CN106910902A - A kind of fuel cell oxygen reduction catalyst and preparation method thereof - Google Patents
A kind of fuel cell oxygen reduction catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 239000000446 fuel Substances 0.000 title claims abstract description 52
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000001301 oxygen Substances 0.000 title claims abstract description 50
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011572 manganese Substances 0.000 claims abstract description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
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- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011345 viscous material Substances 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 5
- 150000004706 metal oxides Chemical class 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 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 description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 40
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 23
- 239000000243 solution Substances 0.000 description 17
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 229910021397 glassy carbon Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
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- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
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- 239000011259 mixed solution Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
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- 238000001354 calcination Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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Classifications
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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
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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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
本发明提供一种燃料电池氧还原催化剂及其制备方法，所述方法包括氧化石墨烯水分散液的制备、锰基配合物的制备以及不同气体氛围下高温焙烧得到不同产物，本发明的方法所用原料廉价易得，操作简便快捷，能耗小，对设备无特殊要求，附加环境污染少，通过控制锰基氧化态种类表现出极佳的氧还原催化性能，在燃料电池领域有着良好的应用前景。并且，本发明制备的产物中，MnO和Mn2O3混合态金属氧化物以及MnO，均为棒状结构，能与石墨烯紧密结合，且比表面积大，电催化效率高。
The invention provides a fuel cell oxygen reduction catalyst and a preparation method thereof. The method includes the preparation of a graphene oxide aqueous dispersion, the preparation of a manganese-based complex, and high-temperature roasting in different gas atmospheres to obtain different products. The method used in the present invention The raw materials are cheap and easy to obtain, the operation is simple and fast, the energy consumption is small, there is no special requirement for the equipment, and there is little additional environmental pollution. By controlling the oxidation state of manganese, it shows excellent oxygen reduction catalytic performance, and has a good application prospect in the field of fuel cells. . Moreover, in the products prepared by the present invention, MnO and Mn 2 O 3 mixed state metal oxides and MnO are all rod-shaped structures, can be closely combined with graphene, and have a large specific surface area and high electrocatalytic efficiency.
Description
技术领域technical field
本发明涉及燃料电池技术领域，尤其涉及一种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 cells, in particular to a fuel cell oxygen reduction catalyst and a preparation method thereof.
背景技术Background technique
随着化石能源的日益枯竭，以及在使用过程中对环境的污染，对尽快开发清洁、可再生能源的要求越来越迫切。燃料电池是目前极具潜力的一种高效绿色清洁能源转换***，是继火力、水力和核能发电之后的第四类发电技术，是一种将燃料（氢气、天然气、醇类等）与氧化剂（氧气）反应的化学能，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。With the depletion of fossil energy and the pollution of the environment in the process of use, it is more and more urgent to develop clean and renewable energy as soon as possible. Fuel cell is a high-efficiency green and clean energy conversion system with great potential at present. It is the fourth type of power generation technology after thermal power, hydropower and nuclear power generation. An electrochemical reaction device that converts the chemical energy of the oxygen) reaction directly into electrical energy through an electrochemical reaction without combustion.
阴极氧还原反应（ORR）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，即四氢四电子的完全还原生成水的过程和二氢二电子的部分还原生成过氧化氢的过程。The cathode oxygen reduction reaction (ORR) is an important factor limiting the performance of proton exchange membrane fuel cells (PEMFC) and direct methanol fuel cells (DMFC). At present, it is believed that ORR mainly occurs through two pathways, namely the complete reduction of tetrahydrogen and four electrons to water and the partial reduction of dihydrogen and two electrons to hydrogen peroxide.
