CN108649241A - The fuel cell oxygen reduction catalyst and preparation method thereof of nitrogen-doped graphene load C oCx/FeCo@C - Google Patents
The fuel cell oxygen reduction catalyst and preparation method thereof of nitrogen-doped graphene load C oCx/FeCo@C Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000001301 oxygen Substances 0.000 title claims abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 38
- 239000000446 fuel Substances 0.000 title claims abstract description 37
- 229910002546 FeCo Inorganic materials 0.000 title claims abstract description 36
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 33
- 230000009467 reduction Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- 238000000034 method Methods 0.000 claims abstract description 21
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims abstract description 15
- 229940044175 cobalt sulfate Drugs 0.000 claims abstract description 15
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims abstract description 15
- UCFIGPFUCRUDII-UHFFFAOYSA-N [Co](C#N)C#N.[K] Chemical compound [Co](C#N)C#N.[K] UCFIGPFUCRUDII-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 11
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 10
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- DQRBSSNRRYZPJZ-UHFFFAOYSA-N [Co](C#N)C#N.[Na] Chemical compound [Co](C#N)C#N.[Na] DQRBSSNRRYZPJZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
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- 239000005457 ice water Substances 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
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- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
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- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 235000002651 pink gum Nutrition 0.000 claims 1
- 244000087877 pink gum Species 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
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- 239000002994 raw material Substances 0.000 abstract description 2
- 229910000358 iron sulfate Inorganic materials 0.000 abstract 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 229910017052 cobalt Inorganic materials 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910000531 Co alloy Inorganic materials 0.000 description 4
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- IDUKLYIMDYXQQA-UHFFFAOYSA-N cobalt cyanide Chemical compound [Co].N#[C-] IDUKLYIMDYXQQA-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- ZDZDKCXMWZGZSA-UHFFFAOYSA-N [Co]C#N.[Co]C#N Chemical compound [Co]C#N.[Co]C#N ZDZDKCXMWZGZSA-UHFFFAOYSA-N 0.000 description 1
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- 150000001868 cobalt Chemical class 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
本发明提供一种氮掺杂石墨烯负载CoCx/FeCo@C的燃料电池氧还原催化剂及其制备方法，所述方法首先制备氧化石墨烯水分散液，然后利用硫酸铁、硫酸钴、钴***及制备的石墨烯水分散液制备出前驱体，然后将制备得到的前驱体在氩气气氛下还原，得到氮掺杂石墨烯负载CoCx/FeCo@C的燃料电池氧还原催化剂，利用本申请的方法制备氮掺杂石墨烯负载CoCx/FeCo@C的燃料电池氧还原催化剂的操作过程简单，所用原料廉价易得，能耗小，对设备无特殊要求，附加环境污染少，且制备得到的产物石墨烯作载体，提供大的比表面积，增加反应速率，以氮掺杂的CoCx/FeCo@C作为活性中心位点，具有很高的氧还原催化活性。
The invention provides a nitrogen-doped graphene-supported CoCx/FeCo@C fuel cell oxygen reduction catalyst and a preparation method thereof. The method first prepares an aqueous dispersion of graphene oxide, and then uses iron sulfate, cobalt sulfate, and cobalt cyanide Potassium and the prepared graphene aqueous dispersion to prepare a precursor, and then reduce the prepared precursor in an argon atmosphere to obtain a nitrogen-doped graphene-loaded CoCx/FeCo@C fuel cell oxygen reduction catalyst, using this application The method for preparing nitrogen-doped graphene-supported CoCx/FeCo@C fuel cell oxygen reduction catalyst has simple operation process, cheap and easy-to-obtain raw materials, low energy consumption, no special requirements for equipment, and less additional environmental pollution, and the prepared The product graphene is used as a carrier to provide a large specific surface area and increase the reaction rate, and the nitrogen-doped CoC x /FeCo@C is used as the active center site, which has a high catalytic activity for oxygen reduction.
Description
技术领域technical field
本发明涉及燃料电池电催化技术领域，与其涉及一种氮掺杂石墨烯负载CoCx/FeCo@C的燃料电池氧还原催化剂及其制备方法。The invention relates to the technical field of fuel cell electrocatalysis, in particular to a nitrogen-doped graphene-supported CoCx/FeCo@C fuel cell oxygen reduction catalyst and a preparation method thereof.
