WO2022021617A1 - 一种核壳催化剂后处理方法和系统 - Google Patents

一种核壳催化剂后处理方法和系统 Download PDF

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WO2022021617A1
WO2022021617A1 PCT/CN2020/121822 CN2020121822W WO2022021617A1 WO 2022021617 A1 WO2022021617 A1 WO 2022021617A1 CN 2020121822 W CN2020121822 W CN 2020121822W WO 2022021617 A1 WO2022021617 A1 WO 2022021617A1
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core
shell catalyst
post
platinum
reaction
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French (fr)
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邵敏华
武希文
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广州市香港科大霍英东研究院
香港科技大学
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Priority to US17/282,033 priority Critical patent/US20230147818A1/en
Priority to JP2022546647A priority patent/JP7426679B2/ja
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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
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
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    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—
    • B01J35/397—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/12—Oxidising
    • B01J37/14—Oxidising with gases containing free oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • H—ELECTRICITY
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    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8853—Electrodeposition
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    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • 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

Definitions

  • the present invention relates to the field of fuel cell materials, in particular to a core-shell catalyst post-processing method and system.
  • a proton exchange membrane fuel cell is an energy supply device that uses small molecular fuel (such as hydrogen, methanol, etc.) and oxygen as reactants, and electrochemical reactions occur in membrane electrodes to generate electricity.
  • small molecular fuel such as hydrogen, methanol, etc.
  • oxygen as reactants
  • electrochemical reactions occur in membrane electrodes to generate electricity.
  • fuel cell the proton exchange membrane fuel cell (PEMFC) using hydrogen as fuel is referred to as fuel cell for short.
  • Cathode electrochemical reactions (oxygen reduction reactions) in fuel cells have slow kinetics and require large amounts of catalysts for device practicality.
  • a core-shell catalyst is a catalyst with a non-platinum metal (such as palladium) or compound (such as titanium nitride) as the core and a single layer or several layers of platinum as the outer shell.
  • the electron and stretching effects of the core material on the platinum atoms in the shell can improve the ORR catalytic activity of the platinum shell.
  • the cathodic protection of the platinum shell by the core material can also reduce the corrosion and dissolution of the platinum shell, inhibit the agglomeration of catalyst particles, and prolong the battery life.
  • palladium or palladium alloys such as palladium cobalt, palladium nickel
  • PGMs platinum group metals
  • the post-treatment of the core-shell catalyst by a chemical method or an electrochemical method can dissolve part of the palladium core and repair the defects of the platinum shell, thereby effectively reducing the amount of palladium in the core-shell catalyst.
  • the dissolved palladium ions can be recovered, purified and reused to further reduce the cost of the catalyst.
  • the core-shell catalysts currently prepared in small batches have the PGM mass activity obtained by the membrane electrode single cell test method mostly less than 0.35A/mg, although this value is more mature than the current technology.
  • Commercial platinum-carbon catalysts are high, but considering the cost of fuel cell vehicles, it is still difficult to achieve large-scale industrialization.
  • the PGM (platinum group metal) mass activity of the catalyst must be further improved.
  • Post-treatment of the core-shell catalyst is one of the methods to improve the PGM mass activity. The desired effect of post-treatment is to be achieved.
  • the current chemical post-treatment method is mostly to use ferric nitrate or ferric chloride in combination with potassium bromide to etch the palladium nucleus in a heated (80-100 °C) oxidizing atmosphere, and the effect of etching is particularly important for the concentration of iron ions It is so sensitive that it is difficult to control, and it is easy to destroy the core-shell structure and morphology, which leads to the attenuation of the catalyst activity.
  • the complicated parameter control of potassium bromide or other additive concentrations and reaction temperature requires additional reactors and reaction steps for the synthesis reaction of core-shell catalysts.
  • this post-processing method using iron ions as an etchant is difficult to achieve reliable batch preparation of high-activity core-shell catalysts.
  • the electrochemical post-treatment method utilizes potential cycling (square wave, triangular wave) to partially dissolve the palladium core and repair the pinholes of the platinum shell.
  • Most of the electrochemical post-treatment methods require the core-shell catalyst to be made into an electrode first, and then connected to an electrochemical workstation for potential cycling under the perchloric acid electrolyte and an oxidizing atmosphere.
