CN106784878A - A kind of preparation method of Mn Graphenes mating type fuel-cell catalyst - Google Patents
A kind of preparation method of Mn Graphenes mating type fuel-cell catalyst Download PDFInfo
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- CN106784878A CN106784878A CN201710030589.3A CN201710030589A CN106784878A CN 106784878 A CN106784878 A CN 106784878A CN 201710030589 A CN201710030589 A CN 201710030589A CN 106784878 A CN106784878 A CN 106784878A
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- carbon material
- manganese
- molybdenum
- cobalt
- platinum
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 32
- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 230000013011 mating Effects 0.000 title claims abstract description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 77
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000010941 cobalt Substances 0.000 claims abstract description 45
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 45
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 45
- 239000011733 molybdenum Substances 0.000 claims abstract description 45
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000011572 manganese Substances 0.000 claims abstract description 43
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 39
- 238000000227 grinding Methods 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000004140 cleaning Methods 0.000 claims abstract description 20
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 239000011261 inert gas Substances 0.000 claims abstract description 13
- 239000012467 final product Substances 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 12
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 12
- 239000011591 potassium Substances 0.000 claims description 12
- 239000012279 sodium borohydride Substances 0.000 claims description 12
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 12
- 235000011150 stannous chloride Nutrition 0.000 claims description 12
- 239000001119 stannous chloride Substances 0.000 claims description 12
- 238000002604 ultrasonography Methods 0.000 claims description 12
- 235000006408 oxalic acid Nutrition 0.000 claims description 11
- 235000007686 potassium Nutrition 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000002134 carbon nanofiber Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- -1 graphite alkene Chemical class 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002091 nanocage Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 244000025254 Cannabis sativa Species 0.000 claims 1
- UBXWAYGQRZFPGU-UHFFFAOYSA-N manganese(2+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Mn++] UBXWAYGQRZFPGU-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000446 fuel Substances 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Classifications
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- 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
- H01M4/923—Compounds thereof with non-metallic elements
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method of Mn Graphenes mating type fuel-cell catalyst, comprise the following steps：By manganese, platinum, molybdenum, cobalt is placed into cleaning device with carbon material and is cleaned, carbon material is dried to put into container, it is subsequently adding salt solution and enters line replacement reaction, manganese is dried to put into container, carbon material distinguishes filtration treatment with manganese, by carbon material and manganese and platinum, molybdenum, the mixture of cobalt is transferred in grinding container, mechanical lapping 5 15 minutes is carried out under hygrometric state condition, carbon material and manganese and platinum, after molybdenum and cobalt are uniformly dispersed in reaction vessel, heated up with 20 DEG C/min speed under inert gas atmosphere protection and be calcined 2 4h at 200 900 DEG C, obtain final product Mn Graphene mating type fuel-cell catalysts.The low cost of fuel-cell catalyst Mn, Graphene in the present invention, and preparation method is simple, the particle size of fuel-cell catalyst is easily controlled, and is adapted for mass industrialized production.
Description
Technical field
The present invention relates to cell art, more particularly to a kind of system of Mn- Graphenes mating type fuel-cell catalyst
Preparation Method.
Background technology
The production of the energy and Consumption relation to global climate change.At present, 80% energy resource consumption by fossil fuel-
Coal and oil.However, traditional energy resource consumption is non-renewable resources in the presence of following drawback coal and oil, can be exhausted quickly；
Because conventional heat engines realize that energy conversion is limited by Carnot cycle, burn very low relative to the utilization rate of the energy；It is big to quantify
The pollutants such as great amount of carbon dioxide and COx, NOx produced by the burning of stone fuel, cause greenhouse effects and acid rain etc. tight
The environmental problem of weight.Traditional energy resource structure and poor efficiency cannot meet future society sustainable development to efficient, cleaning, warp
Ji, the demand of safety energy.