背景技术Background technique
化石燃料的过度开采，对环境造成了很大的污染，威胁人类生存的环境，这就要求我们尽快开发清洁、可再生能源。目前，在已知的新型能源体系中，燃料电池是极具潜力的一种高效、绿色的清洁能源转换***，是人类历史上的又一次重大变革。燃料电池是一种将燃料(如氢气、天然气、醇类等)与氧化剂(氧气等)直接通过电化学反应而不需要经过燃烧，直接转化成电能的电化学反应装置。阴极氧还原反应(ORR)在燃料电池体系中的意义重大，其限制着燃料电池的大规模应用。因此，开发高效、环保的燃料电池阴极氧还原催化剂尤为重要。Excessive exploitation of fossil fuels has caused great pollution to the environment and threatened the living environment of human beings. This requires us to develop clean and renewable energy as soon as possible. At present, among the known new energy systems, fuel cells are an efficient, green and clean energy conversion system with great potential, which is another major change in human history. A fuel cell is an electrochemical reaction device that converts fuels (such as hydrogen, natural gas, alcohols, etc.) and oxidants (oxygen, etc.) directly into electrical energy through electrochemical reactions without burning. The cathodic oxygen reduction reaction (ORR) is of great significance in fuel cell systems, which limits the large-scale application of fuel cells. Therefore, it is particularly important to develop efficient and environmentally friendly fuel cell cathode oxygen reduction catalysts.
阴极氧还原反应是限制质子交换膜燃料电池(PEMFC)和直接甲醇燃料电池(DMFC)性能的重要因素。目前，人们认为ORR主要通过两种途径发生，即氧气完全还原生成水的四电子过程和部分还原生成过氧化氢的二电子过程。The cathodic oxygen reduction reaction is an important factor limiting the performance of proton exchange membrane fuel cells (PEMFC) and direct methanol fuel cells (DMFC). Currently, it is believed that ORR mainly occurs through two pathways, the four-electron process of complete reduction of oxygen to water and the two-electron process of partial reduction of oxygen to hydrogen peroxide.
Pt/C催化剂是目前性能最优的催化剂，但是同样存在很多缺点：首先，Pt电极成本高，限制了其更大规模的应用；其次，耐久性低且易中毒，反应过程产生大量的一氧化碳，使催化剂中毒，从而使其反应效率大为降低，更加制约了燃料电池大规模应用和商业化发展。因此，开发廉价、耐用、高效和稳定的非铂阴极氧还原催化剂是目前燃料电池的重中之重。Pt/C catalyst is the catalyst with the best performance at present, but there are also many disadvantages: first, the high cost of Pt electrodes limits its larger-scale application; The catalyst is poisoned, thereby greatly reducing its reaction efficiency, which further restricts the large-scale application and commercial development of fuel cells. Therefore, the development of cheap, durable, efficient, and stable oxygen reduction catalysts for non-platinum cathodes is a top priority for fuel cells.
发明内容Contents of the invention
本发明针对现有技术的不足，提供一种高效、低价、环境友好的氮掺杂石墨烯负载CoCx/FeCo@C的燃料电池氧还原催化剂及其制备方法。Aiming at the deficiencies of the prior art, the present invention provides a high-efficiency, low-cost, and environment-friendly nitrogen-doped graphene-supported CoCx/FeCo@C fuel cell oxygen reduction catalyst and a preparation method thereof.
本发明是通过如下技术方案实现的：The present invention is achieved through the following technical solutions:
提供一种氮掺杂石墨烯负载CoCx/FeCo@C的燃料电池氧还原催化剂的制备方法，所述方法包括如下步骤：A method for preparing a nitrogen-doped graphene-supported fuel cell oxygen reduction catalyst of CoCx/FeCo@C is provided, the method comprising the steps of:
S01：制备氧化石墨烯水分散液；S01: preparing an aqueous dispersion of graphene oxide;