  • This treatment method also requires additional reactors and reaction steps, and it is difficult to precisely control the potential during large-scale preparation, making it difficult to realize the scale-up preparation of low-cost high-quality core-shell catalysts.
  • a core-shell catalyst post-treatment method comprising the following steps: adding the core-shell catalyst to an electrolyte solution containing citric acid or ethylenediaminetetraacetic acid, feeding a gas containing oxygen into the electrolyte solution, stirring and reacting for a predetermined time, and reacting
  • the open-circuit potential was recorded during the period, and the open-circuit potential was stable at 0.90-1.0V vs. RHE when the reaction was completed;
  • the molar ratio of the citric acid or EDTA to platinum in the core-shell catalyst is 10-1000:1;
  • the volume percentage of oxygen in the oxygen-containing gas is 10-100%.
  • the adsorption of citrate or EDTA anions to metals is selective, and it tends to be adsorbed on the surface of platinum, but only weakly adsorbed on the surface of other metals (such as palladium), and the citrate is adsorbed on the surface of platinum.
  • the reaction rate of core dissolution is slow and controllable, and platinum atoms are rearranged to form a denser shell, and the core-shell structure and morphology can be maintained.
  • the platinum mass activity and PGM mass activity of the obtained core-shell catalyst are significantly improved, and the activity decay rate is small, and has good durability.
  • the post-treatment method of the invention belongs to a chemical method, can be used for the preparation of large-scale core-shell catalysts, and does not need to replace the reactor and electrolyte or add additional additives, thereby realizing reliable one-pot synthesis of high-quality core-shell catalysts.
  • the core-shell catalyst is one of a palladium-platinum-core-shell catalyst, a ruthenium-platinum-core-shell catalyst, and a palladium-alloy platinum-core-shell catalyst.
  • the molar ratio of the citric acid or EDTA to platinum in the core-shell catalyst is 50-70:1.
  • the electrolyte solution is a copper sulfate solution.
  • the oxygen-containing gas is air or pure oxygen.
  • the concentration of the citric acid or EDTA is 5-50 mM.
  • Appropriate concentrations of citric acid or EDTA (5-50 mM) can inhibit the dissolution of the platinum shell when the palladium core is dissolved.
  • concentration of citric acid or EDTA is lower than 5 mM, the protective effect on the platinum shell is very small, resulting in bare core, and the activity of the obtained catalyst is also greatly reduced.
  • the predetermined time is 6-12 hours.
  • the post-processing method further includes a purification step: after the reaction is completed, filtering, retaining the solid, washing, and drying to obtain a core-shell catalyst post-processed by dissolving the core.
  • the purification step can remove most of the citrate, and the residual citrate adsorbed on the platinum surface can be desorbed or decomposed without poisoning the catalyst after high and low potential cycling in the working environment of the fuel cell.
  • the core-shell catalyst is obtained by a copper-platinum replacement reaction.
  • the copper-platinum replacement reaction specifically includes the following steps:
  • the inert gas is argon or nitrogen.
  • the core material is nano-palladium on carbon.
  • One aspect of the present invention also provides a core-shell catalyst post-treatment system, comprising:
  • a reactor which is used to provide a reaction place for the post-processing reaction of the core-shell catalyst, and a stirrer is arranged in the reactor;
  • a gas supply device for supplying oxygen or pure oxygen to the reactor
  • the electrochemical workstation is used to record the open circuit potential of the reaction system in the reactor.
  • the above-mentioned system can realize the post-treatment of a large batch of core-shell catalysts, with high treatment efficiency, and the platinum mass activity and PGM mass activity of the treated core-shell catalyst are significantly improved.
  • the present invention has the following beneficial effects:
  • citrate or ethylenediaminetetraacetate has a protective effect on the platinum shell.
  • the reaction rate of core dissolution is slow and controllable, and at the same time, the platinum atoms are rearranged to form
  • the core-shell structure and morphology can be maintained, and the platinum mass activity and PGM mass activity of the obtained core-shell catalyst are significantly improved.
  • the platinum mass activity reaches 1.01A/mgPt, and the PGM mass activity reaches 0.48A/mgPGM.
