims abstract description 19
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- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011572 manganese Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 17
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 14
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 14
- 235000002867 manganese chloride Nutrition 0.000 claims description 14
- 239000011565 manganese chloride Substances 0.000 claims description 14
- 229940099607 manganese chloride Drugs 0.000 claims description 14
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- YDVGDXLABZAVCP-UHFFFAOYSA-N azanylidynecobalt Chemical compound [N].[Co] YDVGDXLABZAVCP-UHFFFAOYSA-N 0.000 claims description 6
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- 230000035484 reaction time Effects 0.000 claims 1
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- 239000002184 metal Substances 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000002041 carbon nanotube Substances 0.000 abstract description 5
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- 229910000428 cobalt oxide Inorganic materials 0.000 abstract 1
- 239000000446 fuel Substances 0.000 abstract 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
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- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
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- 239000012621 metal-organic framework Substances 0.000 description 3
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- 235000006748 manganese carbonate Nutrition 0.000 description 2
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- 229940093474 manganese carbonate Drugs 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910002514 Co–Co Chemical group 0.000 description 1
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- 150000001869 cobalt compounds Chemical class 0.000 description 1
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 1
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
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- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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Abstract
本发明提出了一种制备Co/MnO/氮掺杂碳复合材料的方法。即利用水热反应制备含锰、钴、氮、碳元素的纳米颗粒前驱体粉末,再将该颗粒状粉末与双氰胺混合后在保护气氛下退火制得。该复合物因含有金属钴、碱式钴盐和氧化锰将具有碱性条件下优异的电催化析氧性能;亦因钴、锰、氮元素掺入碳纳米管或金属钴和氧化锰与之表面耦合成键将具有优异的电催化氧还原性能。此外,该复合物中金属钴、碱式钴盐和氧化锰被碳层包裹将有效提高其稳定性。该催化剂具有用于燃料电池和锌空电池的光明前景。
Description
技术领域
本发明涉及电催化剂及其制备,属于能量存储和转换材料与器件领域。
背景技术
金属-空气电池由于高的能量密度和功率密度而具有其它种类二次电池不可比拟的优势。以锌空电池为例,其标准电压为1.65 V,理论能量密度高达1084 Wh/kg,并具有成本低、安全性好的优势。然而,锌空电池中的空气电极反应却往往十分困难。这是因为放电时的氧还原反应(ORR)和充电时的氧析出反应(OER)都涉及到多种复杂的中间产物,是缓慢的动力学过程。为了加快OER和ORR,各国研发人员争相研发各种催化剂以加速这些反应过程。目前电催化效果最好是Pt/C、Ir/C、IrO2、RuO2等贵金属基催化剂,然而它们成本高和资源稀缺严重阻碍了大规模生产与应用。因此,迫切需要发展低成本、高性能的非贵金属电催化剂。
最近,具有过渡金属-氮-碳(M-N-C)键型结构的①过渡金属、氮共掺杂的碳材料,②过渡金属或其化合物与氮掺杂碳材料形成的界面耦合复合物,展现出了优异的ORR性能,甚至ORR/OER双功能。为了促进M-N-C的可控合成,在含N的有机环境中预先嵌入过渡金属原子M位点的金属有机骨架(MOF)被广泛用作生产M-N-C的前驱体,结合后续保护气氛中碳化常可获得高质量的M-N-C材料。但是,这些MOF前驱体常用配体,例如2-甲基咪唑和2,2-联吡啶价格昂贵且有毒,阻碍了M-N-C的可扩展生产及其实际应用。此外,研究报道(例如:Fu,Geng tao, et al. "Boosting bifunctional oxygen electrocatalysis with 3Dgraphene aerogel‐supported Ni/MnO particles." Advanced materials 30 (2018):1704609.),在合成M-N-C过程中添加少量的另一种过渡金属有助于减小金属颗粒(例中金属Ni)或金属化合物颗粒(例中MnO)尺寸,改善其分散,以及使不同组份间协同增强,进而可大大提高ORR和OER的活性和稳定性。然而,该工作也采用了较昂贵的氧化石墨烯,且制备过程较复杂。
基于以上讨论,本发明旨在制备出一种可用于OER和ORR等反应的,廉价、高效的电催化剂。利用溶剂热制备过渡金属钴Co、N元素含量高、廉价的聚合物作为生产M-N-C的前驱体,替代价格高昂的MOF和氧化石墨烯。再结合化学气相沉积CVD,即在Co-N聚合物退火过程中引入双氰胺,使其生长出均匀的碳纳米管,从而在金属核周围创造更多的表面缺陷活性位点。进而有利于氧气、氢氧根和ORR反应中含氧中间产物的吸附脱附平衡,而将进一步提高对ORR的催化能力。若在CVD反应生成碳纳米管过程中引入Mn元素,Mn元素或将掺入碳层或形成氧化锰与钴和氮掺杂碳材料复合构筑更多的活性位点,从而进一步提高对ORR的催化能力。
发明内容
本发明提供了一种制备Co/MnO/氮掺杂碳复合电催化剂的方法,即将氯化钴、氯化锰与甲酰胺经过水热反应得到粉体再在双氰胺反应气氛下退火制得,具体如下:
步骤1:在室温搅拌条件下,将氯化钴溶于甲酰胺中,其中氯化钴浓度80~200 mM;再将该溶液倒入聚四氟内衬反应釜中,水热温度为180~220 oC、时间为8~24 h。生长出Co-N高聚物颗粒,冷却至室温后,用去离子水和乙醇过滤,真空干燥,可以得到粉体。该水热步骤的反应原理为:
本发明采用了便宜无毒的甲酰胺(FA)作为溶剂分子,其在水热过程中聚合,同时可以与金属钴离子配合生成形成Co-N高聚物(如上式所示)。以Co-N高聚物为前驱物,该前驱物中钴元素被氮原子配合而预先分散(如上式所示),这有助于在后续退火生成小尺寸金属钴,并且初步阻止小尺寸(纳米、原子团、原子尺寸量级的)钴晶粒因具有高表面能而迁移、积聚并长大,从而调控钴尺寸,获得钴颗粒细小且分散均匀的钴基催化剂。