S02：制备前驱体：将硫酸钴、氯化钴和硝酸钴中的一种、以及钴***和钴***中的一种配成溶液后于常温下搅拌至得到粉红色胶装物质，然后加入硫酸铁或氯化铁，于常温下搅拌至得到黑黄色溶胶，再加入制备得到的氧化石墨烯水分散液搅拌均匀，超声分散、洗涤、干燥后，得到前驱体；S02: Prepare the precursor: make a solution of cobalt sulfate, one of cobalt chloride and cobalt nitrate, and one of potassium cobaltcyanide and sodium cobaltcyanide, and stir at room temperature until a pink glue-coated substance is obtained , then add ferric sulfate or ferric chloride, stir at room temperature until a black-yellow sol is obtained, then add the prepared graphene oxide aqueous dispersion and stir evenly, ultrasonically disperse, wash, and dry to obtain a precursor;
使用硫酸钴、钴***和硫酸铁制备前驱体时，钴***提供氮源，反应存在如下步骤：When cobalt sulfate, potassium cobaltcyanide and ferric sulfate are used to prepare the precursor, potassium cobaltcyanide provides a nitrogen source, and the reaction has the following steps:
CoSO4+K3[Co(CN)6]→Co3[Co(CN)6]2 CoSO 4 +K 3 [Co(CN) 6 ]→Co 3 [Co(CN) 6 ] 2
Co3[Co(CN)6]2+Fe2(SO4)3→Fe[Co(CN)6]Co 3 [Co(CN) 6 ] 2 +Fe 2 (SO4) 3 →Fe[Co(CN) 6 ]
有上述反应步骤可知，当钴***被完全取代时需要4mol的硫酸钴，当硫酸铁加入时，会将一部分的钴氰化钴进行置换，剩余的钴***与取代的钴结合，生成钴氰化钴。因此，在最后的生成物中，是Fe[Co(CN)6]与Co3[Co(CN)6]2的共同混合物，Fe[Co(CN)6]大量存在，Co3[Co(CN)6]2少量存在，这也是后期FeCo合金和CoCx生成的重要依据。在第一步反应中，硫酸钴与钴***全部反应生成钴氰化钴，在硫酸铁的加入后，一部分的钴氰化钴中的钴被取代，生成钴氰化铁，这也是反应中CoCx的来源之一。It can be seen from the above reaction steps that when potassium cobaltcyanide is completely replaced, 4mol of cobalt sulfate is required. When ferric sulfate is added, a part of cobalt cobalt cyanide will be replaced, and the remaining potassium cobaltcyanide will be combined with the substituted cobalt. Cobalt cyanide is produced. Therefore, in the final product, it is a common mixture of Fe[Co(CN) 6 ] and Co 3 [Co(CN)6] 2 , Fe[Co(CN) 6 ] exists in large quantities, Co 3 [Co(CN) ) 6 ] 2 exists in a small amount, which is also an important basis for the formation of FeCo alloy and CoCx in the later stage. In the first step reaction, cobalt sulfate and potassium cobaltcyanide react completely to form cobalt cyanide. After the addition of ferric sulfate, the cobalt in a part of cobalt cyanide is replaced to generate ferric cobalt cyanide, which is also a reaction One of the sources of CoCx in.
S03：将所得前驱体在800～1000℃氩气气氛下还原4h，得到氮掺杂石墨烯负载CoCx/FeCo@C的燃料电池氧还原催化剂。S03: The obtained precursor was reduced for 4 hours at 800-1000° C. under an argon atmosphere to obtain a fuel cell oxygen reduction catalyst supported on CoCx/FeCo@C on nitrogen-doped graphene.
前驱体在800～1000℃氩气气氛下还原时，由于高温反应，前驱体发生热解，产生含氮元素的碳层，在高温作用下，铁与钴发生反应，生成铁钴合金，由于在配比中，钴的含量要高于铁，因此，多余的钴会与外层的碳反应，生成CoCx。铁钴合金的活性位相对确定，是以铁和钴为核心，辅以小部分的CoCx为活性位，利用碳层将其包覆，增加了其比表面积，同时也增加了其导电性，对于优良的电催化剂而言，选择性高的活性位点和高的导电性是重要的依据。When the precursor is reduced in an argon atmosphere at 800-1000°C, due to the high-temperature reaction, the precursor is pyrolyzed to produce a carbon layer containing nitrogen elements. Under the action of high temperature, iron and cobalt react to form an iron-cobalt alloy. In the ratio, the content of cobalt is higher than that of iron, so the excess cobalt will react with the carbon in the outer layer to form CoCx. The active site of the iron-cobalt alloy is relatively definite, with iron and cobalt as the core, supplemented by a small part of CoCx as the active site, and covered with a carbon layer, which increases its specific surface area and also increases its conductivity. For an excellent electrocatalyst, highly selective active sites and high electrical conductivity are important basis.