现如今应用较广的燃料电池阴极催化剂是Pt/C催化剂，碳材料由于制备简单、易于大规模生产并有良好的化学性能、机械稳定性，被人们广泛地用于燃料电池催化剂载体。2004年,英国科学家发现了由单层碳原子紧密堆积成二维蜂窝状晶格结构的一种碳质新材料-石墨烯(graphene)。石墨烯是一类十分重要的新型材料，具有比表面积大、导电性和导热性优良以及独特的超薄石墨平面结构等重要性质和结构特征。金属氧化物的电化学活性取决于纳米材料的尺寸及形状，纳米结构具有更大的比表面积和更多的活性中心，在电化学反应中就具有更高的活性。Nowadays, the fuel cell cathode catalyst widely used is Pt/C catalyst. Carbon materials are widely used as fuel cell catalyst supports because of their simple preparation, easy mass production, good chemical properties and mechanical stability. In 2004, British scientists discovered a new carbonaceous material - graphene, which is tightly packed into a two-dimensional honeycomb lattice structure by a single layer of carbon atoms. Graphene is a very important new type of material, which has important properties and structural characteristics such as large specific surface area, excellent electrical and thermal conductivity, and unique ultra-thin graphite planar structure. The electrochemical activity of metal oxides depends on the size and shape of nanomaterials. Nanostructures have larger specific surface areas and more active centers, and thus have higher activity in electrochemical reactions.
但是，由于Pt电极具有成本高、耐久性低、资源缺乏，且易中毒的缺点，严重制约了燃料电池大规模应用和商业化发展。故急需开发廉价、耐用、高效和稳定的非铂基阴极氧还原催化剂。However, due to the disadvantages of high cost, low durability, lack of resources, and easy poisoning of Pt electrodes, the large-scale application and commercial development of fuel cells are seriously restricted. Therefore, there is an urgent need to develop inexpensive, durable, efficient and stable non-platinum-based cathode oxygen reduction catalysts.
发明内容Contents of the invention
本发明针对现有技术的不足，提供一种燃料电池氧还原催化剂及其制备方法，制备出的石墨烯负载Mn基改性材料燃料电池氧还原催化剂，具有高效、低价、环境友好的特点。Aiming at the deficiencies of the prior art, the present invention provides a fuel cell oxygen reduction catalyst and a preparation method thereof. The prepared graphene-supported Mn-based modified material fuel cell oxygen reduction catalyst has the characteristics of high efficiency, low price and environmental friendliness.
本发明是通过如下技术方案实现的，提供一种燃料电池氧还原催化剂，以MnO为活性中心或者以MnO和Mn2O3为活性中心。The present invention is achieved through the following technical scheme, providing a fuel cell oxygen reduction catalyst with MnO as the active center or MnO and Mn 2 O 3 as the active center.
Mn氧化物具有较好的催化氧还原性能，混合价态的氧化物中，由于不同价态的氧化物共存，从而促进了氧还原反应的电子转移，使性能得到增强，表现出更优异的性能。石墨烯负载MnO、Mn2O3混合态氧化物或MnO燃料电池氧还原催化剂，由于其具有一定的稳定性和灵活性，因此，在宏观层面上的纳米级厚度有希望被更加广泛的应用于燃料电池。Mn oxide has good catalytic oxygen reduction performance. Among oxides with mixed valence states, due to the coexistence of oxides with different valence states, the electron transfer of oxygen reduction reaction is promoted, the performance is enhanced, and the performance is more excellent. . Graphene-supported MnO, Mn 2 O 3 mixed state oxide or MnO fuel cell oxygen reduction catalyst, due to its certain stability and flexibility, is expected to be more widely used in nanoscale thickness at the macroscopic level The fuel cell.
