CN114122429B - Application of nitrogen-doped carbon material as carbon carrier of platinum-carbon catalyst in hydrogen fuel cell - Google Patents

Application of nitrogen-doped carbon material as carbon carrier of platinum-carbon catalyst in hydrogen fuel cell Download PDF

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CN114122429B
CN114122429B CN202010877409.7A CN202010877409A CN114122429B CN 114122429 B CN114122429 B CN 114122429B CN 202010877409 A CN202010877409 A CN 202010877409A CN 114122429 B CN114122429 B CN 114122429B
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nitrogen
carbon
carbon material
doped
platinum
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CN114122429A (en
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赵红
荣峻峰
谢南宏
彭茜
顾贤睿
王厚朋
张家康
顾方伟
杜泽学
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to KR1020237010563A priority patent/KR20230058142A/en
Priority to EP21860474.2A priority patent/EP4207394A1/en
Priority to JP2023513711A priority patent/JP2023539876A/en
Priority to PCT/CN2021/114752 priority patent/WO2022042640A1/en
Priority to US18/043,310 priority patent/US20230369609A1/en
Priority to TW110131840A priority patent/TW202218746A/en
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • 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

Abstract

The invention relates to a nitrogen-doped carbon material, a preparation method and application thereof, wherein the material has only one characteristic peak of nitrogen in XPS analysis. The nitrogen-doped carbon material provided by the invention is used as a carrier of a platinum-carbon catalyst, and can be used for obviously improving the mass specific activity and the stability of the platinum-carbon catalyst.

Description

Application of nitrogen-doped carbon material as carbon carrier of platinum-carbon catalyst in hydrogen fuel cell
Technical Field
The invention relates to an application of a nitrogen-doped carbon material as a carbon carrier of a platinum-carbon catalyst in a hydrogen fuel cell.
Background
The carbon material has wide sources and rich properties, and is widely used in various technical fields. In the chemical field, carbon materials are both important supports and commonly used catalysts. The bonding mode of the carbon element is rich, and the carbon material can be modified in various modes so as to obtain better performance.
Oxygen Reduction Reactions (ORR) are key reactions in the electrochemical field, such as in fuel cells and metal-air cells, and are a major factor affecting cell performance. Many materials are available for catalyzing the oxygen reduction reaction, but few are practical. The carbon material doped with atoms can be directly used as a catalyst for oxygen reduction reaction, and the charge distribution of the carbon material can be changed through doping of hetero atoms, so that more active sites are created. Although exhibiting better activity in some of the results of the studies, such catalysts are far from commercial applications. On one hand, the combination mode of hetero atoms and carbon materials and the catalysis mechanism thereof are not fully known in the field; on the other hand, there are various ways of combining the heteroatom with the carbon material, so how to control the way of combining the heteroatom with the carbon material is a difficulty in doping the atom. In addition, such catalysts are generally not suitable for use in acidic environments, particularly Proton Exchange Membrane Fuel Cells (PEMFCs), which are important. Platinum carbon catalysts are more sophisticated oxygen reduction catalysts and are the core technology of proton exchange membrane hydrogen fuel cells. Among metals, platinum has the highest catalytic activity for oxygen reduction reaction, but platinum is expensive and resource-scarce, and is a bottleneck restricting its large-scale application.
The nitrogen element can be doped with carbon materials in various structural forms, such as pyridine nitrogen, graphite nitrogen, pyrrole nitrogen, nitrogen oxide and the like, and the carbon materials have different properties due to different doping forms. So far, there is no report of doping pyrrole-type nitrogen only on the surface of carbon material, nor is there a report of the correlation between pyrrole-type nitrogen and platinum carbon catalyst performance.