优选的，所述步骤S02中，制备前驱体：将硫酸钴、氯化钴和硝酸钴中的一种、以及钴***和钴***中的一种按照1:4的摩尔比配成溶液后于常温下搅拌4～6小时，得到粉红色胶装物质，然后按照与硫酸钴、氯化钴或硝酸钴1:1的摩尔比加入硫酸铁或氯化铁，于常温下搅拌12～14小时，得到黑黄色溶胶，再加入6g/L的氧化石墨烯分散液30～50mL搅拌均匀，超声分散1小时后将所得溶胶洗涤、于80～85℃干燥，得到前驱体。Preferably, in the step S02, the precursor is prepared: one of cobalt sulfate, cobalt chloride and cobalt nitrate, and one of potassium cobalt cyanide and sodium cobalt cyanide are prepared according to a molar ratio of 1:4 After forming a solution, stir at room temperature for 4 to 6 hours to obtain a pink gelatinous substance, then add ferric sulfate or ferric chloride at a molar ratio of 1:1 with cobalt sulfate, cobalt chloride or cobalt nitrate, and stir at room temperature for 12 After ~14 hours, a black-yellow sol was obtained, and then 30-50 mL of a 6 g/L graphene oxide dispersion was added and stirred evenly. After ultrasonic dispersion for 1 hour, the obtained sol was washed and dried at 80-85° C. to obtain a precursor.
优选的，所述步骤S01中，制备氧化石墨烯水分散液的方法为：Preferably, in the step S01, the method for preparing the graphene oxide aqueous dispersion is:
将1～5g石墨粉(325目)与高锰酸钾浓硫酸以质量比为1:5:38的质量比在冰水浴中搅拌12h，得到棕色粘稠物，将此棕色粘稠物缓慢加入200mL超纯水中，接着缓慢滴加15～20mL 30％双氧水，在20～30℃下搅拌30～40min，经过9000r/min离心洗涤6次，每次3～5min，配成6g/L的氧化石墨烯水分散液。Stir 1~5g of graphite powder (325 mesh) and potassium permanganate concentrated sulfuric acid in an ice-water bath for 12 hours at a mass ratio of 1:5:38 to obtain a brown viscous substance, which is slowly added 200mL of ultrapure water, then slowly add 15-20mL of 30% hydrogen peroxide dropwise, stir at 20-30°C for 30-40min, centrifuge and wash at 9000r/min for 6 times, each time for 3-5min, and make 6g/L hydrogen peroxide Graphene aqueous dispersion.
加入双氧水将棕色粘稠物中的杂质离子清洗，然后使用离心机离心分离固液相物质，也可以先进行离心分离，再用溶剂清洗混在沉淀物(即棕色粘稠物)中的杂质离子，或者离心过程中进行洗涤。离心洗涤是将固相和液相物质进行分离，采用离心机进行，离心机的转速设置为9000r/min，第一次加入固液混合物，开启离心机离心，离心5min，离心机停止后得到沉淀物质，然后向得到的沉淀物质中加入溶剂，然后第二次开启离心机离心3～5min，停止离心机后，离心机中只剩沉淀物，再向得到的的沉淀物中加入溶剂，再第三次开启离心机，以此类推，供离心洗涤六次，每次离心3～5min。Add hydrogen peroxide to clean the impurity ions in the brown viscous matter, and then use a centrifuge to centrifuge the solid-liquid phase substances. You can also perform centrifugation first, and then use a solvent to clean the impurity ions mixed in the precipitate (ie brown viscous matter). Or wash during centrifugation. Centrifugal washing is to separate the solid phase and liquid phase substances. It is carried out by a centrifuge. The speed of the centrifuge is set to 9000r/min. The solid-liquid mixture is added for the first time, and the centrifuge is turned on for 5 minutes. After the centrifuge stops, precipitation is obtained. Substance, then add solvent to the obtained precipitate, then turn on the centrifuge for 3 to 5 minutes for the second time, stop the centrifuge, only the precipitate remains in the centrifuge, then add solvent to the obtained precipitate, and then centrifuge for the second time Turn on the centrifuge three times, and so on, for six times of centrifugation and washing, each centrifugation for 3 to 5 minutes.
第二方面，本发明提供一种如权利要求1-3任一项所述方法制备得到的氮掺杂石墨烯负载CoCx/FeCo@C的燃料电池氧还原催化剂。In a second aspect, the present invention provides a fuel cell oxygen reduction catalyst prepared by the method according to any one of claims 1-3, which is a nitrogen-doped graphene-supported CoCx/FeCo@C fuel cell.