本发明还提供一种燃料电池氧还原催化剂的制备方法，包括如下步骤：The present invention also provides a preparation method of a fuel cell oxygen reduction catalyst, comprising the following steps:
S101：制备氧化石墨烯水分散液；S101: preparing a graphene oxide aqueous dispersion;
S102：制备锰基配合物：将硫酸锰和高锰酸钾按照质量比为1:2.5的比例配成溶液，并加入30-50ml氧化石墨烯水分散液搅拌均匀，在140℃条件下反应10-12h获取沉淀物，然后将沉淀物洗涤、干燥，得到锰基配合物；S102: Preparation of manganese-based complexes: make manganese sulfate and potassium permanganate into a solution with a mass ratio of 1:2.5, add 30-50ml of graphene oxide aqueous dispersion and stir evenly, and react at 140°C for 10 -12h to obtain the precipitate, then the precipitate was washed and dried to obtain the manganese-based complex;
S103：将所述锰基配合物在550-600℃的氢气或氨气气氛下还原4h，得到燃料电池氧还原催化剂产物。S103: reducing the manganese-based complex in a hydrogen or ammonia atmosphere at 550-600° C. for 4 hours to obtain a fuel cell oxygen reduction catalyst product.
本发明提供的方法以硫酸锰和高锰酸钾为原料，负载在石墨烯上，控制比例得到锰基配合物，进而在还原气氛下（氢气或氨气）进行还原，氢气还原条件下可以得到MnO和Mn2O3混合态金属氧化物，而氨气气氛还原得到MnO化合物。通常情况下，氨气焙烧的目的是为了掺氮，而本发明则是将氨气作为还原气体；本发明与现有技术相比，制备MnO的原始物料不同，制备出的MnO和Mn2O3混合态金属氧化物以及MnO，均为棒状结构，且能与石墨烯紧密结合。The method provided by the invention uses manganese sulfate and potassium permanganate as raw materials, loads them on graphene, controls the ratio to obtain manganese-based complexes, and then reduces them in a reducing atmosphere (hydrogen or ammonia), and can obtain MnO and Mn 2 O 3 mixed state metal oxides, and ammonia atmosphere reduction to obtain MnO compounds. Normally, the purpose of ammonia roasting is to dope nitrogen, but the present invention uses ammonia as a reducing gas; compared with the prior art, the present invention has different raw materials for preparing MnO, and the prepared MnO and Mn2O 3 Mixed state metal oxides and MnO are both rod-like structures and can be tightly combined with graphene.
优选的，所述步骤S102中，获取沉淀物的方法为：将拌均匀的混合物，加入反应釜中，然后将反应釜放入温度设定为140℃的烘箱中反应10-12h。作为最佳，反应时间为12h。Preferably, in the step S102, the method for obtaining the precipitate is: adding the evenly mixed mixture into the reaction kettle, and then putting the reaction kettle into an oven set at 140° C. for 10-12 hours of reaction. As the optimum, the reaction time is 12h.
优选的，所述步骤S103中，还原气氛为氨气时，得到以MnO为活性中心的石墨烯负载Mn基改性材料燃料电池氧还原催化剂产物。Preferably, in the step S103, when the reducing atmosphere is ammonia gas, a graphene-supported Mn-based modified material fuel cell oxygen reduction catalyst product with MnO as the active center is obtained.
优选的，所述步骤S103中，还原气氛为氢气时，得到以MnO和Mn2O3为活性中心的石墨烯负载Mn基改性材料燃料电池氧还原催化剂产物。Preferably, in the step S103, when the reducing atmosphere is hydrogen, a graphene-supported Mn-based modified material fuel cell oxygen reduction catalyst product with MnO and Mn 2 O 3 as active centers is obtained.
优选的，所述步骤S101中，制备氧化石墨烯水分散液方法包括如下步骤：Preferably, in the step S101, the method for preparing an aqueous dispersion of graphene oxide comprises the following steps:
S1011：将3g石墨粉、15g高锰酸钾和114g浓硫酸在冰水浴中搅拌12h，得到棕色粘稠物；S1011: Stir 3g of graphite powder, 15g of potassium permanganate and 114g of concentrated sulfuric acid in an ice-water bath for 12 hours to obtain a brown sticky substance;
此处的浓硫酸是有效质量，即纯浓硫酸的质量，例如，如果用浓度为98%、密度为1.836g/cm3的浓硫酸则需要加入约64ml。The concentrated sulfuric acid here is the effective mass, i.e. the quality of pure concentrated sulfuric acid, for example, if the concentrated sulfuric acid with a concentration of 98% and a density of 1.836g/ cm3 needs to add about 64ml.
