CN115611274A - Method for quickly graphitizing porous carbon material and application thereof - Google Patents
Method for quickly graphitizing porous carbon material and application thereof Download PDFInfo
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- CN115611274A CN115611274A CN202211118755.2A CN202211118755A CN115611274A CN 115611274 A CN115611274 A CN 115611274A CN 202211118755 A CN202211118755 A CN 202211118755A CN 115611274 A CN115611274 A CN 115611274A
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- chloride
- joule heating
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000010438 heat treatment Methods 0.000 claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 238000005087 graphitization Methods 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000000446 fuel Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000004108 freeze drying Methods 0.000 claims description 12
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 3
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000003837 high-temperature calcination Methods 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 25
- 229910021385 hard carbon Inorganic materials 0.000 description 19
- 239000012300 argon atmosphere Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 229910000765 intermetallic Inorganic materials 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 238000002791 soaking Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229940032296 ferric chloride Drugs 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229960001939 zinc chloride Drugs 0.000 description 1
Images
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- 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
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- 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
- H01M4/921—Alloys or mixtures with metallic elements
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a method for rapidly graphitizing a porous carbon material and application thereof. The method comprises the steps of mixing a graphitization catalyst solution with a porous carbon material, and drying after ultrasonic treatment; carrying out ultra-fast Joule heating on the dried mixed material; and (3) carrying out acid washing on the mixed material subjected to the ultra-fast Joule heating to obtain the graphitized carbon material. The preparation process disclosed by the invention is simple and convenient to operate and rapid in reaction, compared with high-temperature calcination in a tubular furnace, the temperature rise and reduction time can be obviously shortened, the energy saving and the production efficiency improvement are facilitated, the pore collapse of the carbon material caused by long-time calcination is avoided, the high specific surface area of the carbon material is reserved, meanwhile, the temperature required by graphitization can be effectively reduced due to the catalytic graphitization effect of the catalyst, the highly graphitized carbon material can be obtained at a low temperature, and the obtained graphitized carbon with the high specific surface area has excellent corrosion resistance in a high potential test of a fuel cell.
Description
Technical Field
The invention relates to the technical field of new energy materials, in particular to a method for quickly graphitizing a porous carbon material and application thereof.
Background
The excellent characteristics of high energy conversion efficiency and zero pollution emission (water is a product) of a Proton Exchange Membrane Fuel Cell (PEMFC) make the PEMFC become one of important new energy technologies in the 21 st century. Since most of the catalysts used in fuel cells are platinum and platinum-based alloy catalysts, carbon materials are generally used as carriers for dispersion of the catalysts in order to make the catalysts sufficiently usable. However, the carbon carrier can cause severe carbon corrosion when the fuel cell is started, stopped and operated for a long time in actual operation, so that platinum and platinum-based alloy particles loaded on the carbon carrier are agglomerated, the electrochemical active area is reduced, the performance of the fuel cell is reduced, and the better the performance of the catalyst loaded on the carbon carrier is, the more severe the carbon corrosion is. The graphitized carbon carrier can effectively relieve the carbon corrosion phenomenon caused by the start-stop process of the fuel cell. However, most of the carbon prepared by us is hard carbon, and the graphitization degree needs to be improved. High-temperature calcination is the most commonly used graphitization method, however, the high graphitization usually requires a temperature as high as 2300 ℃, and the heating and cooling process is required, which takes a long time, as in chinese patent 202111243337.1. The method is simple to operate, quick in reaction, capable of greatly shortening preparation time, preventing excessive decomposition morphology collapse of a skeleton of the porous carbon material, effectively reserving high specific surface area of the porous carbon material, and realizing graphitization at low temperature.
Disclosure of Invention
The invention aims to rapidly and efficiently improve the graphitization degree of a porous carbon carrier and improve the carbon corrosion resistance of the porous carbon carrier. Meanwhile, the graphitization degree of the porous carbon carrier is improved, and the porous structure of the porous carbon carrier is kept, so that the porous structure of the porous carbon carrier can be used for reducing the time-limited-domain catalyst at high temperature, the agglomeration of the catalyst is prevented, and the dispersion of the catalyst is facilitated.