本发明实施例提供的技术方案可以包含以下有益效果：The technical solutions provided by the embodiments of the present invention may include the following beneficial effects:
本发明提供一种氮掺杂石墨烯负载CoCx/FeCo@C的燃料电池氧还原催化剂及其制备方法，所述方法首先制备氧化石墨烯水分散液，然后利用硫酸铁和氯化铁中的一种、硫酸钴、氯化钴和硝酸钴中的一种、钴***和钴***中的一种、以及制备的石墨烯水分散液制备前驱体，最后将制备得到的前驱体在800～1000℃氩气气氛下还原，还原时由于高温反应，前驱体发生热解，产生含氮元素的碳层，铁与钴发生反应，生成铁钴合金，多余的钴与外层的碳反应，生成CoCx。铁钴合金的活性位相对确定，是以铁和钴为核心，辅以小部分的CoCx为活性位，利用碳层将其包覆，增加了其比表面积，同时也增加了其导电性，增加反应速率，以氮掺杂的CoCx/FeCo@C作为活性中心位点，具有很高的氧还原催化活性。并且，本申请提供的制备方法操作过程简单，所用原料廉价易得，能耗小，对设备无特殊要求，附加环境污染少，在燃料电池领域有着良好的应用前景。The invention provides a nitrogen-doped graphene-supported CoCx/FeCo@C fuel cell oxygen reduction catalyst and a preparation method thereof. The method first prepares a graphene oxide aqueous dispersion, and then utilizes one of ferric sulfate and ferric chloride to one of cobalt sulfate, cobalt chloride and cobalt nitrate, one of potassium cobaltcyanide and sodium cobaltcyanide, and the prepared graphene aqueous dispersion to prepare a precursor, and finally prepare the precursor in Reduction under argon atmosphere at 800-1000°C, during reduction, due to high-temperature reaction, the precursor undergoes pyrolysis to produce a carbon layer containing nitrogen elements, iron and cobalt react to form an iron-cobalt alloy, and the excess cobalt reacts with the carbon in the outer layer , to generate CoCx. The active site of the iron-cobalt alloy is relatively definite, with iron and cobalt as the core, supplemented by a small part of CoCx as the active site, and covered with a carbon layer, which increases its specific surface area and also increases its conductivity. The reaction rate, with nitrogen-doped CoC x /FeCo@C as the active center site, has a high catalytic activity for oxygen reduction. Moreover, the preparation method provided by the present application has simple operation process, cheap and easy-to-obtain raw materials, low energy consumption, no special requirements on equipment, and less additional environmental pollution, and has good application prospects in the field of fuel cells.
附图说明Description of drawings
为了更清楚的说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单介绍，显而易见的，对于本领域技术人员而言，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, for those skilled in the art, Other drawings can also be obtained from these drawings without any creative effort.
图1为本发明实施例1得到的氮掺杂石墨烯负载CoCx/FeCo@C的燃料电池氧还原催化剂的XRD图。Fig. 1 is an XRD pattern of the nitrogen-doped graphene-supported CoCx/FeCo@C fuel cell oxygen reduction catalyst obtained in Example 1 of the present invention.
图2为本发明实施例1得到的氮掺杂石墨烯负载CoCx/FeCo@C的燃料电池氧还原催化剂的SEM图。Fig. 2 is a SEM image of the nitrogen-doped graphene-supported CoCx/FeCo@C fuel cell oxygen reduction catalyst obtained in Example 1 of the present invention.
图3为本发明实施例1的氮掺杂石墨烯负载CoCx/FeCo@C的循环伏安曲线图(CV曲线)。3 is a cyclic voltammetry curve (CV curve) of nitrogen-doped graphene-supported CoC x /FeCo@C in Example 1 of the present invention.
图4为本发明实施例1得到的氮掺杂石墨烯负载CoCx/FeCo@C的燃料电池氧还原催化剂在氧气饱和的0.1M KOH溶液中的旋转圆盘曲线。Fig. 4 is the rotating disk curve of the nitrogen-doped graphene-supported CoCx/FeCo@C fuel cell oxygen reduction catalyst obtained in Example 1 of the present invention in an oxygen-saturated 0.1M KOH solution.
具体实施方式Detailed ways
为了使本技术领域的人员更好地理解本发明中的技术方案,下面对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都应当属于本发明的保护范围。In order to enable those skilled in the art to better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention are clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and Not all examples. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative efforts shall belong to the protection scope of the present invention.
本发明实施例提供的一种氮掺杂石墨烯负载CoCx/FeCo@C的燃料电池氧还原催化剂及其制备方法，所述方法包括：制备氧化石墨烯水分散液、制备前驱体、将制备的前驱体在氩气气氛下还原，最终得到氮掺杂石墨烯负载CoCx/FeCo@C的燃料电池氧还原催化剂。下述实施例均按上述方法流程进行。A nitrogen-doped graphene-supported CoCx/FeCo@C fuel cell oxygen reduction catalyst and a preparation method thereof provided in an embodiment of the present invention, the method includes: preparing a graphene oxide aqueous dispersion, preparing a precursor, and preparing the prepared The precursors were reduced under an argon atmosphere, and a nitrogen-doped graphene-supported CoCx/FeCo@C fuel cell oxygen reduction catalyst was finally obtained. The following examples are all carried out according to the above method flow.