Up to now, the most effective oxygen reduction catalysts are platinum carbon catalysts, and there is an urgent need in the art to greatly improve the catalytic activity and stability thereof in order to promote large-scale commercial application thereof. Many factors and complications affect the activity and stability of the platinum carbon catalyst, and some documents believe that the activity and stability of the platinum carbon catalyst are related to the particle size, morphology, structure of the platinum, as well as the type, nature and platinum loading of the support. The prior art mainly improves the performance of the platinum-carbon catalyst by controlling the particle size, morphology, structure and specific surface area of the carrier and pore structure of the platinum; there are also reports of modification groups attached to the carbon surface to improve the performance of platinum carbon catalysts by modifying the carbon support.
The information disclosed in the foregoing background section is only for enhancement of understanding of the background of the invention and may include information that is not already known to those of ordinary skill in the art.
Disclosure of Invention
A first object of the present invention is to provide a nitrogen-doped carbon material, wherein the surface of the carbon material, nitrogen is substantially bound to the carbon material in the form of pyrrole nitrogen. A second object of the present invention is to provide a carbon material suitable for use as a platinum carbon catalyst support. A third object of the invention is to provide a carbon material suitable for use as a high platinum-carrying platinum-carbon catalyst support.
In order to achieve the above object, the present invention provides the following technical solutions.
1. In N1s spectrum peak of XPS analysis, there is no other characteristic peak between 395ev and 405ev except the characteristic peak between 399ev and 400.5 ev.
2. The nitrogen-doped carbon material according to the above-mentioned aspect is characterized in that the mass fraction of nitrogen in XPS analysis of the nitrogen-doped carbon material is 0.1% to 10%, preferably 0.2% to 5%, more preferably 0.4% to 1.5%.
3. The nitrogen-doped carbon material according to any one of the above, wherein the oxygen mass fraction in XPS analysis of the nitrogen-doped carbon material is >4%, preferably 4% to 15%.
4. The nitrogen-doped carbon material according to any one of the preceding claims, characterized in that the resistivity of the nitrogen-doped carbon material is <10Ω -m, preferably <5Ω -m, more preferably <3Ω -m.
5. The nitrogen-doped carbon material according to any one of the preceding claims, wherein the specific surface area of the nitrogen-doped carbon material is 10m 2 /g～2000m 2 /g。
6. The nitrogen-doped carbon material according to any one of the preceding claims, wherein the nitrogen-doped carbon material is a nitrogen-doped conductive carbon black, nitrogen-doped graphene or nitrogen-doped carbon nanotube.
7. The nitrogen-doped carbon material according to any of the preceding claims, wherein the nitrogen-doped carbon material is EC-300J, EC-600JD, ECP600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
8. The carbon carrier of the platinum carbon catalyst is characterized in that the carbon carrier is nitrogen doped conductive carbon black, and in N1s spectrum peaks analyzed by XPS, no other characteristic peaks exist between 395ev and 405ev except for characteristic peaks between 399ev and 400.5 ev; in XPS analysis, the oxygen mass fraction is 4-15%, and the nitrogen mass fraction is 0.2-5%; its specific surface area is 200m 2 /g～2000m 2 /g。
9. The carbon support according to the foregoing, wherein the conductive carbon Black is EC-300J, EC-600JD, ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLASK 40B2.
10. The carbon support according to any one of the above, wherein the mass fraction of nitrogen in XPS analysis is 0.4% to 1.5%.
11. A method for preparing a nitrogen-doped carbon material, comprising:
(1) A step of impregnating a nitrogen source: mixing and impregnating a carbon material with a nitrogen source aqueous solution to obtain a carbon material impregnated with a nitrogen source;
(2) The method comprises the steps of: heating the carbon material impregnated with the nitrogen source obtained in the step (1) to 1000-1500 ℃ at a speed of 8-15 ℃ per minute in inert gas, and then performing constant temperature treatment for 0.5-10 h.
12. The process according to the above (2), wherein the temperature of the constant temperature treatment is 1150 to 1450 ℃.
13. The process according to any one of the above (2), wherein the constant temperature treatment is carried out for a period of 1 to 5 hours.
14. The preparation method according to any one of the preceding claims, characterized in that the nitrogen source is ammonia and/or urea.