In order to overcome the defects that the prior art needs high temperature higher than 2000 ℃, needs long time for heating and cooling, and is easy to collapse a porous structure, the invention aims to provide a method for rapidly graphitizing a porous carbon material and application thereof (relieving carbon corrosion of a fuel cell).
The object of the present invention is achieved by the following means.
A method for rapidly graphitizing a porous carbon material comprises the following steps:
(1) Mixing a graphite catalyst solution with a porous carbon material, and drying after ultrasonic treatment (the graphite catalyst is fully adsorbed in the carbon material);
(2) Carrying out ultra-fast Joule heating on the dried mixed material obtained in the step (1);
(3) And (3) carrying out acid cleaning (metal particles generated by etching reaction) on the mixed material subjected to the ultra-fast Joule heating in the step (2) to obtain the graphitized porous carbon material.
Preferably, in the step (1), the solvent of the graphitization catalyst solution is water or an organic solvent; further preferably, the organic solvent is ethanol or isopropanol.
Preferably, the graphitization catalyst in the step (1) is a metal salt or boric acid; further preferably, the metal salt is at least one of cobalt chloride, manganese chloride, ferric chloride, nickel chloride, copper chloride, zinc chloride, ferric nitrate, cobalt nitrate, nickel nitrate, manganese nitrate, copper nitrate, ferric acetate, nickel acetate, cobalt acetylacetonate and ferric acetylacetonate;
preferably, the concentration of the graphitization catalyst solution in the step (1) is 0.3-5g/ml.
Preferably, the mass ratio of the graphitization catalyst to the porous carbon material in the step (1) is (0.5-10): 1.
Preferably, the ultrasonic time of the step (1) is 0.5-24h, and the ultrasonic power is 50-200w. The drying treatment is freeze drying or air blast drying or infrared lamp drying. The temperature of a cold well required by freeze drying is 60 ℃ below zero to 40 ℃ below zero, the freezing time is 2 to 6 hours, and the vacuumizing time is 8 to 24 hours. The temperature required by the forced air drying is 40-80 ℃, and the required time is 12-24h. The power of the infrared lamp is 50-100w, and the drying time is 12-24h.
Preferably, the porous carbon material in the step (1) is at least one of porous carbons.
Further preferably, the porous carbon material in step (1) can be commercial carbon black such as XC-72, BP2000, ketjen black, etc., and can also be at least one of porous carbon in hollow carbon spheres, bowl-shaped carbon, porous hard carbon, biomass-derived carbon, MOF-derived carbon;
preferably, the porous carbon material in the step (1) is in a block shape or a powder shape; the porous carbon material is powdery, and the mixed solution containing the graphite catalyst and the porous carbon material is added into a support carrier device for ultrafast Joule heating after being dried. The material of the support carrier device can be carbon paper, carbon cloth, graphite paper and the like.
Preferably, in the step (2), the voltage for the ultra-fast joule heating is 10-40V, the current is 10A-60A, and the heating time is 20s-10min; the ultra-rapid joule heating is performed in an inert gas atmosphere.
Further preferably, in the step (2), the voltage for the ultra-fast joule heating is 20-40V, the current is 20A-50A, and the heating time is 20s-100s; the inert gas is argon.
Preferably, in the step (3), the acid for acid washing is at least one of dilute sulfuric acid, dilute nitric acid, dilute hydrochloric acid and dilute acetic acid, and the concentration is 0.3-4mol/L; the pickling time is 6-24h, and the pickling temperature can be 30-80 ℃.
The graphitized carbon material obtained by the method is applied to the preparation of a fuel cell catalyst.
Preferably, the method comprises the following steps: and (2) impregnating the graphitized carbon material with chloroplatinic acid and a non-noble metal salt solution (wherein the concentration of the chloroplatinic acid is 0.193 mol/L), and performing freeze drying and annealing reduction on the high-temperature hydrogen-argon mixed gas to obtain the carbon-supported platinum-based catalyst of the fuel cell. The high-temperature annealing temperature is 500-900 ℃, and the time is 2-12h; the volume fraction of the hydrogen in the hydrogen-argon mixed gas is 5-20%.