S1012：将所述棕色粘稠物加入200mL超纯水中，然后滴加15mL浓度为30%的双氧水，在30℃下搅拌30min后进行离心洗涤，得到氧化石墨烯水分散液。S1012: Add the brown viscous substance into 200mL of ultrapure water, then dropwise add 15mL of 30% hydrogen peroxide, stir at 30°C for 30min, and perform centrifugal washing to obtain a graphene oxide 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。Add hydrogen peroxide to clean the impurity ions in the brown viscous matter, and then use a centrifuge to separate 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 (that is, the brown viscous matter). Or wash during centrifugation.
优选的，所述步骤S1012中，离心洗涤的条件为：转速9000r/min，离心洗涤6次，每次5min。Preferably, in the step S1012, the conditions of centrifugal washing are as follows: rotating speed 9000r/min, centrifugal washing 6 times, 5 min each time.
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5min。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 the second time and centrifuge for 5min, after stopping the centrifuge, only the precipitate remains in the centrifuge, then add solvent to the obtained precipitate, and then centrifuge for the third time Turn on the centrifuge, and so on, for six times of centrifugation and washing, each centrifugation for 5 minutes.
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:
本发明提供一种燃料电池氧还原催化剂及其制备方法，所述方法包括氧化石墨烯水分散液的制备、锰基配合物的制备以及不同气体氛围下高温焙烧得到不同产物，本发明的方法所用原料廉价易得，操作简便快捷，能耗小，对设备无特殊要求，附加环境污染少，通过控制锰基氧化态种类表现出极佳的氧还原催化性能，在燃料电池领域有着良好的应用前景。并且，本发明制备的产物中，MnO和Mn2O3混合态金属氧化物以及MnO，均为棒状结构，能与石墨烯紧密结合，且比表面积大，电催化效率高。The invention provides a fuel cell oxygen reduction catalyst and a preparation method thereof. The method includes the preparation of a graphene oxide aqueous dispersion, the preparation of a manganese-based complex, and high-temperature roasting in different gas atmospheres to obtain different products. The method used in the present invention The raw materials are cheap and easy to obtain, the operation is simple and fast, the energy consumption is small, there is no special requirement for the equipment, and there is little additional environmental pollution. By controlling the oxidation state of manganese, it shows excellent oxygen reduction catalytic performance, and has a good application prospect in the field of fuel cells. . Moreover, in the products prepared by the present invention, MnO and Mn 2 O 3 mixed state metal oxides and MnO are all rod-shaped structures, can be closely combined with graphene, and have a large specific surface area and high electrocatalytic efficiency.
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为本发明实施例提供的一种燃料电池氧还原催化剂的制备方法的流程示意图。Fig. 1 is a schematic flow chart of a method for preparing an oxygen reduction catalyst for a fuel cell provided by an embodiment of the present invention.
图2为本发明实施例1制备的一种石墨烯负载Mn基改性材料燃料电池氧还原催化剂的X射线衍射图谱。Fig. 2 is an X-ray diffraction pattern of a graphene-supported Mn-based modified material fuel cell oxygen reduction catalyst prepared in Example 1 of the present invention.
图3为本发明实施例1制备的一种石墨烯负载Mn基改性材料燃料电池氧还原催化剂的扫描电镜图。3 is a scanning electron microscope image of a graphene-supported Mn-based modified material fuel cell oxygen reduction catalyst prepared in Example 1 of the present invention.