15. The production method according to any one of the preceding claims, characterized in that the mass ratio of the carbon material to the nitrogen source is 30, based on the mass of the nitrogen contained therein: 1 to 1:2; preferably 25:1 to 1:1.5.
16. the preparation method is characterized in that the carbon material is conductive carbon black, graphene or carbon nano tube.
17. The preparation method is characterized in that the carbon material is EC-300J, EC-600JD, ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
18. The method according to any one of the above methods, wherein the carbon material has an oxygen mass fraction of more than 4%, preferably 4% to 15% in XPS analysis.
19. The method according to any one of the above methods, wherein the carbon material has a resistivity of <10Ω·m, preferably <5Ω·m, and more preferably <2Ω·m.
20. The process according to any one of the preceding claims, characterized in that the specific surface area of the carbon material is 10m 2 /g～2000m 2 /g; the pore volume is 0.02 mL/g-6 mL/g.
21. The process according to any one of the preceding processes, wherein the carbon material has a specific surface area of 200m 2 /g～2000m 2 /g; the pore volume is 0.2 mL/g-3 mL/g.
22. The use of any of the foregoing nitrogen-doped carbon materials or carbon supports as electrode materials in electrochemistry.
23. A fuel cell wherein any of the aforementioned nitrogen-doped carbon materials or carbon supports are used.
24. The fuel cell of claim 23, wherein the fuel cell is a hydrogen fuel cell.
25. A metal-air battery wherein any of the aforementioned nitrogen-doped carbon materials or carbon supports are used.
26. The metal-air battery of claim 25, wherein the metal-air battery is a lithium-air battery.
The hetero atoms and the carbon materials have various combination modes, the doping method and the raw materials and the operation steps and conditions of the doping process are different, the combination modes of the hetero atoms and the carbon materials can be influenced, the property differences of the hetero atoms and the carbon materials are caused, and the functions of the hetero atoms and the carbon materials are changed. How to control the way heteroatoms are bound to carbon materials is a difficulty in the art when doping atoms. If the manner in which the heteroatoms are bound to the carbon material can be controlled is more unique, it is possible to produce a carbon material having more uniform properties of the doping sites, which may make it more suitable for a particular application. The inventor of the application has found through diligent research that a novel nitrogen-doped carbon material can be obtained by adopting a specific method, and only pyrrole-type nitrogen is doped on the surface of the carbon material. Further research has also found that some of the carbon materials of the present invention are particularly suitable as supports for platinum carbon catalysts for hydrogen fuel cells.
Compared with the prior art, the invention can realize the following beneficial technical effects.
1. The invention can control the combination mode of nitrogen and carbon material, and a new material which is doped with one form of nitrogen, namely pyrrole nitrogen, on the surface of the carbon material is manufactured by a simple method.
2. The carbon materials of the invention are particularly suitable for being used as carriers of platinum-carbon catalysts, and can obviously improve the mass specific activity and the stability of the platinum-carbon catalysts.
3. Some of the carbon materials of the present invention can produce high platinum loading platinum carbon catalysts with good performance.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
Fig. 1 is an XPS spectrum of the nitrogen-doped carbon material of example 1.
Fig. 2 is an XPS spectrum of the platinum carbon catalyst of example 1.
Fig. 3 is a polarization curve before and after 5000 turns of the platinum carbon catalyst of example 1.
Fig. 4 is an XPS spectrum of the nitrogen-doped carbon material of example 2.
Fig. 5 is an XPS spectrum of the nitrogen-doped carbon material of example 3.
Fig. 6 is an XPS spectrum of the nitrogen-doped carbon material of example 4.
Fig. 7 is a polarization curve of the platinum carbon catalyst of comparative example 1.
Fig. 8 is a polarization curve of the platinum carbon catalyst of comparative example 2 before and after 5000 turns.
Description of the embodiments
The invention is described in detail below in connection with the embodiments, but it should be noted that the scope of the invention is not limited by these embodiments and the principle explanation, but is defined by the claims.