  • the mass activity is 5 times that of the commercial platinum-carbon catalyst with mature technology; and the mass activity decay rate of the product core-shell catalyst in the aging test is only 22.3%, and the mass activity decay rate of the commercial platinum-carbon catalyst under the same conditions is 55.7%.
  • the core-shell activity after the invention has a small decay rate and good durability.
  • the system of the invention can be used for the preparation and post-treatment of large-scale core-shell catalysts, without the need to replace reactors and electrolytes or add additional additives, and realize reliable one-pot synthesis of high-quality core-shell catalysts.
  • Fig. 1 is a schematic diagram of the preparation and post-treatment reaction flow of the core-shell catalyst
  • Figure 2 shows the results of the quality activity test and aging test of the core-shell catalyst.
  • copper sulfate, potassium chloroplatinate, and citric acid were purchased from Sigma-Aldrich TM , and nano-palladium supported on carbon was provided by Tanaka Precious Metals.
  • the copper sulfate solution was rapidly added with a peristaltic pump, during which the open circuit potential was recorded with an electrochemical workstation. After the copper sulfate solution is completely added (the open circuit potential is stable at about 0.64V), the stirring is turned off to allow the nuclear material to settle naturally, and the electrochemical workstation is set to maintain a constant potential of 0.36V. During the period, after standing for 30 minutes, stir at 300 rpm for 1 minute, until the workstation records The current is stable.
  • the catalyst is subjected to suction filtration, and the filtrate is a blue color of copper sulfate aqueous solution, washed with ultrapure water for many times, and dried in vacuum to obtain a core-shell catalyst without post-processing of core dissolution.
  • the palladium/platinum mass ratio of the unpost-treated core-shell catalyst (Pd@Pt) was 1.80
  • the palladium/platinum mass ratio of the post-treated core-shell catalyst was 1.30.
  • a core-shell catalyst the preparation method and post-treatment method of which are basically the same as those in Example 1, except that in the post-treatment step of the core-shell catalyst, pure oxygen (oxygen content is 99.9992%) is introduced.
  • the palladium/platinum mass ratio of the core-shell catalyst without post-treatment was 1.80, and the palladium/platinum mass ratio of the post-treatment core-shell catalyst was 1.10.
  • the coated platinum shell without citrate Due to the lack of citric acid in the reaction system, the coated platinum shell without citrate is easily destroyed, resulting in bare core, and ultimately resulting in a significant reduction in the activity of the obtained catalyst.
  • Electrodes have faster voltage decay with service life.
  • more core palladium atoms are retained in an oxygen-free atmosphere, most of them do not participate in adjusting the ORR activity of the platinum shell, making the overall PGM mass activity of the catalyst inferior to that of the catalyst post-treated in an oxygen-containing atmosphere.
  • Example 1 The catalysts of Example 1 and Comparative Example 1 were selected, and under the same loading (anode 0.05mg/cm 2 , cathode 0.11mg/cm 2 ), the catalyst activity was tested by the membrane electrode single cell method, test conditions: hydrogen/oxygen, 80°C, 100% relative humidity, active area 5 cm 2 , 1.5 atm back pressure.
  • the platinum mass activity of the post-treated core-shell catalyst reaches 1.01A/mg Pt, and the PGM mass activity reaches 0.48A/mg PGM.
  • the platinum mass activity of d-Pd@Pt/C is five times that of commercial platinum carbon.
  • the PGM mass activity can reach the 2020 target activity of the PGM mass activity set by the U.S. Department of Energy (ie, 0.44A/mg under the membrane electrode single cell test method).
  • Example 2 For the catalyst without post-treatment (Pd@Pt/C) in Example 1, the catalyst with post-treatment (i.e. Example 2, d-Pd@Pt/C) and the commercial platinum-carbon catalyst (i.e. Comparative Example 1, Pt /C) Carry out aging test.
  • the test refers to the aging test method formulated by the US Department of Energy. The aging test conditions of single cell membrane electrode: hydrogen/nitrogen, 80°C, 100% relative humidity, active area 5cm 2 , 1.5atm back pressure, platinum load Amount of 0.1mg/cm 2 , 30,000 square wave cycles, 0.60, 0.95V constant voltage for 3 seconds.
  • the core-shell catalyst post-treatment method of the present invention can realize simple, reliable and effective gram-level batch treatment.