该水热过程中也可以加入氯化锰,氯化锰浓度为16~80 mM(其与Co-N高聚物中钴元素的原子比为 0.05~0.1 :1),从而获得锰基化合物与含钴、氮高聚物组成的复合物前驱体颗粒。
步骤2:将双氰胺与第一步得到的前驱体颗粒粉体均匀混合,在Ar气氛下退火。或者将双氰胺、氯化锰与含Co-N高聚物(第一步中不加入氯化锰)的粉体均匀混合,在Ar气氛下退火得到Co/MnO/氮掺杂碳复合电催化剂。退火的温度为800~900℃,退火时间为2~4 h。该步骤的CVD反应原理为:①钴元素逐步从高聚物及其反应物中析出而形成Co-Co金属键和金属钴(附图9中有金属钴的XRD峰);②这些新生成的金属钴作为催化剂将催化双氰胺的分解产物生成氮掺杂碳纳米管(附图7a中可见管径20-30 nm长数μm的纳米管);③锰基化合物(例如:碳酸锰,二氧化锰,氯化锰)亦在双氰胺的分解气氛(含氨气)中被还原为一氧化锰(对比附图8和9即可知第一步水热产生的碳酸锰和二氧化锰,经第二步CVD退火被还原为一氧化锰);④另外,钴、一氧化锰、氮掺杂碳纳米管将形成良好的异质界面,协同提高ORR性能。
本发明的优势还在于,通过水热-化学气相沉积法制备的Co/MnO/氮掺杂碳复合电催化剂,具有制备工艺简单,原料廉价易得,电催化性能优异和可重复性好等优点。
附图说明
图1实施例1所制备样品的ORR线性伏安扫描(LSV)。
图2实施例2所制备样品的ORR线性伏安扫描(LSV)。
图3实施例3所制备样品的ORR线性伏安扫描(LSV)。
图4实施例4所制备样品的ORR线性伏安扫描(LSV)。
图5实施例5所制备样品的ORR线性伏安扫描(LSV)。
图6实施例2所制备样品退火前的SEM图。
图7实施例2所制备样品退火后的SEM图。
图8实施例2所制备样品退火前的XRD图。
图9实施例2所制备样品退火后的XRD图。
图10实施例2所制备样品退火后的EDX图。
具体实施方案
发明实施例中ORR性能LSV测试方法:
1.称取5mg电催化剂粉体,加入到1.96mL乙醇与水的混合溶剂中(乙醇与水的体积比为1:1),同时加入40 μL Nafion溶液,超声2h,得到黑色均匀分散浆料。取6.2 μL上述浆料滴涂在玻碳电极表面,其中玻碳电极直径为3mm,自然晾干。
2.采用三电极系统测试,以滴有催化剂浆料玻碳电极为工作电极、以碳棒为对电极、以饱和Hg/HgO电极为参比电极,ORR测试前都需要通入氧气达到氧饱和后才能进行测试。ORR测试所用电解质为:0.1M KOH水溶液,扫描速度为10mV/s,测试过程中工作电极1600rmp旋转。
实施例1:
室温下,将60mM氯化钴、60 mM氯化锰溶于60mL甲酰胺溶液,在200oC下水热反应12h;冷却至室温后,用去离子水和乙醇反复过滤洗涤冲洗于真空干燥箱干燥过夜制得锰基化合物与含钴、氮高聚物组成的复合物前驱体粉体。将0.1 g前驱体粉体和0.4 g双氰胺一起研磨混合后,放入管式炉中,在Ar气流下900 oC反应1 h,自然冷却至室温后取出。
图1为实施例1所制备样品电极的ORR线性伏安扫描(LSV)图。由图可知ORR反应对应的半波电位为E1/2 = 0.86 V,1600 rmp 旋转的情况下极限电流密度能达到~7.14 mA/cm2。
实施例2:
室温下,将60 mM氯化钴、60 mM氯化锰溶于60 mL甲酰胺溶液,在200 oC下水热反应12h;冷却至室温后,用去离子水和乙醇反复过滤洗涤冲洗于真空干燥箱干燥过夜制得锰基化合物与含钴、氮高聚物组成的复合物前驱体粉体。将0.1 g前驱体粉体和0.4 g双氰胺一起研磨混合后,放入管式炉中,在Ar气流下900 oC反应2 h,自然冷却至室温后取出。
图2为实施例2所制备样品电极的ORR线性伏安扫描(LSV)图。由图可知ORR反应对应的半波电位为E1/2 = 0.862 V,1600 rmp 旋转的情况下极限电流密度能达到~7.23 mA/cm2。
图6为实施例2所制备样品退火前的SEM图。由图可知经过水热反应生长出了均匀的尺寸约100 nm的前驱物纳米颗粒,这些均匀细小的颗粒有助于第二步退火形成比表面大的催化剂。本发明采用了甲酰胺作为溶剂分子,其在水热过程中聚合,同时可以与金属钴离子配合生成形成Co-N高聚物,而锰元素与其它元素化合形成的化合物的尺寸都在~100 nm,这充分证明了该水热步骤在制备M-N-C前驱物上的有效性。
图7为实施例2所制备样品退火后的SEM图。由图可知经CVD反应后生长出了管径20-30 nm长数μm的纳米管。对比实施例2样品在CVD反应前后形态的变化,说明CVD反应过程中前驱物分解,尺寸也由初期~100 nm变化至~20 nm。