Polymer electrolyte fuel cells (PEFCs) have that power density is high, pollution-free, low-temperature operation (60-90 DEG C) and
Environment-friendly the features such as, it is considered to be the green energy resource technology of 21 century first-selection.Compared with other fuel cells, PEFCs can be
It is quick at room temperature to start, and can quickly change power output according to load request, be most rising following electric automobile,
The preferable substitute electric power of distributing power station, stand-by power supply and portable electronics, catalyst prepared by prior art has operation
The uppity shortcoming of more complicated, course of reaction, it is impossible to which meeting fuel cell industrialization well must ask, it is therefore proposed that
A kind of preparation method of Mn- Graphenes mating type fuel-cell catalyst.
The content of the invention
The present invention proposes a kind of preparation method of Mn- Graphenes mating type fuel-cell catalyst, to solve the above-mentioned back of the body
The problem proposed in scape technology.
The present invention proposes a kind of preparation method of Mn- Graphenes mating type fuel-cell catalyst, comprises the following steps：
S1, selection manganese, platinum, molybdenum, cobalt and carbon material are raw material, and manganese, platinum, molybdenum, cobalt and carbon material are placed into cleaning dress
Cleaned in putting, and the number of times of cleaning is 3-6 times, to ensure that manganese, platinum, molybdenum, cobalt and carbon material cleannes in itself are higher than hundred
/ nine ten five, dried after cleaning；
S2, the carbon material that dries processed in S1 is put into container, and adds pure water, and carbon material and pure water weight
Than being 1: 3, protection gas is passed through after ultrasound, adds reducing agent, the reaction time is 5-10 minutes, and ensure that the temperature reacted is
50-75 degrees Celsius, it is subsequently adding salt solution and enters line replacement reaction, the time for replacing reaction is 3-7 minutes, after the completion of, it is standby；
S3, the manganese that dries processed in S1 is put into container, and add pure water, and carbon material is with the weight ratio of pure water
1: 2, oxidant is added after ultrasound, react 5-10 minutes, and ensure that the temperature reacted is 50-75 degrees Celsius, after the completion of, it is standby；
S4, by S2 and S3 process carbon material and manganese each lead into filter, carry out filtration treatment, during treatment guarantor
Demonstrate,prove respective independence；
S5, the carbon material and manganese in S4 are uniformly dispersed in reaction vessel after, the mixture of carbon material and manganese is shifted
Into grinding container, carried out under hygrometric state condition mechanical lapping 15-35 minutes, in process of lapping, it is ensured that grinding temperature is 40-
60 degrees Celsius；
S6, by after platinum, molybdenum, cobalt are uniformly dispersed in reaction vessel in S1, the mixture of platinum, molybdenum, cobalt is transferred to grinding
In container, carried out under hygrometric state condition mechanical lapping 5-15 minutes, in process of lapping, it is ensured that grinding temperature is that 60-80 is Celsius
Degree；
S7, will be ground through S5 and S6 after product carry out filtration treatment respectively, it is ensured that carbon material and manganese and platinum, molybdenum and cobalt
Granular size is 5-10 microns；
S8, carbon material in S7 and manganese and platinum, molybdenum and cobalt are uniformly dispersed in reaction vessel after, inert gas atmosphere protect
To be calcined 2-4h at 200-900 DEG C of 20 DEG C/min speed intensification under shield, and programming rate is 200 DEG C/h, it is ensured that at reaction vessel
In vacuum state, Mn- Graphene mating type fuel-cell catalysts are obtained final product.
Preferably, the reducing agent in S2 is the mixture of stannous chloride, oxalic acid, potassium borohydride, sodium borohydride and ethanol,
And the weight ratio of stannous chloride, oxalic acid, potassium borohydride, sodium borohydride and ethanol is 1: 0.7: 1.2: 0.8.
Preferably, the oxidant in S3 is the concentrated sulfuric acid, nitric acid, manganese dioxide, the mixture of di-iron trioxide, and dense sulphur
Acid, nitric acid, manganese dioxide, the weight ratio of di-iron trioxide are 1.1: 0.9: 1.15: 0.8.