图4为本发明实施例1制备的一种石墨烯负载Mn基改性材料燃料电池氧还原催化剂在0.1MKOH溶液中不同扫速（5、10、20、50、100mVs-1）下的循环伏安曲线图（CV曲线）。Figure 4 shows the cyclic volts of a graphene-supported Mn-based modified material fuel cell oxygen reduction catalyst prepared in Example 1 of the present invention at different sweep rates (5, 10, 20, 50, 100 mVs -1 ) in 0.1M KOH solution Safety curve diagram (CV curve).
图5本发明实施例1制备的一种石墨烯负载Mn基改性材料燃料电池氧还原催化剂在氧气饱和的0.1mol•L-1KOH溶液中的旋转圆盘曲线图。Fig. 5 is a rotating disc curve of a graphene-supported Mn-based modified material fuel cell oxygen reduction catalyst prepared in Example 1 of the present invention in an oxygen-saturated 0.1 mol•L -1 KOH solution.
图6为本发明实施例2制备的一种石墨烯负载Mn基改性材料燃料电池氧还原催化剂的X射线衍射图谱。Fig. 6 is an X-ray diffraction pattern of a graphene-supported Mn-based modified material fuel cell oxygen reduction catalyst prepared in Example 2 of the present invention.
图7为本发明实施例2制备的一种石墨烯负载Mn基改性材料燃料电池氧还原催化剂的扫描电镜图。7 is a scanning electron microscope image of a graphene-supported Mn-based modified material fuel cell oxygen reduction catalyst prepared in Example 2 of the present invention.
图8为本发明实施例2制备的一种石墨烯负载Mn基改性材料燃料电池氧还原催化剂在0.1MKOH溶液中不同扫速（5、10、20、50、100mVs-1）下的循环伏安曲线图（CV曲线）。Figure 8 shows the cyclic volts of a graphene-supported Mn-based modified material fuel cell oxygen reduction catalyst prepared in Example 2 of the present invention at different sweep rates (5, 10, 20, 50, 100 mVs -1 ) in 0.1M KOH solution Safety curve diagram (CV curve).
图9为本发明实施例2制备的一种石墨烯负载Mn基改性材料燃料电池氧还原催化剂在在氧气饱和的0.1mol•L-1KOH溶液中的旋转圆盘曲线。Fig. 9 is a rotating disc curve of a graphene-supported Mn-based modified material fuel cell oxygen reduction catalyst prepared in Example 2 of the present invention in an oxygen-saturated 0.1 mol·L -1 KOH solution.
具体实施方式detailed description
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,下面将结合本发明实施例中的附图，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 will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described The embodiments are only some of the embodiments of the present invention, not all of them. 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.
参见图1，所示为本发明实施例提供的一种燃料电池氧还原催化剂的制备方法的流程示意图。下述实施例均以图1所示的方法流程为基础。Referring to FIG. 1 , it is a schematic flowchart of a method for preparing an oxygen reduction catalyst for a fuel cell provided by an embodiment of the present invention. The following embodiments are all based on the method flow shown in FIG. 1 .
首先制备氧化石墨烯水分散液，将石墨粉采用改进的Hummers法制备，制备过程如下：将3g石墨粉（325目）、15g高锰酸钾和64ml浓度为98%的浓硫酸在冰水浴中搅拌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15mL浓度为30%的双氧水，在30℃下搅拌30min，然后经过9000r/min离心洗涤6次，每次5min，离心洗涤后加入蒸馏水中，最终配成6g/L的氧化石墨烯水分散液。下述实施例均使用上述制备的的氧化石墨烯水分散液。First prepare the graphene oxide aqueous dispersion, the graphite powder is prepared by the improved Hummers method, the preparation process is as follows: 3g of graphite powder (325 mesh), 15g of potassium permanganate and 64ml of concentrated sulfuric acid with a concentration of 98% in an ice-water bath Stir for 12 hours to obtain a brown viscous substance, slowly add this brown viscous substance into 200mL ultrapure water, then slowly add 15mL of 30% hydrogen peroxide dropwise, stir at 30°C for 30min, and then centrifuge and wash at 9000r/min for 6 time, 5min each time, centrifuged and washed, added to distilled water, and finally made into a 6g/L graphene oxide aqueous dispersion. The following examples all use the graphene oxide aqueous dispersion prepared above.