首先制备氧化石墨烯水分散液，石墨粉采用改进的Hummers法制备，制备过程如下：将1～5g石墨粉(325目)与高锰酸钾及浓硫酸以质量比为1:5:38的质量比在冰水浴中搅拌12h，得到棕色粘稠物，然后将此棕色粘稠物缓慢加入200mL超纯水中，接着缓慢滴加15～20mL 30％双氧水，在20～30℃下搅拌30～40min，经过9000r/min离心洗涤6次，每次3～5min，配成6g/L的氧化石墨烯水分散液。First prepare graphene oxide aqueous dispersion, graphite powder is prepared by improved Hummers method, the preparation process is as follows: 1 ~ 5g graphite powder (325 mesh) and potassium permanganate and concentrated sulfuric acid are 1:5:38 in mass ratio Stir in an ice-water bath for 12 hours to obtain a brown viscous substance, then slowly add the brown viscous substance to 200mL ultrapure water, then slowly add 15-20mL 30% hydrogen peroxide dropwise, and stir at 20-30°C for 30- After 40 minutes, centrifuge and wash at 9000r/min for 6 times, each time for 3-5 minutes, and prepare a 6g/L graphene oxide aqueous dispersion.
下述实施例使用的氧化石墨烯水分散液均为上述制备得到的。The graphene oxide aqueous dispersions used in the following examples are all prepared above.
实施例1Example 1
将硫酸钴和钴***按照1:4的摩尔比配成溶液，得到粉红色溶液，常温搅拌4小时，得到粉红色胶装物质，按照与硫酸钴或者氯化钴1:1的摩尔比加入硫酸铁，常温搅拌12小时，得到黑黄色溶胶，再加入6g/L的氧化石墨烯分散液30mL，搅拌均匀后，超声分散1小时，然后将所得溶胶洗涤，80℃干燥，得到前驱体；Make cobalt sulfate and potassium cobalt cyanide into a solution according to the molar ratio of 1:4 to obtain a pink solution, stir at room temperature for 4 hours to obtain a pink gelatinous substance, according to the molar ratio of 1:1 with cobalt sulfate or cobalt chloride Add ferric sulfate, stir at room temperature for 12 hours to obtain a black-yellow sol, then add 30 mL of a 6 g/L graphene oxide dispersion, stir evenly, disperse ultrasonically for 1 hour, then wash the obtained sol and dry at 80°C to obtain a precursor;
将所得前驱体在800℃氩气气氛下还原4h，得到氮掺杂石墨烯负载CoCx/FeCo@C的燃料电池氧还原催化剂。The resulting precursor was reduced at 800 °C under an argon atmosphere for 4 h to obtain a fuel cell oxygen reduction catalyst supported by nitrogen-doped graphene supported on CoCx/FeCo@C.
如图1所示，为本实施例所得的氮掺杂石墨烯负载CoCx/FeCo@C催化剂的X射线衍射图谱，经过Jade软件分析能够得到石墨烯上负载的物质为CoCx和FeCo合金，由于石墨烯为单层结构，无衍射峰。As shown in Figure 1, it is the X-ray diffraction pattern of the nitrogen-doped graphene-supported CoCx /FeCo@C catalyst obtained in this example. After analysis by Jade software, it can be obtained that the substance supported on the graphene is CoCx and FeCo alloy. Since graphene is a single-layer structure, there are no diffraction peaks.
图2为本实施例所得的氮掺杂石墨烯负载CoCx/FeCo@C催化剂的扫描电镜图片，由图2可知，本实施例制得的CoCx/FeCo@C均为核壳结构，平均粒径为200～300nm，有利于氧还原反应的进行。当催化剂的单个粒子直径在纳米级别时，其比表面积会得到巨大的提升，有利于与电解质和氧气接触，提升反应速率，提高反应活性。Figure 2 is a scanning electron microscope image of the nitrogen-doped graphene-supported CoC x /FeCo@C catalyst obtained in this example. It can be seen from Figure 2 that the CoC x /FeCo@C prepared in this example has a core-shell structure, with an The particle size is 200-300nm, which is conducive to the oxygen reduction reaction. When the single particle diameter of the catalyst is at the nanometer level, its specific surface area will be greatly improved, which is conducive to contact with the electrolyte and oxygen, increase the reaction rate, and increase the reaction activity.