Preferably, the inert gas in S8 is nitrogen, and the oxygen content of vacuum state is not higher than 2 percent.
Preferably, carbon material is activated carbon, carbon nano-fiber, nano cages, Graphene or oxygen or graphite alkene.
Preferably, the grinding rate of the grinding container in preparation process need to be maintained at 3000-3500 turns/min.
The low cost of fuel-cell catalyst Mn, Graphene in the present invention, and preparation method is simple, easily operation, fuel
The particle size of cell catalyst is easily controlled, and is adapted for mass industrialized production, has a good application prospect.
Specific embodiment
With reference to specific embodiment, the present invention will be further described.
Embodiment 1
The present invention proposes a kind of preparation method of Mn- Graphenes mating type fuel-cell catalyst, comprises the following steps：
S1, to choose manganese, platinum, molybdenum, cobalt and carbon material be raw material, carbon material be activated carbon, carbon nano-fiber, nano cages,
Graphene or oxygen or graphite alkene, and manganese, platinum, molybdenum, cobalt and carbon material are placed into cleaning device are cleaned, and cleaning
Number of times be 3 times, to ensure manganese, platinum, molybdenum, cobalt and carbon material cleannes in itself higher than 95 percent, dried after cleaning；
S2, the carbon material that dries processed in S1 is put into container, and adds pure water, and carbon material and pure water weight
Than being 1: 3, protection gas is passed through after ultrasound, adds reducing agent, reducing agent is stannous chloride, oxalic acid, potassium borohydride, sodium borohydride
It is 1: 0.7: 1.2 with the weight ratio of the mixture of ethanol, and stannous chloride, oxalic acid, potassium borohydride, sodium borohydride and ethanol:
0.8, the reaction time is 5 minutes, and ensures that the temperature reacted is 50 degrees Celsius, is subsequently adding salt solution and enters line replacement reaction, displacement
The time of reaction is 3 minutes, after the completion of, it is standby；
S3, the manganese that dries processed in S1 is put into container, and add pure water, and carbon material is with the weight ratio of pure water
1: 2, add oxidant after ultrasound, oxidant is the concentrated sulfuric acid, nitric acid, manganese dioxide, the mixture of di-iron trioxide, and dense sulphur
Acid, nitric acid, manganese dioxide, the weight ratio of di-iron trioxide are 1.1: 0.9: 1.15: 0.8, are reacted 5-10 minutes, and ensure reaction
Temperature be 50 degrees Celsius, after the completion of, it is standby；
S4, by S2 and S3 process carbon material and manganese each lead into filter, carry out filtration treatment, during treatment guarantor
Demonstrate,prove respective independence；
S5, the carbon material and manganese in S4 are uniformly dispersed in reaction vessel after, the mixture of carbon material and manganese is shifted
Into grinding container, mechanical lapping 15 minutes is carried out under hygrometric state condition, in process of lapping, it is ensured that grinding temperature is 40 Celsius
Degree；
S6, by after platinum, molybdenum, cobalt are uniformly dispersed in reaction vessel in S1, the mixture of platinum, molybdenum, cobalt is transferred to grinding
In container, mechanical lapping 5 minutes is carried out under hygrometric state condition, in process of lapping, it is ensured that grinding temperature is 60 degrees Celsius；
S7, will be ground through S5 and S6 after product carry out filtration treatment respectively, it is ensured that carbon material and manganese and platinum, molybdenum and cobalt
Granular size is 5 microns；
S8, carbon material in S7 and manganese and platinum, molybdenum and cobalt are uniformly dispersed in reaction vessel after, inert gas atmosphere protect
Heated up with 20 DEG C/min speed under shield and be calcined 2h at 200 DEG C, and programming rate is 200 DEG C/h, inert gas is nitrogen, and vacuum
The oxygen content of state is not higher than 2 percent, it is ensured that reaction vessel is in vacuum state, obtains final product Mn- Graphene mating types fuel electricity
Pond catalyst.
