CN106299387A - Utilize the method that straw prepares Proton Exchange Membrane Fuel Cells gas-diffusion electrode - Google Patents
Utilize the method that straw prepares Proton Exchange Membrane Fuel Cells gas-diffusion electrode Download PDFInfo
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- CN106299387A CN106299387A CN201610893214.5A CN201610893214A CN106299387A CN 106299387 A CN106299387 A CN 106299387A CN 201610893214 A CN201610893214 A CN 201610893214A CN 106299387 A CN106299387 A CN 106299387A
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- 239000010902 straw Substances 0.000 title claims abstract description 92
- 238000009792 diffusion process Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000000446 fuel Substances 0.000 title claims abstract description 22
- 239000012528 membrane Substances 0.000 title claims abstract description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 48
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 230000001681 protective effect Effects 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 238000005245 sintering Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 235000021307 Triticum Nutrition 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 13
- 235000007164 Oryza sativa Nutrition 0.000 claims description 12
- 235000009566 rice Nutrition 0.000 claims description 12
- 241000345998 Calamus manan Species 0.000 claims description 11
- 238000007731 hot pressing Methods 0.000 claims description 11
- 235000012950 rattan cane Nutrition 0.000 claims description 11
- 229920000742 Cotton Polymers 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229910052734 helium Inorganic materials 0.000 claims description 9
- 239000001307 helium Substances 0.000 claims description 9
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 9
- 238000009954 braiding Methods 0.000 claims description 8
- UEUDBBQFZIMOQJ-UHFFFAOYSA-K ferric ammonium oxalate Chemical compound [NH4+].[NH4+].[NH4+].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UEUDBBQFZIMOQJ-UHFFFAOYSA-K 0.000 claims description 8
- -1 Acyl Ferrocene Chemical compound 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 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 6
- 238000002156 mixing Methods 0.000 claims description 6
- 240000008042 Zea mays Species 0.000 claims description 4
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 4
- 235000005822 corn Nutrition 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- FPFSGDXIBUDDKZ-UHFFFAOYSA-N 3-decyl-2-hydroxycyclopent-2-en-1-one Chemical compound CCCCCCCCCCC1=C(O)C(=O)CC1 FPFSGDXIBUDDKZ-UHFFFAOYSA-N 0.000 claims description 3
- CEQKTLFMTIWDBQ-UHFFFAOYSA-N C(C)[Fe](C1C=CC=C1)C1C=CC=C1 Chemical compound C(C)[Fe](C1C=CC=C1)C1C=CC=C1 CEQKTLFMTIWDBQ-UHFFFAOYSA-N 0.000 claims description 3
- 240000008436 Ipomoea aquatica Species 0.000 claims description 3
- 235000018694 Solanum laxum Nutrition 0.000 claims description 3
- 235000000305 Solanum wendlandii Nutrition 0.000 claims description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 3
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 235000005637 Brassica campestris Nutrition 0.000 claims 1
- 241001301148 Brassica rapa subsp. oleifera Species 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 244000098338 Triticum aestivum Species 0.000 claims 1
- GPRSOIDYHMXAGW-UHFFFAOYSA-N cyclopenta-1,3-diene cyclopentanecarboxylic acid iron Chemical compound [CH-]1[CH-][CH-][C-]([CH-]1)C(=O)O.[CH-]1C=CC=C1.[Fe] GPRSOIDYHMXAGW-UHFFFAOYSA-N 0.000 claims 1
- LXGKRVAPVVIDQW-UHFFFAOYSA-N cyclopenta-1,3-diene;1-cyclopenta-1,3-dien-1-ylbutan-1-one;iron(2+) Chemical compound [Fe+2].C=1C=C[CH-]C=1.CCCC(=O)C1=CC=C[CH-]1 LXGKRVAPVVIDQW-UHFFFAOYSA-N 0.000 claims 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract 1
- 241000209140 Triticum Species 0.000 description 16
- 241000209094 Oryza Species 0.000 description 11
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000126 substance 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
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses a kind of method utilizing straw to prepare Proton Exchange Membrane Fuel Cells gas-diffusion electrode; with straw as raw material; after the precursor solution of ferrum impregnates and dries; use pressure sintering in protective gas atmosphere once property fabricated in situ contain the gas-diffusion electrode of Fe N C non-platinum catalyst; the inventive method is implemented reliable; cost-effective, and can be by the utilization of the value maximization of straw, it is to avoid unnecessary waste.