Further preferably, the non-noble metal salt is at least one of cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetate, cobalt acetylacetonate, nickel nitrate, ferric nitrate, zinc chloride, ferric chloride, manganese chloride and chromium chloride.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, a simple, rapid and efficient Joule heating method is adopted to prepare the highly graphitized porous carbon carrier, the graphitized catalyst, the porous carbon and other carbon materials are fully impregnated, and after drying, the metal particles are removed by ultra-rapid Joule heating and acid washing, so that the highly graphitized carbon carrier is obtained. The method can be used for quickly preparing the highly graphitized carbon carrier, long-time high-temperature calcination is not needed, the reaction time is effectively shortened, the preparation efficiency is improved, and the quick temperature rise is favorable for retaining the pore structure of the carbon material, so that the porous structure of the carbon carrier can be utilized to reduce the time-limited catalyst at high temperature, the agglomeration of the catalyst is prevented, and the dispersion of the catalyst is favorable. The graphitization can be realized at low temperature through the catalytic action of the transition metal, which is beneficial to saving energy.
Drawings
Fig. 1 is a schematic view of a joule-heated support carrier device of example 1.
Fig. 2 is an XRD comparison pattern of the porous hard carbons of different graphitization degrees and the non-graphitization degree prepared in examples 4-6.
Fig. 3 is a raman comparison graph of porous hard carbons of different graphitization degrees and non-graphitized porous hard carbons prepared in examples 4-6.
FIG. 4 shows the graphitized hard carbon and untreated hard carbon supported intermetallic compound Pt prepared in example 7 3 XRD contrast pattern of Co.
FIG. 5 is the graphitized hard carbon, untreated hard carbon-supported intermetallic compound Pt prepared in example 7 3 Comparison of redox performance before and after high potential accelerated aging test of Co and JM Pt/C.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and the process parameters specifically noted may be performed with reference to conventional techniques.
Example 1
(1) Adding 1g of ferric chloride hexahydrate into 3ml of water, fully dissolving, adding 500mg of XC-72, fully soaking and ultrasonically treating for 10 hours, and freeze-drying;
(2) Putting the sample obtained in the step (1) into an ultra-fast heating supporting carrier device, as shown in figure 1. Setting constant current at 20A, voltage at 40V and time at 50s, and carrying out ultra-fast Joule heating in argon atmosphere;
(3) And (3) taking the sample subjected to Joule heating in the step (2) out of the supporting device, immersing the sample into 2M dilute hydrochloric acid solution, carrying out acid washing for 10h, then filtering, washing the sample to be neutral by deionized water, and then drying the sample at 60 ℃ to obtain the highly graphitized XC-72.
Example 2
(1) Adding 1g of iron acetate into 3ml of water, fully dissolving, adding 500mgBP2000, fully soaking and ultrasonically treating for 10 hours, and freeze-drying;
(2) Putting the sample obtained in the step (1) into an ultra-fast heating support carrier device. Setting constant current at 20A, voltage at 40V and time at 50s, and carrying out ultra-fast Joule heating in argon atmosphere;
(3) And (3) ultrasonically treating the sample subjected to Joule heating in the step (2) from a carbon support, immersing the sample into 0.5M dilute hydrochloric acid solution, carrying out acid washing for 10 hours, then filtering, washing the sample to be neutral by deionized water, and then drying the sample at 60 ℃ to obtain the highly graphitized BP2000.
Example 3
(1) Adding 1g of manganese chloride tetrahydrate into 3ml of water, fully dissolving, adding 1g of Ketjen black, fully soaking and ultrasonically treating for 10 hours, and freeze-drying;
(2) Putting the sample obtained in the step (1) into an ultra-fast heating support carrier device. Setting constant current to be 20A, voltage to be 40V and time to be 50s, and carrying out ultra-fast Joule heating in an argon atmosphere;
(3) And (3) ultrasonically treating the sample subjected to Joule heating in the step (2) from a carbon support, immersing the sample into 0.5M dilute hydrochloric acid solution, carrying out acid washing for 10 hours, filtering, washing the sample to be neutral by deionized water, and drying the sample at 60 ℃ to obtain the highly graphitized Ketjen black.