The grinding rate of the grinding container in preparation process need to be maintained at 3000 turns/min.
Embodiment 2
The present invention proposes a kind of preparation method of Mn- Graphenes mating type fuel-cell catalyst, comprises the following steps：
S1, to choose manganese, platinum, molybdenum, cobalt and carbon material be raw material, carbon material be activated carbon, carbon nano-fiber, nano cages,
Graphene or oxygen or graphite alkene, and manganese, platinum, molybdenum, cobalt and carbon material are placed into cleaning device are cleaned, and cleaning
Number of times be 4 times, to ensure manganese, platinum, molybdenum, cobalt and carbon material cleannes in itself higher than 95 percent, dried after cleaning；
S2, the carbon material that dries processed in S1 is put into container, and adds pure water, and carbon material and pure water weight
Than being 1: 3, protection gas is passed through after ultrasound, adds reducing agent, reducing agent is stannous chloride, oxalic acid, potassium borohydride, sodium borohydride
It is 1: 0.7: 1.2 with the weight ratio of the mixture of ethanol, and stannous chloride, oxalic acid, potassium borohydride, sodium borohydride and ethanol:
0.8, the reaction time is 6.5 minutes, and ensures that the temperature reacted is 55 degrees Celsius, is subsequently adding salt solution and enters line replacement reaction, is put
The time of reaction is changed for 4 minutes, after the completion of, it is standby；
S3, the manganese that dries processed in S1 is put into container, and add pure water, and carbon material is with the weight ratio of pure water
1: 2, add oxidant after ultrasound, oxidant is the concentrated sulfuric acid, nitric acid, manganese dioxide, the mixture of di-iron trioxide, and dense sulphur
Acid, nitric acid, manganese dioxide, the weight ratio of di-iron trioxide are 1.1: 0.9: 1.15: 0.8, are reacted 6.5 minutes, and ensure reaction
Temperature be 55 degrees Celsius, after the completion of, it is standby；
S4, by S2 and S3 process carbon material and manganese each lead into filter, carry out filtration treatment, during treatment guarantor
Demonstrate,prove respective independence；
S5, the carbon material and manganese in S4 are uniformly dispersed in reaction vessel after, the mixture of carbon material and manganese is shifted
Into grinding container, mechanical lapping 20 minutes is carried out under hygrometric state condition, in process of lapping, it is ensured that grinding temperature is 45 Celsius
Degree；
S6, by after platinum, molybdenum, cobalt are uniformly dispersed in reaction vessel in S1, the mixture of platinum, molybdenum, cobalt is transferred to grinding
In container, mechanical lapping 8 minutes is carried out under hygrometric state condition, in process of lapping, it is ensured that grinding temperature is 65 degrees Celsius；
S7, will be ground through S5 and S6 after product carry out filtration treatment respectively, it is ensured that carbon material and manganese and platinum, molybdenum and cobalt
Granular size is 6.5 microns；
S8, carbon material in S7 and manganese and platinum, molybdenum and cobalt are uniformly dispersed in reaction vessel after, inert gas atmosphere protect
Heated up with 20 DEG C/min speed under shield and be calcined 2.5h at 400 DEG C, and programming rate is 200 DEG C/h, inert gas is nitrogen, and very
The oxygen content of dummy status is not higher than 2 percent, it is ensured that reaction vessel is in vacuum state, obtains final product Mn- Graphene mating type fuel
Cell catalyst.
The grinding rate of the grinding container in preparation process need to be maintained at 3100 turns/min.