Description
Technical field
The present invention relates to fuel cell electrode field, especially one utilizes straw to prepare Proton Exchange Membrane Fuel Cells gas
The method of bulk diffusion electrode.
Background technology
Proton Exchange Membrane Fuel Cells has the advantages such as the high and low pollution of efficiency, is therefore considered as preferable energy conversion
One of mode.In recent decades, Proton Exchange Membrane Fuel Cells is paid high attention to by government, enterprise and scientific research institution, obtains
Great development, but Proton Exchange Membrane Fuel Cells is mainly using noble metal platinum and platinum base alloy as catalyst, and platinum is high
Price significantly limit the commercialization of Proton Exchange Membrane Fuel Cells, non-platinum catalyst and the gas containing non-platinum catalyst
The research of diffusion electrode is risen.
Research in recent years finds, containing ferrum (Fe), nitrogen (N), the catalyst of carbon (C) three kinds of elements shows can be with platinum
Oxygen reduction reaction (ORR) activity that catalyst compares favourably, makes non-platinum catalyst and the diffusion of the gas containing non-platinum catalyst
It is expected to replace platinum after electrode and is applied to fuel battery cathode with proton exchange film gas-diffusion electrode.
China is a large agricultural country, and the substantial amounts of straw of annual generation, along with the development of economic society, rural area is fewer and feweri
Ground use straw is as life fuel, and selects the mode of on-site incineration compost to process straw, and this not only brings great ring
Border is endangered, and also makes the value of stalk resource not be fully utilized.Owing to straw containing abundant C, N, H, O element
(accounting for the 75% of straw gross mass), the Organic substance fiber such as these elementary composition cellulose, hemicellulose, lignins is straw
Main component, therefore will can be used conveniently to prepare the non-platinum gas-diffusion electrode of Proton Exchange Membrane Fuel Cells after straw-carbonized.
Summary of the invention
In order to solve the deficiencies in the prior art, the present invention provides that a kind of preparation cost is low, method is simple and workable
Utilize the method that straw prepares Proton Exchange Membrane Fuel Cells gas-diffusion electrode.
In order to realize above-mentioned technical purpose, the technical scheme is that one utilizes straw to prepare PEM
The method of fuel cell gas diffusion electrode, its process is: with straw as raw material, and the precursor solution through ferrum impregnates and dries
After, use the gas diffusion electricity that once property fabricated in situ contains Fe-N-C non-platinum catalyst to pressure sintering in protective gas atmosphere
Pole.
Further, it specifically includes following steps:
(1) straw is cut into a length of 5～10cm, width be 0.1～1cm straw billet；
(2) above-mentioned straw billet is made straw net；
(3) being immersed in the precursor solution of ferrum by above-mentioned straw net, the impregnation process time is 10～90min；
(4) the straw net being disposed taking-up is dried；
(5) take 3～10 layers above-mentioned dry after straw net be overlapped being placed in hot press, simultaneously in hot press, be passed through guarantor
Protect gas, make straw net under protective gas atmosphere with 1～5Mpa pressure, carry out at a temperature of 200～500 DEG C hot pressing 15～
120min, i.e. can obtain the gas-diffusion electrode containing Fe-N-C non-platinum catalyst after compacting.
Further, described straw include wheat stalk, rice straw, corn straw, Caulis Sacchari sinensis stem and leaf, cotton stalk,
One or more in rape stalk, Rhizoma Dioscoreae esculentae rattan, potato vine.
Further, the concentration of the precursor solution of described ferrum is 0.01～5mol/L.