将本实施例制备得到的催化剂按如下方法进行性能测试：The catalyst that present embodiment prepares is carried out performance test as follows:
将氮掺杂石墨烯负载CoCx/FeCo@C的燃料电池氧还原催化剂修饰到电极上。测试前将玻碳电极(直径3mm)经过如下步骤处理：先用50nm的Al2O3粉膜打磨，然后分别用乙醇、超纯水清洗(在超声仪器中)，在空气中晾干。工作电极的制备如下：取5mg催化剂加入450μL超纯水，加入50μL质量分数为5％的Nafion溶液中，超声分散1小时，用微量移液枪取上述催化剂溶液5μL于玻碳电极上，在空气中晾干。旋转圆盘电极(直径5mm)经过同样的处理方法，然后取10μL滴在电极表面，在空气中晾干。Nitrogen-doped graphene-supported CoC x /FeCo@C fuel cell oxygen reduction catalyst modified onto electrodes. Before the test, the glassy carbon electrode (diameter 3mm) was processed by the following steps: first, it was polished with 50nm Al 2 O 3 powder film, then cleaned with ethanol and ultrapure water (in an ultrasonic instrument), and dried in the air. The preparation of the working electrode is as follows: Take 5 mg of the catalyst, add 450 μL of ultrapure water, add 50 μL of Nafion solution with a mass fraction of 5%, and disperse it by ultrasonic for 1 hour, take 5 μL of the above catalyst solution on the glassy carbon electrode with a micropipette, to dry. The rotating disc electrode (5 mm in diameter) was treated in the same way, and then 10 μL was dropped on the surface of the electrode and dried in the air.
具体条件如下：用CHI 760e型电化学工作站(上海辰华仪器有限公司)进行电化学性质测试，将所制备的催化剂涂在玻碳电极上作为工作电极，Hg/Hg2Cl2电极和碳电极用作参比电极和辅助电极，在0.1M氢氧化钾溶液中测试得到循环伏安图(CV图)。The specific conditions are as follows: CHI 760e electrochemical workstation (Shanghai Chenhua Instrument Co., Ltd.) was used to test the electrochemical properties, the prepared catalyst was coated on the glassy carbon electrode as the working electrode, the Hg/Hg 2 Cl 2 electrode and the carbon electrode It is used as a reference electrode and an auxiliary electrode, and it is tested in a 0.1M potassium hydroxide solution to obtain a cyclic voltammogram (CV diagram).
图3为本实施例制备的氮掺杂石墨烯负载CoCx/FeCo@C催化剂在氧气饱和的0.1mol·L-1KOH溶液中在不同扫速下的循环伏安曲线。扫描时，CoCx/FeCo@C在1.0V开始出峰，峰位置为0.75V到1.0V，电流密度峰值为-4.0mA cm-2。催化剂的起始电位越大，电流密度越高，说明其催化性能越优异，本实施例催化剂的起始点位交啊，催化性能优异。Figure 3 is the cyclic voltammetry curves of the nitrogen-doped graphene-supported CoC x /FeCo@C catalyst prepared in this example in an oxygen-saturated 0.1 mol L -1 KOH solution at different scan rates. During scanning, CoC x /FeCo@C begins to peak at 1.0V, the peak position is from 0.75V to 1.0V, and the peak current density is -4.0mA cm -2 . The larger the onset potential and the higher the current density of the catalyst, the better the catalytic performance. The starting point of the catalyst in this example is cross-ah, and the catalytic performance is excellent.
图4为本实施例的CoCx/FeCo@C催化剂在氧气饱和的0.1mol·L-1KOH溶液中的旋转圆盘曲线，计算得出对于催化剂CoCx/FeCo@C在0.61、0.56、0.51、0.46V处转移电子数n分别为3.80、3.82、3.84、3.88。通常认为的反应过程有两个，一个是氧气、2个电子和水生成过氧化氢，再由过氧化氢继续反应生成OH-的过程，另一个过程则是氧气、4个电子和水反应直接生成OH-的过程，这个过程对氧还原反应来说是有利的，因此，转移电子数越接近4，反应活性越高，催化效果越好，本实施例转移电子数n达3.88，反应活性高，催化效果好。Figure 4 is the rotating disk curve of the CoC x /FeCo@C catalyst in this example in an oxygen-saturated 0.1mol L -1 KOH solution, and it is calculated that for the catalyst CoC x /FeCo@C at 0.61, 0.56, 0.51 , 0.46V place transfer electron number n are 3.80, 3.82, 3.84, 3.88 respectively. There are two generally considered reaction processes, one is the process in which oxygen, 2 electrons and water generate hydrogen peroxide, and then the hydrogen peroxide continues to react to generate OH- , and the other process is the direct reaction of oxygen, 4 electrons and water The process of generating OH - is beneficial to the oxygen reduction reaction. Therefore, the closer the number of transferred electrons is to 4, the higher the reactivity and the better the catalytic effect. In this embodiment, the number n of transferred electrons reaches 3.88, and the reactivity is high. , good catalytic effect.