Embodiment 3
The present invention proposes a kind of preparation method of Mn- Graphenes mating type fuel-cell catalyst, comprises the following steps：
S1, to choose manganese, platinum, molybdenum, cobalt and carbon material be raw material, carbon material be activated carbon, carbon nano-fiber, nano cages,
Graphene or oxygen or graphite alkene, and manganese, platinum, molybdenum, cobalt and carbon material are placed into cleaning device are cleaned, and cleaning
Number of times be 5 times, to ensure manganese, platinum, molybdenum, cobalt and carbon material cleannes in itself higher than 95 percent, dried after cleaning；
S2, the carbon material that dries processed in S1 is put into container, and adds pure water, and carbon material and pure water weight
Than being 1: 3, protection gas is passed through after ultrasound, adds reducing agent, reducing agent is stannous chloride, oxalic acid, potassium borohydride, sodium borohydride
It is 1: 0.7: 1.2 with the weight ratio of the mixture of ethanol, and stannous chloride, oxalic acid, potassium borohydride, sodium borohydride and ethanol:
0.8, the reaction time is 8 minutes, and ensures that the temperature reacted is 66 degrees Celsius, is subsequently adding salt solution and enters line replacement reaction, displacement
The time of reaction is 6 minutes, after the completion of, it is standby；
S3, the manganese that dries processed in S1 is put into container, and add pure water, and carbon material is with the weight ratio of pure water
1: 2, add oxidant after ultrasound, oxidant is the concentrated sulfuric acid, nitric acid, manganese dioxide, the mixture of di-iron trioxide, and dense sulphur
Acid, nitric acid, manganese dioxide, the weight ratio of di-iron trioxide are 1.1: 0.9: 1.15: 0.8, are reacted 8 minutes, and ensure reaction
Temperature is 68 degrees Celsius, after the completion of, it is standby；
S4, by S2 and S3 process carbon material and manganese each lead into filter, carry out filtration treatment, during treatment guarantor
Demonstrate,prove respective independence；
S5, the carbon material and manganese in S4 are uniformly dispersed in reaction vessel after, the mixture of carbon material and manganese is shifted
Into grinding container, mechanical lapping 30 minutes is carried out under hygrometric state condition, in process of lapping, it is ensured that grinding temperature is 55 Celsius
Degree；
S6, by after platinum, molybdenum, cobalt are uniformly dispersed in reaction vessel in S1, the mixture of platinum, molybdenum, cobalt is transferred to grinding
In container, mechanical lapping 12 minutes is carried out under hygrometric state condition, in process of lapping, it is ensured that grinding temperature is 75 degrees Celsius；
S7, will be ground through S5 and S6 after product carry out filtration treatment respectively, it is ensured that carbon material and manganese and platinum, molybdenum and cobalt
Granular size is 8 microns；
S8, carbon material in S7 and manganese and platinum, molybdenum and cobalt are uniformly dispersed in reaction vessel after, inert gas atmosphere protect
Heated up with 20 DEG C/min speed under shield and be calcined 3.5h at 700 DEG C, and programming rate is 200 DEG C/h, inert gas is nitrogen, and very
The oxygen content of dummy status is not higher than 2 percent, it is ensured that reaction vessel is in vacuum state, obtains final product Mn- Graphene mating type fuel
Cell catalyst.
The grinding rate of the grinding container in preparation process need to be maintained at 3300 turns/min.