Example 4
(1) 100mg of porous hard carbon material was placed in an ultra-fast heating support carrier device. Setting constant current at 10A, voltage at 10V and time at 50s, and carrying out ultra-fast Joule heating in argon atmosphere;
(2) And (2) immersing the sample subjected to Joule heating in the step (1) into a 0.5M dilute sulfuric acid solution, carrying out acid washing for 10h, then filtering, washing with deionized water to be neutral, and then drying at 60 ℃ to obtain the treated hard carbon.
Example 5
(1) Adding 50mg of ferric chloride hexahydrate into 3ml of water, fully dissolving, adding 100mg of porous hard carbon, fully soaking and ultrasonically treating for 10 hours, and freeze-drying;
(2) Putting the sample obtained in the step (1) into an ultra-fast heating support carrier device. Setting constant current to be 10A, voltage to be 10V and time to be 50s, and carrying out ultra-fast Joule heating in an argon atmosphere;
(3) And (3) immersing the sample subjected to Joule heating in the step (2) into a 0.5M dilute sulfuric acid solution, carrying out acid washing for 10 hours, then filtering, washing to be neutral by using deionized water, and then drying at 60 ℃ to obtain the treated hard carbon.
Example 6
(1) Adding 100mg of ferric chloride hexahydrate into 3ml of water, fully dissolving, adding 100mg of porous hard carbon, fully soaking and ultrasonically treating for 10 hours, and freeze-drying;
(2) Putting the sample obtained in the step (1) into an ultra-fast heating support carrier device. Setting constant current at 20A, voltage at 40V and time at 50s, and carrying out ultra-fast Joule heating in argon atmosphere;
(3) And (3) immersing the sample subjected to Joule heating in the step (2) into a 0.5M dilute sulfuric acid solution, carrying out acid washing for 10h, then filtering, washing to be neutral by using deionized water, and then drying at 60 ℃ to obtain the highly graphitized porous hard carbon.
Fig. 2 is an XRD comparison pattern of hard carbon of different graphitization degree and non-graphitization degree prepared in example 4, example 5, and example 6. Fig. 3 is a raman comparison graph of porous hard carbons with different graphitization degrees and non-graphitization porous hard carbons prepared in example 4, example 5, and example 6.
As can be seen from fig. 2, the diffraction angle of the (002) crystal plane of the untreated hard carbon is about 25 degrees, and is a relatively wide large-bump diffraction peak, which indicates that the diffraction angle is amorphous carbon, and the hard carbon after graphitization has a strong diffraction peak near 26.2 degrees, which indicates that the material has undergone significant graphitization. Meanwhile, as can be seen from the raman chart of fig. 3, id/Ig =0.6 of the hard carbon obtained in example 6 after graphitization indicates that the order degree of the carbon material is increased and the graphitization degree is enhanced. And the hard carbon which is not graphitized Id/Ig =1.03, has higher defect degree and lower graphitization degree.
Example 7
(1) Adding 2g of ferric chloride hexahydrate into 3ml of water, fully dissolving, adding 2g of porous hard carbon, fully soaking and ultrasonically treating for 10 hours, and freeze-drying;
(2) Putting the sample obtained in the step (1) into an ultra-fast heating support carrier device. Setting constant current at 20A, voltage at 40V and time at 50s, and carrying out ultra-fast Joule heating in argon atmosphere;
(3) And (3) taking out the sample subjected to joule heating in the step (2), immersing the sample in 0.5M dilute sulfuric acid solution, carrying out acid washing for 10 hours, then filtering, washing the sample to be neutral by using deionized water, and then drying the sample at 60 ℃ to obtain the highly graphitized hard carbon.
(4) Dipping the sample obtained in the step (3) in chloroplatinic acid and cobalt salt, and obtaining a load intermetallic compound Pt through freeze drying and high-temperature annealing (750 ℃, 2h,5 ℃/min) 3 Highly graphitized carbon composites of Co and their use in fuel cell high potential corrosion resistance tests. (untreated porous carbon-supported intermetallic compound Pt 3 The preparation method of Co is the same as the step (4)).