图8为实施例2所制备样品退火前的XRD图。由图可知水热后的粉体出现了二氧化锰和碳酸锰的特征峰。而无金属钴及钴化合物的特征峰,说明钴分散到甲酰胺形成的高聚物中。本发明采用了甲酰胺作为溶剂分子,其在水热过程中聚合,同时可以与金属钴离子配合生成形成Co-N高聚物。该前驱物中钴元素被氮原子配合而预先分散,无法形成Co-Co键和金属钴。
图9为实施例2所制备样品退火后的XRD图。由图可知经过双氰胺CVD退火后出现立方相金属钴(PDF# 15-0806)和部分碱式碳酸钴,以及石墨碳(PDF# 41-1487)的特征峰,二氧化锰和碳酸锰转变成了一氧化锰(PDF# 07-0230),生成了Co/MnO/氮掺杂碳复合物。
图10为实施例2所制备样品退火后的EDX图。由图可知Co/MnO/氮掺杂碳复合电催化剂含有Co、N、C、O、Mn元素,结合XRD其中Co来自于金属钴,O、Mn来自于一氧化锰MnO,N、C来自于氮掺杂的碳。结合以上分析可知,经过水热和CVD退火两个步骤,制得Co/MnO/氮掺杂碳复合材料。
实施例3
室温下,将80 mM氯化钴、40 mM氯化锰溶于60 mL甲酰胺溶液,在200 oC下水热反应12h;冷却至室温后,用去离子水和乙醇反复过滤洗涤冲洗于真空干燥箱干燥过夜制得锰基化合物与含钴、氮高聚物组成的复合物前驱体粉体。将0.1 g前驱体粉体和0.4 g双氰胺一起研磨混合后,放入管式炉中,在Ar气流下900 oC反应2.5 h,自然冷却至室温后取出。
图3为实施例3所制备样品电极的ORR线性伏安扫描(LSV)图。由图可知ORR反应对应的半波电位为E1/2 = 0.862 V,1600 rmp 旋转的情况下极限电流密度能达到~6.31 mA/cm2。
实施例4:
室温下,将100 mM氯化钴、20 mM氯化锰溶于60 mL甲酰胺溶液,在200 oC下水热反应12h;冷却至室温后,用去离子水和乙醇反复过滤洗涤冲洗于真空干燥箱干燥过夜制得锰基化合物与含钴、氮高聚物组成的复合物前驱体粉体。将0.1 g前驱体粉体和0.4 g双氰胺一起研磨混合后,放入管式炉中,在Ar气流下900 oC反应3 h,自然冷却至室温后取出。
图4为实施例4所制备样品电极的ORR线性伏安扫描(LSV)图。由图可知ORR反应对应的半波电位为E1/2 = 0.85 V,1600 rmp 旋转的情况下极限电流密度能达到~6.56 mA/cm2。
实施例5:
室温下,将120 mM氯化钴溶于60 mL甲酰胺溶液,在200 oC下水热反应12 h;冷却至室温后,用去离子水和乙醇反复过滤洗涤冲洗于真空干燥箱干燥过夜制得含钴、氮高聚物组成的复合物前驱体粉体。将0.1 g前驱体粉体、0.01 g氯化锰和0.4 g双氰胺一起研磨混合后,放入管式炉中,在Ar气流下900 oC反应2.5 h,自然冷却至室温后取出。
图5为实施例5所制备样品电极的ORR线性伏安扫描(LSV)图。由图可知ORR反应对应的半波电位为E1/2 = 0.871 V,1600 rmp 旋转的情况下极限电流密度能达到~6.04 mA/cm2。
Claims (6)
1.一种制备Co/MnO/氮掺杂碳复合电催化剂的方法,其特征在于,具体制备方法为:
(1)将氯化钴、氯化锰溶于甲酰胺中,利用水热反应后,再经过滤、洗涤、真空干燥,得到生长有锰基化合物与含钴、氮高聚物组成的复合物颗粒;
(2)将上述复合物颗粒与双氰胺混合后于保护气氛中退火反应,得到Co/MnO/氮掺杂碳复合电催化剂。
2.根据权利要求1所述的制备Co/MnO/氮掺杂碳复合电催化剂的方法,其特征在于,所述的氯化锰还可以在步骤(2)退火过程中引入。
3.根据权利要求1所述的制备Co/MnO/氮掺杂碳复合电催化剂的方法,其特征在于,所述的氯化锰与氯化钴中的锰元素与钴元素的原子比为0.1~1:1。
4. 根据权利要求3所述的制备Co/MnO/氮掺杂碳复合电催化剂的方法,其特征在于,所述的步骤(1)中氯化钴溶于甲酰胺溶液的浓度为80~200 mM,水热反应过程中温度为180~220 oC、反应时间为8~24 h。
5. 根据权利要求1所述的制备Co/MnO/氮掺杂碳复合电催化剂的方法,其特征在于,所述步骤(2)中所述的保护气氛包括Ar气或N2气,退火的温度为800~900℃,退火时间为2~4h。
6. 根据权利要求1所述的制备Co/MnO/氮掺杂碳复合电催化剂的方法,其特征在于,所述步骤(2)中的双氰胺与复合物颗粒的质量比为3~8 :1。
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