Further, the precursor solution of described ferrum is ferric nitrate, iron chloride, ferric oxalate, ferrocene methanol, ferrocene
Formic acid, Iron sulfuret., ammonium ferric oxalate, Ferrox., ethyl dicyclopentadienyl iron, ferric acetyl acetonade, ferric ammonium sulfate, ferrous sulfate
Ammonium, diacetyl group ferrocene, benzoyl ferrocene, vinyl ferrocene, normal-butyl ferrocene, trifluoromethanesulfonic acid ferrum, butyryl
One or more mixing compositions in base ferrocene.
Further, described protective gas is one or more mixing compositions in nitrogen, argon, helium.
Further, it is braiding or compressing that straw billet is made the method for straw net by described step (2).
By above-mentioned technical scheme, the invention have the benefit that by with straw for preparing raw material, being impregnated in
It is taken out again after the precursor solution of ferrum drying, makes the precursor solution of ferrum be supported on straw surface, at the gas of protective gas
The straw that debt has under atmosphere the presoma of ferrum carries out hot pressing, makes the presoma of ferrum decompose, and iron atom is tight with straw surface
Closely connected conjunction, and meet with carbon, nitrogen element during straw-carbonized, form Fe-N-C non-platinum catalyst, due to hot pressing
In journey, straw generation carbonization is also with generation and the diffusion of the gases such as carbon monoxide, and final straw forms perforated grill structure, suitable
Diffusion in gaseous oxidant is circulated.
Accompanying drawing explanation
The present invention is further elaborated with detailed description of the invention below in conjunction with the accompanying drawings:
Fig. 1 is that the preparation flow that the present invention prepares Proton Exchange Membrane Fuel Cells non-platinum catalyst gas-diffusion electrode with straw shows
It is intended to.
Detailed description of the invention
As it is shown in figure 1, the inventive method is with straw as raw material, after the precursor solution of ferrum impregnates and dries, use
Pressure sintering in protective gas atmosphere once property fabricated in situ contain the gas-diffusion electrode of Fe-N-C non-platinum catalyst.
Further, it specifically includes following steps:
(1) straw is cut into a length of 5～10cm, width be 0.1～1cm straw billet；
(2) above-mentioned straw billet is made straw net；
(3) being immersed in the precursor solution of ferrum by above-mentioned straw net, the impregnation process time is 10～90min；
(4) the straw net being disposed taking-up is dried；
(5) take 3～10 layers above-mentioned dry after straw net be overlapped being placed in hot press, simultaneously in hot press, be passed through guarantor
Protect gas, make straw net under protective gas atmosphere with 1～5Mpa pressure, carry out at a temperature of 200～500 DEG C hot pressing 15～
120min, i.e. can obtain the gas-diffusion electrode containing Fe-N-C non-platinum catalyst after compacting.
Further, described straw include wheat stalk, rice straw, corn straw, Caulis Sacchari sinensis stem and leaf, cotton stalk,
One or more in rape stalk, Rhizoma Dioscoreae esculentae rattan, potato vine.
Further, the concentration of the precursor solution of described ferrum is 0.01～5mol/L.
Further, the precursor solution of described ferrum is ferric nitrate, iron chloride, ferric oxalate, ferrocene methanol, ferrocene
Formic acid, Iron sulfuret., ammonium ferric oxalate, Ferrox., ethyl dicyclopentadienyl iron, ferric acetyl acetonade, ferric ammonium sulfate, ferrous sulfate
Ammonium, diacetyl group ferrocene, benzoyl ferrocene, vinyl ferrocene, normal-butyl ferrocene, trifluoromethanesulfonic acid ferrum, butyryl
One or more mixing compositions in base ferrocene.
Further, described protective gas is one or more mixing compositions in nitrogen, argon, helium.
Further, it is braiding or compressing that straw billet is made the method for straw net by described step (2).