Abstract

一种核壳催化剂后处理方法和系统，涉及燃料电池材料领域。后处理方法包括以下步骤：将核壳催化剂加入至含有柠檬酸或乙二胺四乙酸的电解质溶液中，向电解质溶液中通入含有氧气的气体，搅拌反应预定时间，反应期间记录开路电位，反应完成时开路电位稳定在0.90～1.0V vs.RHE；所述柠檬酸或乙二胺四乙酸与核壳催化剂中的铂的摩尔比为10～1000：1；所述含有氧气的气体中氧气的体积百分数为10～100％。该后处理方法可显著提升核壳催化剂的铂质量活性和PGM质量活性，以及催化剂的耐久性。

Description

一种核壳催化剂后处理方法和系统 技术领域
本发明涉及燃料电池材料领域，特别是涉及一种核壳催化剂后处理方法和系统。
背景技术
质子交换膜燃料电池是一种以小分子燃料(例如氢气、甲醇等)和氧气为反应物，在膜电极内发生电化学反应以进行发电的供能装置。现时对车用燃料电池的研发大多聚焦在以氢气为燃料的质子交换膜燃料电池，因为与其他燃料相比其具有更高的能量密度、更简单的反应机理和快速的反应动力学。以下对以氢气为燃料的质子交换膜燃料电池(PEMFC)，简称为燃料电池。燃料电池中的阴极电化学反应(氧还原反应)动力学缓慢，需要大量催化剂以实现装置实用性。现时已商品产业化的燃料电池大多以碳载纳米铂作为电池的催化剂，因铂金属为最能够有效催化氧还原反应的元素，同时相较于其他金属，铂具有较好的抗氧化耐腐蚀性。因此以碳载纳米铂作为催化剂，可使燃料电池得以输出较大的功率密度和实现较长时间的使用寿命。但铂是贵金属，来源稀少且价格昂贵，以纳米颗粒的形式虽可提高铂催化剂的利用率，但随着在氧化性的工作环境下运行，铂纳米颗粒将逐渐团聚而使得燃料电池功率输出性能不可逆得衰减。
如何在降低燃料电池膜电极铂载量，并且保持电池输出功率密度和延长使用寿命，是现今燃料电池领域的主要研究课题。从催化剂本身着手，铂合金、核壳结构、单原子等新型催化剂相继问世，大幅提升了催化剂中单位质量铂的催化活性，为实现高性能低铂膜电极的大规模产业化向前迈进了关键一步。核壳结构催化剂是一种以非铂的金属(例如钯)或化合物(例如氮化钛)作为内核，单层或数层原子厚度的铂作为外壳的催化剂，此特殊结构可大幅提升铂原子的利用率，且内核材料对外壳铂原子造成的电子、拉伸作用可提高铂壳的ORR催化活性。内核材料对铂壳的阴极保护，亦可减少铂壳腐蚀溶解而抑制催化剂颗粒团聚，延长电池寿命。
核壳催化剂制备关键在于精确控制外壳的生长，壳层厚度和包覆均匀性将直接影响催化剂活性和耐久性。铂单原子层催化剂的制备方法最早是由美国Brookhaven National Laboratory的Adzic团队所提出，其中涉及在核材料纳米颗粒(例如钯、钌、铑、金等)表面以欠电位沉积法(UPD)生长单原子层模板(例如铅、氢、铜)，再引入铂离子使其与模板发生表面氧 化还原置换反应(SLRR)，形成铂单原子壳层。在上述反应步骤的基础上，许多提升核壳催化剂性能及放大批量制备的方法被相继提出，其中以钯或钯合金(例如钯钴、钯镍)作为核心能够有效提高铂单原子层的催化活性，但钯同样为铂族金属(PGM)来源稀少且价格昂贵。以化学法或是电化学法对核壳催化剂进行后处理，可溶解部分钯核及修补铂壳缺陷，实现有效降低核壳催化剂中的钯用量。溶解出的钯离子可回收提纯再利用，达到进一步降低催化剂成本的目的。