In the present invention, any matters or matters not mentioned are directly applicable to those known in the art without modification except for those explicitly stated. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are all considered as part of the original disclosure or original description of the present invention, and should not be considered as new matters not disclosed or contemplated herein unless such combination would obviously be unreasonable to one skilled in the art.
All of the features disclosed in this invention may be combined in any combination which is known or described in the present invention and should be interpreted as specifically disclosed and described in the present invention unless the combination is obviously unreasonable by those skilled in the art. The numerical points disclosed in the present specification include not only the numerical points specifically disclosed in the embodiments but also the end points of each numerical range in the specification, and any combination of these numerical points should be considered as a disclosed or described range of the present invention.
Technical and scientific terms used in the present invention are defined to have their meanings, and are not defined to have their ordinary meanings in the art.
The "doping element" in the present invention means nitrogen, sulfur, phosphorus, boron, fluorine, chlorine, bromine and iodine.
In the present invention, other references to "carbon material" refer to carbon material that does not contain a doping element, except that it may be explicitly "carbon material that contains a doping element" depending on the context or definition itself; the same is true of the underlying concept of carbon materials.
In the present invention, "carbon black" and "carbon black" are interchangeable terms of art.
The "inert gas" in the present invention refers to a gas that does not have any appreciable effect on the properties of the nitrogen-doped carbon material in the preparation method of the present invention.
In the present invention, other references to "pore volume" refer to the total pore volume of single point adsorption at maximum P/P0, except where the context or definition itself may dictate.
The invention provides a nitrogen-doped carbon material, wherein in N1s spectrum peak analyzed by XPS, no other characteristic peak is arranged between 395ev and 405ev except for the characteristic peak between 399ev and 400.5ev
The nitrogen-doped carbon material according to the present invention does not contain other doping elements than nitrogen.
The nitrogen-doped carbon material according to the present invention is free of metal elements.
The nitrogen-doped carbon material according to the present invention is not particularly limited in its oxygen content.
The nitrogen-doped carbon material according to the present invention has a nitrogen mass fraction of 0.1% to 10%, preferably 0.2% to 5%, more preferably 0.4% to 1.5% in XPS analysis.
The nitrogen-doped carbon material according to the invention has a resistivity of <10.0 Ω.m, preferably <5.0 Ω.m, more preferably <3.0 Ω.m.
The nitrogen-doped carbon material according to the invention can vary over a wide range in specific surface area, for example 10m 2 /g～2000m 2 And/g. The pore volume of the nitrogen-doped carbon material may be 0.02mL/g to 6.0mL/g.
The nitrogen-doped carbon material according to the present invention may be a nitrogen-doped conductive carbon black, nitrogen-doped graphene or nitrogen-doped carbon nanotube.
The nitrogen-doped carbon material according to the present invention, the conductive carbon black may be a general conductive carbon black (Conductive Blacks), a super conductive carbon black (Super Conductive Blacks) or a special conductive carbon black (Extra Conductive Blacks), for example, the conductive carbon black may be one or more of Ketjen black series super conductive carbon black, cabot series conductive carbon black and series conductive carbon black manufactured by wining dezaocys company; preferably Ketjen Black EC-300J, ketjen Black EC-600JD, ketjen Black ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
According to the nitrogen-doped carbon material of the invention, the preparation method and the source of the conductive carbon black are not limited. The conductive carbon black can be acetylene black, furnace black and the like.
According to the nitrogen-doped carbon material, the graphene or the carbon nanotube can be graphene or carbon nanotube which is not subjected to oxidation treatment or graphene or carbon nanotube which is subjected to oxidation treatment.
A carbon carrier of a platinum carbon catalyst, wherein the carbon carrier is nitrogen doped conductive carbon black, and in N1s spectrum peaks analyzed by XPS, no other characteristic peaks exist between 395ev and 405ev except for characteristic peaks between 399ev and 400.5 ev; in XPS analysis, the oxygen mass fraction is 4-15%, and the nitrogen mass fraction is 0.2-5%; its specific surface area is 200m 2 /g～2000m 2 /g。
The carbon support according to the present invention does not contain other doping elements than nitrogen.