Embodiment 1
(1) wheat stalk cuts into a length of 10cm, width is the wheat stalk billet of 1cm；
(2) wheat stalk net is made in above-mentioned wheat stalk billet braiding；
(3) above-mentioned wheat stalk net is immersed in the ammonium ferric oxalate solution that concentration is 3mol/L, impregnation process 70min；
(4) the wheat stalk net processed is taken out from ammonium ferric oxalate solution dry；
(5) take 3 layers above-mentioned dry after wheat stalk net be overlapped being placed in hot press, simultaneously in hot press, be passed through nitrogen
Gas, makes wheat stalk net with 3Mpa pressure, carry out hot pressing 100min at a temperature of 300 DEG C under the protective atmosphere of nitrogen, compacting
After i.e. can obtain the gas-diffusion electrode containing Fe-N-C non-platinum catalyst.
Embodiment 2
(1) rice straw cuts into a length of 8cm, width is the rice straw billet of 0.5cm；
(2) rice straw net is made in above-mentioned rice straw billet braiding；
(3) above-mentioned rice straw net is immersed in the iron nitrate solution that concentration is 3mol/L, impregnation process 80min；
(4) the rice straw net processed is taken out from ammonium ferric oxalate solution dry；
(5) take 6 layers above-mentioned dry after rice straw net be overlapped being placed in hot press, simultaneously in hot press, be passed through helium
Gas, makes rice straw net with 4Mpa pressure, carry out hot pressing 90min at a temperature of 400 DEG C under the protective atmosphere of helium, has suppressed
The gas-diffusion electrode containing Fe-N-C non-platinum catalyst i.e. can be obtained after Biing.
Embodiment 3
(1) cotton stalk cuts into a length of 5cm, width is the cotton stalk billet of 0.1cm；
(2) cotton stalk net is made in above-mentioned corn straw billet braiding；
(3) above-mentioned cotton stalk net is immersed in the ammonium ferric oxalate solution that concentration is 1mol/L, impregnation process 90min；
(4) the cotton stalk net processed is taken out from ammonium ferric oxalate solution dry；
(5) take 4 layers above-mentioned dry after cotton stalk net be overlapped being placed in hot press, simultaneously in hot press, be passed through argon
Gas, makes cotton stalk net with 5Mpa pressure, carry out hot pressing 50min at a temperature of 460 DEG C under the protective atmosphere of argon, has suppressed
The gas-diffusion electrode containing Fe-N-C non-platinum catalyst i.e. can be obtained after Biing.
Embodiment 4
(1) rape stalk cuts into a length of 6cm, width is the rape stalk billet of 0.6cm；
(2) rape stalk net is made in above-mentioned wheat stalk billet braiding；
(3) above-mentioned rape stalk net is immersed in the benzoyl solution of ferrocene that concentration is 0.01mol/L, impregnation process
10min；
(4) the rape stalk net processed is taken out from benzoyl solution of ferrocene dry；
(5) take 10 layers above-mentioned dry after rape stalk net be overlapped being placed in hot press, be passed through in hot press simultaneously
Nitrogen and helium volume ratio are the mixed gas of 1:1, make rape stalk net press with 1Mpa under the protective atmosphere of nitrogen and helium
Power, carry out hot pressing 120min at a temperature of 200 DEG C, i.e. can obtain the gas containing Fe-N-C non-platinum catalyst after compacting and expand
Dissipate electrode.
Embodiment 5
(1) Rhizoma Dioscoreae esculentae rattan straw is cut into a length of 7cm, width is the Rhizoma Dioscoreae esculentae rattan straw billet of 0.7cm；
(2) above-mentioned Rhizoma Dioscoreae esculentae rattan straw billet is made Rhizoma Dioscoreae esculentae rattan straw net；
(3) above-mentioned Rhizoma Dioscoreae esculentae rattan straw net is immersed in the acetylacetone,2,4-pentanedione ferrous solution that concentration is 5mol/L, impregnation process
60min；
(4) the Rhizoma Dioscoreae esculentae rattan straw net processed is taken out from acetylacetone,2,4-pentanedione ferrous solution dry；
(5) take 7 layers above-mentioned dry after Rhizoma Dioscoreae esculentae rattan straw net be overlapped being placed in hot press, be passed through in hot press simultaneously
Argon and helium volume ratio are the mixed gas of 1:1, make Rhizoma Dioscoreae esculentae rattan straw net with 2Mpa under the protective atmosphere of argon and helium
Pressure, carry out hot pressing 15min at a temperature of 500 DEG C, after compacting, i.e. can obtain the gas containing Fe-N-C non-platinum catalyst
Diffusion electrode.