Embodiment 4
The present invention proposes a kind of preparation method of Mn- Graphenes mating type fuel-cell catalyst, comprises the following steps：
S1, to choose manganese, platinum, molybdenum, cobalt and carbon material be raw material, carbon material be activated carbon, carbon nano-fiber, nano cages,
Graphene or oxygen or graphite alkene, and manganese, platinum, molybdenum, cobalt and carbon material are placed into cleaning device are cleaned, and cleaning
Number of times be 6 times, to ensure manganese, platinum, molybdenum, cobalt and carbon material cleannes in itself higher than 95 percent, dried after cleaning；
S2, the carbon material that dries processed in S1 is put into container, and adds pure water, and carbon material and pure water weight
Than being 1: 3, protection gas is passed through after ultrasound, adds reducing agent, reducing agent is stannous chloride, oxalic acid, potassium borohydride, sodium borohydride
It is 1: 0.7: 1.2 with the weight ratio of the mixture of ethanol, and stannous chloride, oxalic acid, potassium borohydride, sodium borohydride and ethanol:
0.8, the reaction time is 10 minutes, and ensures that the temperature reacted is 75 degrees Celsius, is subsequently adding salt solution and enters line replacement reaction, displacement
The time of reaction is 7 minutes, after the completion of, it is standby；
S3, the manganese that dries processed in S1 is put into container, and add pure water, and carbon material is with the weight ratio of pure water
1: 2, add oxidant after ultrasound, oxidant is the concentrated sulfuric acid, nitric acid, manganese dioxide, the mixture of di-iron trioxide, and dense sulphur
Acid, nitric acid, manganese dioxide, the weight ratio of di-iron trioxide are 1.1: 0.9: 1.15: 0.8, are reacted 10 minutes, and ensure reaction
Temperature is 75 degrees Celsius, after the completion of, it is standby；
S4, by S2 and S3 process carbon material and manganese each lead into filter, carry out filtration treatment, during treatment guarantor
Demonstrate,prove respective independence；
S5, the carbon material and manganese in S4 are uniformly dispersed in reaction vessel after, the mixture of carbon material and manganese is shifted
Into grinding container, mechanical lapping 35 minutes is carried out under hygrometric state condition, in process of lapping, it is ensured that grinding temperature is 60 Celsius
Degree；
S6, by after platinum, molybdenum, cobalt are uniformly dispersed in reaction vessel in S1, the mixture of platinum, molybdenum, cobalt is transferred to grinding
In container, mechanical lapping 15 minutes is carried out under hygrometric state condition, in process of lapping, it is ensured that grinding temperature is 80 degrees Celsius；
S7, will be ground through S5 and S6 after product carry out filtration treatment respectively, it is ensured that carbon material and manganese and platinum, molybdenum and cobalt
Granular size is 10 microns；
S8, carbon material in S7 and manganese and platinum, molybdenum and cobalt are uniformly dispersed in reaction vessel after, inert gas atmosphere protect
Heated up with 20 DEG C/min speed under shield and be calcined 4h at 900 DEG C, and programming rate is 200 DEG C/h, inert gas is nitrogen, and vacuum
The oxygen content of state is not higher than 2 percent, it is ensured that reaction vessel is in vacuum state, obtains final product Mn- Graphene mating types fuel electricity
Pond catalyst.
The grinding rate of the grinding container in preparation process need to be maintained at 3500 turns/min.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technology according to the present invention scheme and its
Inventive concept is subject to equivalent or change, should all be included within the scope of the present invention.
Claims (6)
1. a kind of preparation method of Mn- Graphenes mating type fuel-cell catalyst, it is characterised in that comprise the following steps：
S1, selection manganese, platinum, molybdenum, cobalt and carbon material are raw material, and manganese, platinum, molybdenum, cobalt and carbon material are placed into cleaning device
Cleaned, and the number of times of cleaning is 3-6 times, to ensure that manganese, platinum, molybdenum, cobalt and carbon material cleannes in itself are higher than percent
95, dried after cleaning；
S2, the carbon material that dries processed in S1 is put into container, and add pure water, and carbon material is with the weight ratio of pure water
1: 3, protection gas is passed through after ultrasound, reducing agent is added, the reaction time is 5-10 minutes, and ensures that the temperature reacted is 50-75
Degree Celsius, it is subsequently adding salt solution and enters line replacement reaction, the time for replacing reaction is 3-7 minutes, after the completion of, it is standby；
S3, the manganese that dries processed in S1 is put into container, and add pure water, and carbon material and the weight ratio of pure water are 1: 2,
Oxidant is added after ultrasound, is reacted 5-10 minutes, and ensure that the temperature reacted is 50-75 degrees Celsius, after the completion of, it is standby；
S4, by S2 and S3 process carbon material and manganese each lead into filter, carry out filtration treatment, during treatment ensure respectively
From independence；
S5, the carbon material and manganese in S4 are uniformly dispersed in reaction vessel after, carbon material is transferred to the mixture of manganese and is ground
In mill container, carried out under hygrometric state condition mechanical lapping 15-35 minutes, in process of lapping, it is ensured that grinding temperature is taken the photograph for 40-60
Family name's degree；
S6, by after platinum, molybdenum, cobalt are uniformly dispersed in reaction vessel in S1, the mixture of platinum, molybdenum, cobalt is transferred to grinding container
In, carried out under hygrometric state condition mechanical lapping 5-15 minutes, in process of lapping, it is ensured that grinding temperature is 60-80 degrees Celsius；
S7, will be ground through S5 and S6 after product carry out filtration treatment respectively, it is ensured that the particle of carbon material and manganese and platinum, molybdenum and cobalt
Size is 5-10 microns；
S8, carbon material in S7 and manganese and platinum, molybdenum and cobalt are uniformly dispersed in reaction vessel after, inert gas atmosphere protection under
To be calcined 2-4h at 200-900 DEG C of 20 DEG C/min speed intensification, and programming rate is 200 DEG C/h, it is ensured that reaction vessel is in true
Dummy status, obtains final product Mn- Graphene mating type fuel-cell catalysts.