The carbon support according to the present invention, which is free of metal elements.
The carbon support according to the invention has a resistivity <10.0 Ω.m, preferably <5.0 Ω.m, more preferably <3.0 Ω.m.
The carbon support according to the present invention may be a general conductive carbon black (Conductive Blacks), a super conductive carbon black (Super Conductive Blacks) or a special conductive carbon black (Extra Conductive Blacks), for example, the conductive carbon black may be one or more of Ketjen black series super conductive carbon black, cabot series conductive carbon black and series conductive carbon black produced by wining dezasie corporation; preferably Ketjen Black EC-300J, ketjen Black EC-600JD, ketjen Black ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
The carbon support according to the present invention is not limited in the production method and source of the conductive carbon black. The conductive carbon black can be acetylene black, furnace black and the like.
A method for preparing a nitrogen-doped carbon material, comprising:
(1) A step of impregnating a nitrogen source: mixing and impregnating a carbon material with a nitrogen source aqueous solution to obtain a carbon material impregnated with a nitrogen source;
(2) The method comprises the steps of: heating the carbon material impregnated with the nitrogen source obtained in the step (1) to 1000-1500 ℃ at a speed of 8-15 ℃ per minute in inert gas, and then performing constant temperature treatment for 0.5-10 h.
According to the preparation method of the nitrogen-doped carbon material, the temperature of the constant temperature treatment is preferably 1150-1450 ℃, and the time of the constant temperature treatment is preferably 1-5 h.
According to the preparation method of the nitrogen-doped carbon material, the nitrogen source can be ammonia water and/or urea.
According to the preparation method of the nitrogen-doped carbon material, the mass ratio of the carbon material to the nitrogen source is 30:1 to 1:2; preferably 25:1 to 1:1.5.
according to the preparation method of the nitrogen-doped carbon material, the carbon material can be conductive carbon black, graphene or carbon nano tube.
According to the preparation method of the nitrogen-doped carbon material, the graphene or the carbon nanotube can be graphene or carbon nanotube which is not subjected to oxidation treatment or graphene or carbon nanotube which is subjected to oxidation treatment.
According to the preparation method of the nitrogen-doped carbon material, the conductive carbon black can be common conductive carbon black (Conductive Blacks), super conductive carbon black (Super Conductive Blacks) or special conductive carbon black (Extra Conductive Blacks), for example, the conductive carbon black can be one or more of Ketjen black series super conductive carbon black, cabot series conductive carbon black and series conductive carbon black produced by Yingchangzhucai company; preferably EC-300J, EC-600JD, ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
According to the preparation method of the nitrogen-doped carbon material, the preparation method and the source of the conductive carbon black are not limited. The conductive carbon black can be acetylene black, furnace black and the like.
According to the method for preparing the nitrogen-doped carbon material of the present invention, the ID/IG value of the conductive carbon black is generally 0.8 to 5, preferably 1 to 4. In the Raman spectrum, the peak located near 1320cm-1 is the D peak, the peak located near 1580cm-1 is the G peak, ID represents the intensity of the D peak, and IG represents the intensity of the G peak.
According to the preparation method of the nitrogen-doped carbon material, in XPS analysis of the conductive carbon black, the mass fraction of oxygen is more than 4%, and preferably 4% -15%.
According to the method for preparing the nitrogen-doped carbon material, the resistivity of the conductive carbon black is less than 10.0 omega-m, preferably less than 5.0 omega-m, more preferably less than 2.0 omega-m.
According to the method for preparing the nitrogen-doped carbon material of the present invention, the specific surface area of the carbon material in (1) may be 10m2/g to 2000m2/g. The pore volume of the carbon material may be 0.02mL/g to 6mL/g.