在以上改进核壳催化剂合成方法的研发基础上，现时以小批量制备的核壳催化剂，其以膜电极单电池测试方法得到的PGM质量活性多数小于0.35A/mg，虽然此数值比现时技术成熟商用铂碳催化剂高，但以燃料电池汽车成本为考量，仍难以实现大规模产业化。欲进一步降低燃料电池汽车内贵金属的用量，催化剂的PGM(铂族金属)质量活性必须再进一步提高，对核壳催化剂进行后处理是提高PGM质量活性的方法之一，后处理欲达成的理想效果是在部分溶解出钯核的同时保持铂壳的完整及修补针孔缺陷，如图1所示。现时的化学后处理法多是在加热(80～100℃)的氧化气氛下，以硝酸铁或氯化铁配合溴化钾对钯核进行刻蚀，其中刻蚀的效果对铁离子的浓度特别灵敏以致难以控制，容易破坏核壳结构形貌使得催化剂活性衰减，再加上对溴化钾或其他添加剂浓度、反应温度繁复的参数控制，以及需要核壳催化剂合成反应另外的反应器、反应步骤，此以铁离子为刻蚀剂的后处理法难实现可靠的高活性核壳催化剂的批量制备。电化学后处理法利用电位循环(方波、三角波)达到部分溶解钯核、修补铂壳针孔的目的。电化学后处理方法多数需要将核壳催化剂先制成电极，在高氯酸电解质配合氧化气氛下，连接电化学工作站以对其进行电位循环。此处理方法同样需要额外的反应器、反应步骤，且大批量制备时难以精确控制电位，使其难以实现低成本的优质核壳催化剂放大制备。
发明内容
基于此，有必要针对上述问题，提供一种核壳催化剂后处理方法，可实现大批量核壳催化剂后处理，经处理的核壳催化剂的铂质量活性和PGM质量活性显著提升。
一种核壳催化剂后处理方法，包括以下步骤：将核壳催化剂加入至含有柠檬酸或乙二胺四乙酸的电解质溶液中，向电解质溶液中通入含有氧气的气体，搅拌反应预定时间，反应期间记录开路电位，反应完成时开路电位稳定在0.90～1.0V vs.RHE；
所述柠檬酸或乙二胺四乙酸与核壳催化剂中的铂的摩尔比为10～1000：1；
所述含有氧气的气体中氧气的体积百分数为10～100％。
上述核壳催化剂后处理方法，柠檬酸根或乙二胺四乙酸根阴离子对金属的吸附具有选择 性，其偏向于吸附在铂表面，而仅微弱吸附在其它金属(如钯)表面，在柠檬酸根或乙二胺四乙酸根对铂壳的保护下，以酸性及氧化气氛下，核溶解反应速率缓慢可控，同时铂原子进行重排，形成更致密的壳，核壳结构形貌可得到保持，得到的核壳催化剂的铂质量活性和PGM质量活性显著提升，而且活性衰减率小，具有很好的耐久性。本发明的后处理方法属于化学方法，可用于大批量核壳催化剂制备，且不需更换反应器及电解质或额外加入添加剂，实现可靠一锅法合成优质核壳催化剂。
在其中一个实施例中，所述核壳催化剂为钯铂-核壳催化剂、钌铂-核壳催化剂、钯合金铂-核壳催化剂中的一种。
在其中一个实施例中，所述柠檬酸或乙二胺四乙酸与核壳催化剂中的铂的摩尔比为50～70：1。
在其中一个实施例中，所述电解质溶液为硫酸铜溶液。
在其中一个实施例中，所述含有氧气的气体为空气或纯氧。
在其中一个实施例中，所述柠檬酸或乙二胺四乙酸的浓度为5～50mM。合适的柠檬酸或或乙二胺四乙酸浓度(5～50mM)可在溶解钯核时抑制铂壳的溶解。柠檬酸或乙二胺四乙酸的浓度低于5mM时，对铂壳的保护作用非常小，导致核心裸露，得到的催化剂的活性也会大幅度降低。
在其中一个实施例中，所述预定时间为6～12h。
在其中一个实施例中，所述后处理方法还包括净化步骤：反应完成后，过滤，保留固体，清洗，干燥，即得经核溶解后处理的核壳催化剂。净化步骤可移除大部分的柠檬酸根，残余吸附在铂表面的柠檬酸根在燃料电池工作环境下高低电位循环后可脱附或分解，而不会对催化剂产生毒化。
在其中一个实施例中，所述核壳催化剂通过铜铂置换反应得到。
在其中一个实施例中，所述铜铂置换反应具体包括以下步骤：
S1、将核材料加入反应器中，加水混合，加入硫酸溶液，开启搅拌，通入惰性气体除去反应器内的氧气，通入氢气，脱附核材料表面吸附的杂质，通入惰性气体除去氢气，通过氧气或空气使嵌入晶格内的氢脱出，通入惰性气体去除溶液中的溶氧；