实施例1Example 1
取0.2g的MnSO4·H2O、0.5g的KMnO4和30mL氧化石墨烯（6g/L）水分散液加入15mL的去离子水中搅拌均匀，将混合溶液置于50mL反应釜中，放入烘箱，将烘箱温度调至140℃保持10小时，得到沉淀物，然后将沉淀物用去离子水洗涤，洗涤后在85℃下干燥，得到锰基配合物；再将得到的锰基配合物于氢气气氛下还原，550℃焙烧4小时得到一种以MnO和Mn2O3为活性中心的石墨烯负载Mn基改性材料燃料电池氧还原催化剂，记为MnxOy-RGO催化剂，其中用RGO表示还原氧化石墨烯。Take 0.2g of MnSO 4 ·H 2 O, 0.5g of KMnO 4 and 30mL of graphene oxide (6g/L) water dispersion, add 15mL of deionized water and stir evenly, put the mixed solution in a 50mL reaction kettle, put Oven, adjust the temperature of the oven to 140°C for 10 hours to obtain a precipitate, then wash the precipitate with deionized water, and dry it at 85°C after washing to obtain a manganese-based complex; then place the obtained manganese-based complex in Reduction under hydrogen atmosphere, calcination at 550°C for 4 hours to obtain a graphene-supported Mn-based modified material fuel cell oxygen reduction catalyst with MnO and Mn 2 O 3 as active centers, denoted as Mn x O y -RGO catalyst, in which RGO stands for reduced graphene oxide.
参见图2，所示为本实施例提供的方法制备的一种石墨烯负载Mn基改性材料燃料电池氧还原催化剂的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MnO和Mn2O3，由于石墨烯为单层结构，所以图2中无石墨烯的特征衍射峰。Referring to Fig. 2, shown is the X-ray diffraction spectrum of a kind of graphene-loaded Mn-based modified material fuel cell oxygen reduction catalyst prepared by the method provided in this embodiment, the substance loaded on the graphene can be obtained as MnO through Jade software analysis and Mn 2 O 3 , since graphene has a single-layer structure, there is no characteristic diffraction peak of graphene in Fig. 2 .
参见图3，所示为本实施例提供的方法制备的一种石墨烯负载Mn基改性材料燃料电池氧还原催化剂的扫描电镜图，由图3可知，制得的混合价态氧化物MnO和Mn2O3均为棒状结构，平均粒径为4μm，有利于氧还原反应的进行。Referring to Fig. 3, it shows a scanning electron microscope image of a kind of graphene-loaded Mn-based modified material fuel cell oxygen reduction catalyst prepared by the method provided in this example. As can be seen from Fig. 3, the prepared mixed valence oxide MnO and Mn 2 O 3 has a rod-like structure with an average particle size of 4 μm, which is beneficial to the oxygen reduction reaction.
将本实施例制得的催化剂按如下方法进行性能测试，得到如图4所示的循环伏安曲线图和图5所示的旋转圆盘曲线图：The catalyst prepared by the present embodiment is tested for performance as follows, and the cyclic voltammetry curve as shown in Figure 4 and the rotating disk curve as shown in Figure 5 are obtained:
将MnxOy-RGO催化剂修饰到电极上。测试前将玻碳电极（直径3mm）经过如下步骤进行处理：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。The MnxOy-RGO catalyst was modified onto the electrode. Before the test, the glassy carbon electrode (3mm in diameter) 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 air.
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。The preparation of the working electrode is as follows: take 5 mg of catalyst, add 450 μL of ultrapure water, add 50 μL of Nafion solution with a mass fraction of 5%, ultrasonically disperse for 1 hour, take 5 μL of the above catalyst solution on the glassy carbon electrode with a micropipette, and place it in the air 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.