According to the preparation method of the nitrogen-doped carbon material, in one embodiment, the carbon material is mixed with a nitrogen source aqueous solution, soaked (generally for 12-72 h), dried (generally for 70-120 ℃) and then placed in a tube furnace, the tube furnace is heated (the heating rate can be 8-15 ℃/min) under the protection of inert gas, and then the nitrogen-doped carbon material is obtained after constant temperature treatment for a period of time (can be 0.5-10 h, preferably 1-5 h) at high temperature (can be 1000-1500 ℃, preferably 1150-1450 ℃).
In the method for producing a nitrogen-doped carbon material of the present invention, a metal-containing catalyst is not used.
The invention also provides a nitrogen-doped carbon material produced by any of the methods described above.
The invention also provides an application of the nitrogen-doped carbon material or the carbon carrier as an electrode material in electrochemistry.
A fuel cell wherein any of the foregoing nitrogen-doped carbon materials or carbon supports are used in the fuel cell. According to the foregoing fuel cell, the fuel cell is preferably a hydrogen fuel cell.
A metal-air battery wherein any of the foregoing nitrogen-doped carbon materials or carbon supports are used in the metal-air battery. According to the foregoing metal-air battery, the metal-air battery is preferably a lithium-air battery.
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way.
Reagents, instruments and tests
Unless otherwise specified, all reagents used in the present invention are analytically pure and commercially available.
The analysis and test in the invention are all carried out by the following instruments and methods.
The invention detects the elements on the surface of the material by an X-ray photoelectron spectroscopy (XPS). The X-ray photoelectron spectroscopy analyzer used was an ESCALab220i-XL type radiation electron spectroscopy manufactured by VG scientific company and equipped with Avantage V5.926 software, and the X-ray photoelectron spectroscopy analysis test conditions were: the excitation source was monochromatized A1K alpha X-rays with a power of 330W and a base vacuum of 3X 10-9mbar at the analytical test. In addition, the electron binding energy was corrected by the C1s peak (284.3 eV) of elemental carbon, and the post-peak splitting treatment software was XPSPEAK.
Instrument and method for elemental analysis, conditions: elemental analyzer (Vario EL Cube), reaction temperature 1150 ℃, 5mg of sample, reduction temperature 850 ℃, carrier gas helium flow rate 200mL/min, oxygen flow rate 30 mL/min, and oxygen introduction time 70s.
The model of the high-resolution transmission electron microscope (HRTEM) adopted by the invention is JEM-2100 (HRTEM) (Japanese electronics Co., ltd.) and the test conditions of the high-resolution transmission electron microscope are as follows: the acceleration voltage was 200 kV. The particle size of the nano particles in the sample is measured by an electron microscope picture.
BET test method: in the present invention, the pore structure properties of the sample were determined by a Quantachrome AS-6B type analyzer, and the specific surface area and pore volume of the catalyst were obtained by the Brunauer-Emmett-Taller (BET) method.
The Raman detection of the invention adopts a LabRAM HR UV-NIR laser confocal Raman spectrometer manufactured by HORIBA company of Japan, and the laser wavelength is 532nm.
Electrochemical performance testing, instrument models Solartron analytical EnergyLab and Princeton Applied Research (Model 636A), methods and test conditions: the catalyst polarization curve LSV was tested in 0.1M HClO4 saturated with O2 at 1600rpm and CV curve was tested in 0.1M HClO4 under Ar atmosphere, thereby calculating the electrochemical active area ECSA. After 5000 cycles of scanning in 0.1M HClO4 saturated with O2 in the range of 0.6V to 0.95V at the time of stability test, LSV and ECSA were tested as described above. The catalyst is prepared into slurry which is uniformly dispersed during the test, and the slurry is coated on a glassy carbon electrode with the diameter of 5mm, wherein the platinum content of the catalyst on the electrode is 3-4 mug.
Resistivity test four-probe resistivity tester, instrument model KDY-1, method and test conditions: the applied pressure was 3.9.+ -. 0.03 MPa and the current was 500.+ -. 0.1mA.