S2、持续通入惰性气体，停止搅拌，待核材料沉降后，进行电位CV扫描，每静置20～40min开启搅拌10～70s，停止搅拌，待核材料沉降后，继续进行电位CV扫描，直到CV曲线稳定；
S3、向反应器中加入硫酸铜溶液，期间记录开路电位，硫酸铜溶液加入完毕，停止搅拌，待材料沉降后，进行恒电位控制，每静置20～40min开启搅拌10～70s，直到记录的电流稳定；
S4、配制含有铂离子、柠檬酸、硫酸的前驱体溶液，通入惰性气体，得铂前驱体溶液， 待恒电位步骤结束，停止电位控制，开启搅拌，滴加铂前驱体溶液进行铜铂置换反应，置换反应完成，过滤，保留固体，清洗，干燥，即得未经核溶解后处理的核壳催化剂。
在其中一个实施例中，所述惰性气体为氩气或氮气。
在其中一个实施例中，所述核材料为碳载纳米钯。
本发明一方面还提供一种核壳催化剂后处理系统，包括：
反应器，用于为核壳催化剂后处理反应提供反应场所，所述反应器内设有搅拌器；
供气装置，用于为反应器提供氧气或纯氧；
电化学工作站，用于记录反应器内反应体系的开路电位。
上述系统能实现大批量核壳催化剂后处理，处理效率高，经处理的核壳催化剂的铂质量活性和PGM质量活性显著提升。
与现有技术相比，本发明具有以下有益效果：
本发明的核壳催化剂后处理方法，柠檬酸根或乙二胺四乙酸根对铂壳具有保护作用，在酸性和氧化气氛围下，核溶解反应速率缓慢可控，同时铂原子进行重排，形成更致密的壳，核壳结构形貌可得到保持，得到的核壳催化剂的铂质量活性和PGM质量活性显著提升，铂质量活性达到1.01A/mgPt，PGM质量活性达到0.48A/mgPGM，其中铂质量活性是现时技术成熟商用铂碳催化剂活性的5倍；而且在衰老测试中产品核壳催化剂质量活性衰减率仅为22.3％，相同条件测试下商用铂碳质量活性衰减率为55.7％，说明本发明处理后的核壳活性衰减率小，具有很好的耐久性。
本发明的系统，可用于大批量核壳催化剂制备和后处理，且不需更换反应器及电解质或额外加入添加剂，实现可靠一锅法合成优质核壳催化剂。
附图说明
图1为核壳催化剂制备和后处理反应流程示意图；
图2为核壳催化剂质量活性测试和衰老测试结果。
具体实施方式
为了便于理解本发明，以下将给出较佳实施例对本发明进行更全面的描述。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人 员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。
以下实施例中，硫酸铜、氯铂酸钾、柠檬酸均购买自Sigma-Aldrich TM，碳载纳米钯由田中贵金属公司提供。
实施例1
一、制备核壳催化剂
(1)将1000mg碳载纳米钯置入玻璃瓶中，加入适量超纯水混合，倒入反应器内，用硫酸溶液润洗玻璃瓶，倒入反应器内，直到反应器内硫酸溶液浓度为50mM，总体积为600mL。在反应器内通入氩气30min，除去氧气，再通入氢气大约40min，使钯核表面吸附的杂质脱附，随后通氩气30min，除去溶液中溶氧。各通气步骤器件皆以300rpm搅拌悬浮液。此步骤完成后，反应器内保持通氩气或氮气直至铜铂置换反应结束。
(2)关闭搅拌使核材料自然沉降，设置电化学工作站进行电位CV扫描(0.36～0.45V vs.RHE可逆氢电极，5mV/s扫速，以下所有电位皆以RHE为参照)，期间每静置30min后以300rpm搅拌1min，直到工作站记录的CV曲线稳定。此步骤是以外加电力除去核材料表面杂质和氧化物，通常需要2h，搅拌4次以上。CV扫描步骤结束前1h，配制硫酸铜溶液，其浓度按加入后反应器内铜离子浓度50mM计算。以蠕动泵快速加入硫酸铜溶液，期间以电化学工作站记录开路电位。完全加入硫酸铜溶液后(开路电位约稳定在0.64V)，关闭搅拌使核材料自然沉降，设置电化学工作站进行恒电位保持0.36V，期间每静置30min后以300rpm搅拌1min，直到工作站记录的电流稳定。