FIG. 4 shows the graphitized porous carbon and untreated porous carbon loaded intermetallic compound Pt prepared in example 7 3 XRD pattern of Co. From XRD, pt can be seen 3 Co is successfully synthesized, and the prepared Pt can be obtained through a half-peak width and a Xiele formula 3 Co particles are very small, which indicates that the graphitized porous carbon still keeps an excellent pore channel structure and can still effectively disperse the catalyst in the high-temperature reduction process, which is beneficial to the increase of the electrochemical active area of the catalyst and the improvement of the oxidation reduction performance.
FIG. 5 shows high potentials (1-1) of the porous carbon (hard carbon) loaded intermetallic compounds Pt3Co (wherein the Pt3Co content is 20%) and JM Pt/C (JM Pt/C from Johnson Matthey, USA, wherein the Pt content is 20%) before and after graphitization prepared in example 75V) comparison of Linear Sweep Voltammetry (LSV) performance before and after accelerated aging test (ADT). According to the LSV performance comparison graph, the porous carbon loaded intermetallic compound Pt before and after graphitization 3 The catalytic performance of Co is better than that of JM Pt/C, but the redox performance of the non-graphitized porous carbon-based catalyst is reduced by 58mV after ten thousand cycles of high-potential accelerated aging test, and the graphitized Pt 3 The redox performance of the Co catalyst was attenuated by only 5mV and that of commercial JM Pt/C by 10mV, showing superior corrosion resistance to commercial Pt-C.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, it is possible to make various improvements and modifications to the present invention, and those improvements and modifications also fall within the scope of protection of the claims of the present invention, and are implemented in other embodiments. Therefore, the present invention will not be limited to these embodiments.
Claims (10)
1. A method for rapidly graphitizing a porous carbon material is characterized by comprising the following steps:
(1) Mixing the graphitized catalyst solution with a porous carbon material, and drying after ultrasonic treatment;
(2) Carrying out ultra-fast Joule heating on the dried mixed material obtained in the step (1);
(3) And (3) carrying out acid washing on the mixed material subjected to the ultra-fast Joule heating in the step (2) to obtain the graphitized carbon material.
2. The method according to claim 1, wherein in the step (1), the porous carbon material is at least one of porous carbon, and the solvent of the graphitization catalyst solution is water or an organic solvent; the graphitizing catalyst is metal salt or boric acid; the concentration of the graphitization catalyst solution is 0.3-5g/ml.
3. The method of claim 2, wherein the metal salt is at least one of cobalt chloride, manganese chloride, ferric chloride, nickel chloride, copper chloride, zinc chloride, ferric nitrate, cobalt nitrate, nickel nitrate, manganese nitrate, copper nitrate, ferric acetate, nickel acetate, cobalt acetylacetonate, and ferric acetylacetonate;
the organic solvent is ethanol or isopropanol.
4. The method according to claim 1, wherein the mass ratio of the graphitization catalyst to the porous carbon material in step (1) is (0.5-10): 1.
5. The method according to claim 1, wherein the time of the ultrasound in the step (1) is 0.5-24h; the drying treatment is freeze drying or forced air drying or infrared lamp drying;
the porous carbon material in the step (1) is blocky or powdery; the porous carbon material is in a powder shape, and is added into a support carrier device for ultrafast Joule heating after being dried.
6. The method according to claim 1, wherein in the step (2), the voltage for the ultra-fast joule heating is 10-40V, the current is 10A-60A, and the time is 20s-10min; the ultra-rapid joule heating is performed in an inert gas atmosphere.
7. The method according to claim 1, wherein in the step (3), the acid to be acid-washed is at least one of dilute sulfuric acid, dilute nitric acid, dilute hydrochloric acid and dilute acetic acid, and the concentration is 0.3-4mol/L; the pickling time is 6-24h, and the temperature is 30-80 ℃.
8. Use of the graphitized carbon material obtained by the process of any one of claims 1 to 7 in the preparation of a fuel cell catalyst.
9. Use according to claim 8, characterized in that it comprises the following steps: and (3) impregnating the graphitized carbon material with chloroplatinic acid and a non-noble metal salt solution, and performing freeze drying and high-temperature annealing to obtain the fuel cell catalyst.
10. The use according to claim 9, wherein the non-noble metal salt is at least one of cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetate, cobalt acetylacetonate, nickel nitrate, ferric nitrate, zinc chloride, ferric chloride, manganese chloride and chromium chloride.
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