VXC72 (Vulcan XC72, manufactured by cabot corporation, usa) is available from energy technologies limited in wing Long, su. The test by the instrument method shows that: the specific surface area is 258m2/g, the pore volume is 0.388mL/g, the oxygen mass fraction is 8.72%, the ID/IG is 1.02, and the resistivity is 1.22 Ω.m.
Ketjenback ECP600JD (Ketjen Black, manufactured by Lion corporation, japan) was purchased from Suzhou wing Long energy technologies Co. The test by the instrument method shows that: the specific surface area is 1362m2/g, the pore volume is 2.29mL/g, the oxygen mass fraction is 6.9%, the ID/IG is 1.25, and the resistivity is 1.31 Ω.m.
Commercial platinum carbon catalyst (trade name HISPEC4000, manufactured by Johnson Matthey Co.) was purchased from Alfa Aesar. The test results show that: the mass fraction of platinum was 40.2%.
Example 1
This example illustrates the preparation of a nitrogen-doped carbon support of the present invention.
1g Vulcan XC72 is immersed in 20mL of 2.5wt% ammonia water solution for 24h; drying in an oven at 100 ℃; then placing the mixture into a tube furnace, heating the tube furnace to 1100 ℃ at a speed of 8 ℃/min, and carrying out constant temperature treatment for 3 hours; and naturally cooling to obtain the nitrogen-doped carbon carrier, wherein the number of the nitrogen-doped carbon carrier is the carbon carrier A.
Dispersing the carbon carrier A in deionized water according to the proportion of 250mL of water used per gram of carbon carrier, adding 3.4mmol of chloroplatinic acid per gram of carbon carrier, performing ultrasonic dispersion to form suspension, and adding 1 mol/L of sodium carbonate aqueous solution to enable the pH value of the system to be 10; heating the suspension to 80 ℃, adding formic acid under stirring to perform reduction reaction, wherein the molar ratio of the formic acid to the chloroplatinic acid is 50:1, and continuously maintaining the reaction for 10 hours; filtering the reacted mixture, washing the mixture with deionized water until the pH value of the filtrate is neutral, filtering the mixture, and drying the mixture at 100 ℃ to obtain the platinum-carbon catalyst.
Sample characterization and testing
1. Carbon support
The mass fraction of nitrogen analyzed by XPS is 1.43%; the mass fraction of oxygen analyzed by XPS was 9.31%; the specific surface area is 239 m2/g; the resistivity was 1.28. Omega. M.
Fig. 1 is an XPS spectrum of the nitrogen-doped carbon material of example 1.
2. Platinum carbon catalyst
The platinum mass fraction of the platinum carbon catalyst was 39.7%.
The half-wave potential was 0.92v.
Fig. 2 is an XPS spectrum of the platinum carbon catalyst of example 1.
Fig. 3 is a polarization curve before and after 5000 turns of the platinum carbon catalyst of example 1.
Example 2
This example illustrates the preparation of a nitrogen-doped carbon support of the present invention.
1g Vulcan XC72 is immersed in 15mL of 0.7wt% urea aqueous solution for 24h; drying in an oven at 100 ℃; then placing the mixture into a tube furnace, heating the tube furnace to 1200 ℃ at a speed of 10 ℃/min, and carrying out constant temperature treatment for 3 hours; and naturally cooling to obtain the nitrogen-doped carbon carrier, wherein the number of the nitrogen-doped carbon carrier is the carbon carrier B.
Sample characterization and testing
The mass fraction of nitrogen analyzed by XPS is 0.68%; the mass fraction of oxygen analyzed by XPS is 8.92%; the resistivity was 1.25. Omega. M.
Fig. 4 is an XPS spectrum of the nitrogen-doped carbon material of example 2.
Example 3
This example illustrates the preparation of a nitrogen-doped carbon support of the present invention.
10mL of absolute ethanol was added to 1g Ketjenblack ECP600JD, followed by 25mL of 10wt% aqueous ammonia solution for 24h; drying in an oven at 100 ℃; then placing the mixture into a tube furnace, heating the tube furnace to 1100 ℃ at a speed of 8 ℃/min, and carrying out constant temperature treatment for 3 hours; naturally cooling to obtain the nitrogen-doped carbon carrier, wherein the number of the nitrogen-doped carbon carrier is C.