2. the preparation method of Mn- Graphenes mating type fuel-cell catalyst according to claim 1, it is characterised in that
Reducing agent in S2 is the mixture of stannous chloride, oxalic acid, potassium borohydride, sodium borohydride and ethanol, and stannous chloride, grass
The weight ratio of acid, potassium borohydride, sodium borohydride and ethanol is 1: 0.7: 1.2: 0.8.
3. the preparation method of Mn- Graphenes mating type fuel-cell catalyst according to claim 1, it is characterised in that
Oxidant in S3 is the concentrated sulfuric acid, nitric acid, manganese dioxide, the mixture of di-iron trioxide, and the concentrated sulfuric acid, nitric acid, titanium dioxide
Manganese, the weight ratio of di-iron trioxide are 1.1: 0.9: 1.15: 0.8.
4. the preparation method of Mn- Graphenes mating type fuel-cell catalyst according to claim 1, it is characterised in that
Inert gas in S8 is nitrogen, and the oxygen content of vacuum state is not higher than 2 percent.
5. the preparation method of Mn- Graphenes mating type fuel-cell catalyst according to claim 1, it is characterised in that
Carbon material is activated carbon, carbon nano-fiber, nano cages, Graphene or oxygen or graphite alkene.
6. the preparation method of Mn- Graphenes mating type fuel-cell catalyst according to claim 1, it is characterised in that
The grinding rate of the grinding container in preparation process need to be maintained at 3000-3500 and turn/min.
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| CN111095638A (en) * | 2017-09-27 | 2020-05-01 | 田中贵金属工业株式会社 | Catalyst for solid polymer fuel cell and method for producing same |
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| CN103035926A (en) * | 2011-10-07 | 2013-04-10 | 现代自动车株式会社 | Fuel cell electrode and method for manufacturing membrane-electrode assembly using the same |
| CN104412431A (en) * | 2012-06-25 | 2015-03-11 | 田中贵金属工业株式会社 | Catalyst for solid polymer fuel cell and method for producing same |
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2017
- 2017-01-17 CN CN201710030589.3A patent/CN106784878A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103035926A (en) * | 2011-10-07 | 2013-04-10 | 现代自动车株式会社 | Fuel cell electrode and method for manufacturing membrane-electrode assembly using the same |
| CN104412431A (en) * | 2012-06-25 | 2015-03-11 | 田中贵金属工业株式会社 | Catalyst for solid polymer fuel cell and method for producing same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111095638A (en) * | 2017-09-27 | 2020-05-01 | 田中贵金属工业株式会社 | Catalyst for solid polymer fuel cell and method for producing same |
| CN111095638B (en) * | 2017-09-27 | 2022-08-12 | 田中贵金属工业株式会社 | Catalyst for solid polymer fuel cell and method for producing same |
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