实施例2Example 2
将氯化钴、钴***按照1:4的摩尔比配成溶液，得到粉红色溶液，常温搅拌6小时，得到粉红色胶装物质，按照与硫酸钴或者氯化钴1:1的摩尔比加入氯化铁，常温搅拌14小时，得到黑黄色溶胶，再加入6g/L的氧化石墨烯分散液50mL，搅拌均匀后，超声分散1小时，然后将所得溶胶洗涤，85℃干燥，得到前驱体；Mix cobalt chloride and sodium cobalt cyanide into a solution at a molar ratio of 1:4 to obtain a pink solution, stir at room temperature for 6 hours to obtain a pink gummed substance, and mix it with cobalt sulfate or cobalt chloride at a molar ratio of 1:1 Add ferric chloride and stir for 14 hours at room temperature to obtain a black-yellow sol, then add 50 mL of a 6 g/L graphene oxide dispersion, stir evenly, disperse ultrasonically for 1 hour, then wash the obtained sol and dry at 85°C to obtain a precursor body;
将所得前驱体在1000℃氩气气氛下还原4h，得到氮掺杂石墨烯负载CoCx/FeCo@C的燃料电池氧还原催化剂。The resulting precursor was reduced under an argon atmosphere at 1000 °C for 4 h to obtain a fuel cell oxygen reduction catalyst supported by nitrogen-doped graphene supported on CoCx/FeCo@C.
实施例3Example 3
将硝酸钴、钴***按照1:4的摩尔比配成溶液，得到粉红色溶液，常温搅拌5小时，得到粉红色胶装物质，按照与硫酸钴或者氯化钴1:1的摩尔比加入硫酸铁或氯化铁，常温搅拌13小时，得到黑黄色溶胶，再加入6g/L的氧化石墨烯分散液40mL，搅拌均匀后，超声分散1小时，然后将所得溶胶洗涤，83℃干燥，得到前驱体；Make cobalt nitrate and potassium cobalt cyanide into a solution at a molar ratio of 1:4 to obtain a pink solution, stir at room temperature for 5 hours to obtain a pink gelatinous substance, and use a molar ratio of 1:1 to cobalt sulfate or cobalt chloride Add ferric sulfate or ferric chloride, stir at room temperature for 13 hours to obtain a black-yellow sol, then add 40 mL of 6 g/L graphene oxide dispersion, stir evenly, disperse ultrasonically for 1 hour, then wash the obtained sol, and dry it at 83°C. get the precursor;
将所得前驱体在900℃氩气气氛下还原4h，得到氮掺杂石墨烯负载CoCx/FeCo@C的燃料电池氧还原催化剂。The resulting precursor was reduced at 900 °C under an argon atmosphere for 4 h to obtain an oxygen reduction catalyst for fuel cells supported by nitrogen-doped graphene supported on CoCx/FeCo@C.
将实施例2和实施例3得到的产品与实施例1进行相同的测试，测试结果与实施例1相差不大，说明本发明实施例提供的方法制备得到的产品的反应活性较高，催化性能优良。The product obtained in Example 2 and Example 3 is subjected to the same test as in Example 1, and the test results are not much different from Example 1, which shows that the product prepared by the method provided by the embodiment of the present invention has higher reactivity and catalytic performance. excellent.
当然，上述说明也并不仅限于上述举例，本发明未经描述的技术特征可以通过或采用现有技术实现，在此不再赘述；以上实施例仅用于说明本发明的技术方案并非是对本发明的限制，参照优选的实施方式对本发明进行了详细说明，本领域的普通技术人员应当理解，本技术领域的普通技术人员在本发明的实质范围内所做出的变化、改型、添加或替换都不脱离本发明的宗旨，也应属于本发明的权利要求保护范围。Of course, the above description is not limited to the above examples, and the undescribed technical features of the present invention can be realized by or using existing technologies, and will not be repeated here; The present invention has been described in detail with reference to preferred embodiments, and those of ordinary skill in the art should understand that changes, modifications, additions or substitutions made by those of ordinary skill in the art within the true scope of the present invention All of them do not deviate from the gist of the present invention, and should also belong to the protection scope of the claims of the present invention.
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