(3)配制含有铂离子浓度约4～10mM、柠檬酸约0.2M、硫酸50mM的前驱体溶液，通氩气30min。恒电位步骤结束时，停止工作站电位控制，开启400rpm搅拌，以蠕动泵慢速滴加入铂前驱体溶液进行铜铂置换反应，期间以电化学工作站记录开路电位。开路电位随铂离子的加入逐渐上升，滴加完铂前驱体溶液后维持搅拌40min，确保置换反应完成。
(4)反应结束，对催化剂进行抽滤，滤液为硫酸铜水溶液的蓝色，以超纯水多次清洗，真空干燥，得到未经核溶解后处理的核壳催化剂。
二、核壳催化剂后处理
(1)铜铂置换反应完成后，在含有柠檬酸(柠檬酸：铂的摩尔比约60：1)的电解质溶液中通入空气，柠檬酸的浓度为40mM，搅拌12h，期间以电化学工作站记录开路电位，反应完成时开路电位稳定在0.97V vs.RHE。
(2)反应完成后，真空抽滤，滤液为黄绿色，保留固体，以超纯水多次清洗，真空干燥，即得经核溶解后处理的核壳催化剂。
本实施例中，未经后处理核壳催化剂(Pd@Pt)的钯/铂质量比为1.80，经后处理的核壳催化剂的钯/铂质量比为1.30。
实施例2
一种核壳催化剂，其制备方法和后处理方法与实施例1基本相同，区别在于核壳催化剂后处理步骤中，通入的是纯氧(氧气含量为99.9992％)。
本实施例中，未经后处理核壳催化剂(Pd@Pt)的钯/铂质量比为1.80，经后处理的核壳催化剂的钯/铂质量比为1.10。
对比例1
商业铂碳催化剂，由燃料电池催化剂研发制造商田中贵金属公司提供。
对比例2
一种核壳催化剂，其制备方法和后处理方法与实施例1基本相同，区别在于核壳催化剂后处理步骤中，电解质溶液中未添加柠檬酸。
由于反应体系中缺少柠檬酸，没有柠檬酸根的包覆铂壳容易被破坏，导致核心裸露，最终导致得到的催化剂活性大幅降低。
对比例3
一种核壳催化剂，其制备方法和后处理方法与实施例1基本相同，区别在于核壳催化剂后处理步骤中，不通入含有氧气的气体，而通入氩气。
在此反应条件下铂壳未经重整，表面的针孔缺陷未得到修补，导致铂壳包覆不全、部分核心裸露，催化剂稳定性不如经含氧气氛后处理的催化剂，体现在燃料电池膜电极随使用寿命更快速的电压衰减。另外，由于在无氧气氛下保留更多核心钯原子，其中大部分并未参与调整铂壳ORR活性，使得催化剂整体PGM质量活性不如经含氧气氛后处理的催化剂。
实验例1
选取实施例1和对比例1的催化剂，在同样的载量下(阳极0.05mg/cm 2，阴极0.11mg/cm 2)，以膜电极单电池法测试催化剂活性，测试条件：氢气/氧气，80℃，100％相对湿度，活性面积5cm 2，1.5atm背压。
经后处理的核壳催化剂(d-Pd@Pt/C)的铂质量活性达到1.01A/mg Pt，PGM质量活性达到0.48A/mg PGM。d-Pd@Pt/C的铂质量活性是商业铂碳的5倍。PGM质量活性可以达到美国能源部制定的PGM质量活性2020年目标活性(即膜电极单电池测试方法下达到0.44A/mg)。
实验例2