Sample characterization and testing
The mass fraction of nitrogen analyzed by XPS is 1.48%; the mass fraction of oxygen analyzed by XPS is 11.22%; the specific surface area is 1369m2/g; the resistivity was 1.36. Omega. M.
Fig. 5 is an XPS spectrum of the nitrogen-doped carbon material of example 3.
Example 4
This example illustrates the preparation of a nitrogen-doped carbon support of the present invention.
10mL of absolute ethanol was added to 1g Ketjenblack ECP600JD, followed by 20mL of 1wt% aqueous urea solution for 24 hours; drying in an oven at 100 ℃; then placing the mixture into a tube furnace, heating the tube furnace to 1300 ℃ at a speed of 10 ℃/min, and carrying out constant temperature treatment for 3 hours; and naturally cooling to obtain the nitrogen-doped carbon carrier, wherein the number of the nitrogen-doped carbon carrier is the carbon carrier D.
Sample characterization and testing
The mass fraction of nitrogen analyzed by XPS is 1.31%; the mass fraction of oxygen analyzed by XPS was 9.54%; the resistivity was 1.34. Omega. M.
Fig. 6 is an XPS spectrum of the nitrogen-doped carbon material of example 4.
Comparative example 1
A platinum carbon catalyst was prepared according to the method in example 1, except that: the vector is Vulcan XC72.
Sample characterization and testing
The platinum mass fraction of the platinum carbon catalyst was 40.2%.
The half-wave potential was 0.89v.
Fig. 7 is a polarization curve of the platinum carbon catalyst of comparative example 1.
Comparative example 2
The platinum carbon catalyst is a commercially available catalyst, under the trade designation HISPEC4000.
Sample characterization and testing
The platinum mass fraction of the platinum carbon catalyst was 40.2%.
The half-wave potential was 0.88v.
Fig. 8 is a polarization curve of the platinum carbon catalyst of comparative example 2 before and after 5000 turns.

Claims (6)

1. The application of nitrogen-doped carbon material as carbon carrier of platinum carbon catalyst in hydrogen fuel cell is characterized by that the described nitrogen-doped carbon material is nitrogen-doped conductive carbon black, and in its XPS analyzed N 1s In the spectrum peak, no other characteristic peak is arranged between 395ev and 405ev except for the characteristic peak between 399ev and 400.5 ev; in XPS analysis, the oxygen mass fraction is 4-15%, and the nitrogen mass fraction is 0.2-5%; its specific surface area is 200m 2 /g～2000m 2 /g；
The nitrogen-doped carbon material is prepared by the following method:
(1) A step of impregnating a nitrogen source: mixing and impregnating a carbon material with a nitrogen source aqueous solution to obtain a carbon material impregnated with a nitrogen source; the nitrogen source is ammonia water; the carbon material is conductive carbon black;
(2) The method comprises the steps of: heating the carbon material impregnated with the nitrogen source obtained in the step (1) to 1150-1500 ℃ at a speed of 8-15 ℃ per minute in inert gas, and then performing constant temperature treatment for 0.5-10 h.
2. The use according to claim 1, wherein in (2) the temperature of the thermostatic treatment is 1150 ℃ to 1450 ℃.
3. The use according to claim 1, wherein the conductive carbon Black is EC-300J, EC-600JD, ECP600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
4. Use according to claim 1, characterized in that the resistivity of the nitrogen-doped carbon material is <10Ω -m.
5. The use according to claim 1, wherein in (1), the mass ratio of the carbon material to the nitrogen source, based on the mass of the nitrogen contained therein, is 30:1 to 1:2.
6. the use according to claim 5, wherein in (1), the mass ratio of the carbon material to the nitrogen source, based on the mass of the nitrogen contained therein, is 25:1 to 1:1.5.
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