参见图4，所示为本实施例提供的方法制备的一种石墨烯负载Mn基改性材料燃料电池氧还原催化剂在0.1M的KOH溶液中不同扫速（5、10、20、50、100mVs-1）下的循环伏安曲线图（CV曲线）。由图4可知，扫描时，MnxOy-RGO在-0.2V附近开始出峰，峰位置为-0.2V到-0.4V，电流密度峰值为-0.9mAcm-2。Referring to Fig. 4, it is shown that a kind of graphene-loaded Mn-based modified material fuel cell oxygen reduction catalyst prepared by the method provided in this embodiment has different scan rates (5, 10, 20, 50, 100mVs) in 0.1M KOH solution -1 ) under the cyclic voltammetry plot (CV curve). It can be seen from Figure 4 that during scanning, Mn x O y -RGO begins to peak around -0.2V, the peak position is from -0.2V to -0.4V, and the peak current density is -0.9mAcm -2 .
具体条件如下：用CHI660d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/HgO电极和Pt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: the electrochemical properties were tested with CHI660d electrochemical workstation (Shanghai Chenhua Instrument Co., Ltd.), the prepared catalyst was coated on the glassy carbon electrode as the working electrode, and the Hg/HgO electrode and the Pt electrode were used as the reference Electrodes and auxiliary electrodes were tested in 0.1M potassium hydroxide solution to obtain cyclic voltammograms (CV diagrams).
参见图5，所示为本实施例提供的方法制备的一种石墨烯负载Mn基改性材料燃料电池氧还原催化剂在氧气饱和的0.1mol•L-1KOH溶液中的旋转圆盘曲线图，计算得出对于催化剂MnxOy-RGO在-0.45、-0.47、-0.49、-0.5V处转移电子数n分别为3.22、3.39、3.43、3.45。Referring to Fig. 5, it is shown that a graphene-loaded Mn-based modified material fuel cell oxygen reduction catalyst prepared by the method provided in this example is a rotating disk curve in an oxygen-saturated 0.1mol L -1 KOH solution, It is calculated that the number n of transferred electrons at -0.45, -0.47, -0.49, -0.5V for the catalyst Mn x O y -RGO is 3.22, 3.39, 3.43, 3.45, respectively.
实施例2Example 2
取0.2g的MnSO4·H2O、0.5g的KMnO4和50mL氧化石墨烯水分散液（6g/L）加入15mL的去离子水中搅拌均匀，将混合溶液置于50mL反应釜中，放入烘箱，在140℃下保持12小时，获得沉淀物，然后将沉淀物洗涤，再在80℃下干燥，得到锰基配合物；将得到的锰基配合物于氨气气氛下600℃焙烧4小时，得到一种以MnO为活性中心的石墨烯负载Mn基改性材料燃料电池氧还原催化剂，记为MnO-RGO催化剂，其中用RGO表示还原氧化石墨烯。Take 0.2g of MnSO 4 ·H 2 O, 0.5g of KMnO 4 and 50mL of graphene oxide aqueous dispersion (6g/L) into 15mL of deionized water and stir evenly, put the mixed solution in a 50mL reaction kettle, put Oven, keep at 140°C for 12 hours to obtain a precipitate, then wash the precipitate, and then dry at 80°C to obtain a manganese-based complex; roast the obtained manganese-based complex at 600°C under an ammonia atmosphere for 4 hours , to obtain a graphene-supported Mn-based modified material fuel cell oxygen reduction catalyst with MnO as the active center, denoted as MnO-RGO catalyst, where RGO represents reduced graphene oxide.