对实施例1中未经后处理的催化剂(Pd@Pt/C)、经后处理的催化剂(即实施例2，d-Pd@Pt/C)以及商用铂碳催化剂(即对比例1，Pt/C)进行衰老测试，测试参照美国能源部制定的衰老测试方法，单电池膜电极衰老测试条件：氢气/氮气，80℃，100％相对湿度，活性面积5cm 2，1.5atm背压，铂载量0.1mg/cm 2，3万圈方波循环，0.60、0.95V恒电压保持3秒。测试结果如图2所示，Pd@Pt/C质量活性衰减率为50.0％，Pt/C质量活性衰减率为55.7％，而经本发明后处理方法处理过的催化剂d-Pd@Pt/C质量活性衰减率仅为22.3％。而且，在衰老测试任何阶段d-Pd@Pt/C的PGM活性都明显大于商业铂碳的PGM活性。
综合以上，本发明的核壳催化剂后处理方法可实现简单、可靠、有效的克级批量处理。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (10)

  1. 一种核壳催化剂后处理方法，其特征在于，包括以下步骤：将核壳催化剂加入至含有柠檬酸或乙二胺四乙酸的电解质溶液中，向电解质溶液中通入含有氧气的气体，搅拌反应预定时间，反应期间记录开路电位，反应完成时开路电位稳定在0.90～1.0V vs.RHE；
    所述柠檬酸或乙二胺四乙酸与核壳催化剂中的铂的摩尔比为10～1000：1；
    所述含有氧气的气体中氧气的体积百分数为10～100％。
  2. 根据权利要求1所述的核壳催化剂后处理方法，其特征在于，所述核壳催化剂为钯铂-核壳催化剂、钌铂-核壳催化剂、钯合金铂-核壳催化剂中的一种。
  3. 根据权利要求1所述的核壳催化剂后处理方法，其特征在于，所述电解质溶液为硫酸铜溶液；所述含有氧气的气体为空气或纯氧。
  4. 根据权利要求1所述的核壳催化剂后处理方法，其特征在于，所述柠檬酸或乙二胺四乙酸的浓度为5～50mM。
  5. 根据权利要求1所述的核壳催化剂后处理方法，其特征在于，所述预定时间为6～12h。
  6. 根据权利要求1所述的核壳催化剂后处理方法，其特征在于，所述后处理方法还包括净化步骤：反应完成后，过滤，保留固体，清洗，干燥，即得经核溶解后处理的核壳催化剂。
  7. 根据权利要求1～6任一项所述的核壳催化剂后处理方法，其特征在于，所述核壳催化剂通过铜铂置换反应得到。
  8. 根据权利要求7所述的核壳催化剂后处理方法，其特征在于，所述铜铂置换反应具体包括以下步骤：
    S1、将核材料加入反应器中，加水混合，加入硫酸溶液，开启搅拌，通入惰性气体除去反应器内的氧气，通入氢气，脱附核材料表面吸附的杂质，通入惰性气体除去氢气，通过氧气或空气使嵌入晶格内的氢脱出，通入惰性气体去除溶液中的溶氧；
    S2、持续通入惰性气体，停止搅拌，待核材料沉降后，进行电位CV扫描，每静置20～40min开启搅拌10～70s，停止搅拌，待核材料沉降后，继续进行电位CV扫描，直到CV曲线稳定；
    S3、向反应器中加入硫酸铜溶液，期间记录开路电位，硫酸铜溶液加入完毕，停止搅拌，待材料沉降后，进行恒电位控制，每静置20～40min开启搅拌10～70s，直到记录的电流稳定；
    S4、配制含有铂离子、柠檬酸、硫酸的前驱体溶液，通入惰性气体，得铂前驱体溶液，待恒电位步骤结束，停止电位控制，开启搅拌，滴加铂前驱体溶液进行铜铂置换反应，置换反应完成，过滤，保留固体，清洗，干燥，即得未经核溶解后处理的核壳催化剂。
  9. 根据权利要求8所述的核壳催化剂后处理方法，其特征在于，所述核材料为碳载纳米钯。
  10. 一种核壳催化剂后处理系统，其特征在于，包括：
    反应器，用于为核壳催化剂后处理反应提供反应场所，所述反应器内设有搅拌器；
    供气装置，用于为反应器提供氧气或纯氧；
    电化学工作站，用于记录反应器内反应体系的开路电位。
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