参见图6，所示为本实施例提供的方法制备出的石墨烯负载Mn基改性材料燃料电池氧还原催化剂的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MnO，由于石墨烯为单层，所以XRD无法得到衍射峰。Referring to Fig. 6, it shows the X-ray diffraction pattern of the graphene-loaded Mn-based modified material fuel cell oxygen reduction catalyst prepared by the method provided in this example. After analysis by Jade software, it can be obtained that the substance loaded on the graphene is MnO, Since graphene is a single layer, no diffraction peaks can be obtained by XRD.
参见图7，所示为本实施例提供的方法制备出的石墨烯负载Mn基改性材料燃料电池氧还原催化剂的扫描电镜图，观察图7可知，MnO为大部分为棒状结构,平均粒径为4μm，从图中可以看出石墨烯呈单层状附着在MnO上。Referring to Figure 7, it shows the scanning electron microscope image of the graphene-loaded Mn-based modified material fuel cell oxygen reduction catalyst prepared by the method provided in this example. It can be seen from Figure 7 that most of MnO is a rod-shaped structure, and the average particle diameter is It can be seen from the figure that graphene is attached to MnO in a single layer.
将本实施例制得的催化剂按如下方法进行性能测试，得到如图8所示的循环伏安曲线图和图9所示的旋转圆盘曲线图：：The catalyst prepared by the present embodiment is tested for performance as follows, and the cyclic voltammetry curve as shown in Figure 8 and the rotating disk curve as shown in Figure 9 are obtained:
将MnO-RGO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。The MnO-RGO catalyst was modified onto the electrode. Before the test, the glassy carbon electrode (3mm in diameter) 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.
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。The preparation of the working electrode is as follows: take 5 mg of catalyst, add 450 μL of ultrapure water, add 50 μL of Nafion solution with a mass fraction of 5%, ultrasonically disperse for 1 hour, take 5 μL of the above catalyst solution on the glassy carbon electrode with a micropipette, and place it in the air 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.
参见图8，所示为本实施例提供的方法制备出的石墨烯负载Mn基改性材料燃料电池氧还原催化剂在0.1M的KOH溶液中不同扫速（5、10、20、50、100mVs-1）下的循环伏安曲线图（CV曲线）。扫描时，MnO-RGO催化剂在-0.3V附近开始出峰，峰位置为-0.3V到-0.5V，电流密度峰值为-0.6mAcm-2。Referring to Fig. 8, it is shown that the graphene-supported Mn-based modified material fuel cell oxygen reduction catalyst prepared by the method provided in this example has different scan rates (5, 10, 20, 50, 100 mVs - 1 ) The cyclic voltammetry curve (CV curve) below. When scanning, the MnO-RGO catalyst began to peak around -0.3V, the peak position was from -0.3V to -0.5V, and the peak current density was -0.6mAcm -2 .
具体条件如下：用CHI660d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/HgO电极和Pt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: the electrochemical properties were tested with CHI660d electrochemical workstation (Shanghai Chenhua Instrument Co., Ltd.), the prepared catalyst was coated on the glassy carbon electrode as the working electrode, and the Hg/HgO electrode and the Pt electrode were used as the reference Electrodes and auxiliary electrodes were tested in 0.1M potassium hydroxide solution to obtain cyclic voltammograms (CV diagrams).
参见图9，所示为本实施例的方法制备出的石墨烯负载Mn基改性材料燃料电池氧还原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MnO-RGO在-0.45、-0.47、-0.49、-0.5V处转移电子数n分别为2.00、2.09、2.18、2.19。Referring to Figure 9, it shows the rotating disk curve of the graphene-supported Mn-based modified material fuel cell oxygen reduction catalyst prepared by the method of this embodiment in an oxygen-saturated 0.1mol L -1 KOH solution, calculated For the catalyst MnO-RGO at -0.45, -0.47, -0.49, -0.5V, the number n of transferred electrons is 2.00, 2.09, 2.18, 2.19, respectively.
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；以上实施例及附图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 above embodiments and drawings are only used to illustrate that the technical solutions of the present invention are not is a limitation of the present invention, and 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, Neither addition nor replacement deviates 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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