Embodiment 6
(1) wheat stalk and rice straw are cut into a length of 10cm, width is the wheat stalk billet of 1cm；
(2) straw net is made in above-mentioned wheat stalk billet braiding；
(3) above-mentioned straw net is immersed in the ferrocene methanol solution that concentration is 2mol/L, impregnation process 30min；
(4) the straw net processed is taken out from ferrocene methanol solution dry；
(5) take 8 layers above-mentioned dry after wheat stalk net be overlapped being placed in hot press, simultaneously in hot press, be passed through nitrogen
Gas, makes wheat stalk net with 1.5Mpa pressure, carry out hot pressing 60min at a temperature of 480 DEG C under the protective atmosphere of nitrogen, compacting
After i.e. can obtain the gas-diffusion electrode containing Fe-N-C non-platinum catalyst.
The foregoing is only presently preferred embodiments of the present invention, for the ordinary skill in the art, without departing from
In the case of the principle of the present invention and spirit, all equalizations made according to scope of the present invention patent change, revise, replace and become
Type, all should belong to the covering scope of the present invention.
Claims (7)
1. one kind utilizes the method that straw prepares Proton Exchange Membrane Fuel Cells gas-diffusion electrode, it is characterised in that: with straw
For raw material, after the precursor solution of ferrum impregnates and dries, use pressure sintering once property conjunction in situ in protective gas atmosphere
Become the gas-diffusion electrode containing Fe-N-C non-platinum catalyst.
The method utilizing straw to prepare Proton Exchange Membrane Fuel Cells gas-diffusion electrode the most according to claim 1, its
It is characterised by: specifically include following steps:
(1) straw is cut into a length of 5～10cm, width be 0.1～1cm straw billet；
(2) above-mentioned straw billet is made straw net；
(3) being immersed in the precursor solution of ferrum by above-mentioned straw net, the impregnation process time is 10～90min；
(4) the straw net being disposed taking-up is dried；
(5) take 3～10 layers above-mentioned dry after straw net be overlapped being placed in hot press, simultaneously in hot press, be passed through guarantor
Protect gas, make straw net under protective gas atmosphere with 1～5Mpa pressure, carry out at a temperature of 200～500 DEG C hot pressing 15～
120min, i.e. can obtain the gas-diffusion electrode containing Fe-N-C non-platinum catalyst after compacting.
The method utilizing straw to prepare Proton Exchange Membrane Fuel Cells gas-diffusion electrode the most according to claim 1 and 2,
It is characterized in that: described straw includes wheat stalk, rice straw, corn straw, Caulis Sacchari sinensis stem and leaf, cotton stalk, Brassica campestris L straw
One or more in stalk, Rhizoma Dioscoreae esculentae rattan, potato vine.
The method utilizing straw to prepare Proton Exchange Membrane Fuel Cells gas-diffusion electrode the most according to claim 1 and 2,
It is characterized in that: the concentration of the precursor solution of described ferrum is 0.01～5mol/L.
The method utilizing straw to prepare Proton Exchange Membrane Fuel Cells gas-diffusion electrode the most according to claim 1 and 2,
It is characterized in that: the precursor solution of described ferrum be ferric nitrate, iron chloride, ferric oxalate, ferrocene methanol, ferrocenecarboxylic acid,
Iron sulfuret., ammonium ferric oxalate, Ferrox., ethyl dicyclopentadienyl iron, ferric acetyl acetonade, ferric ammonium sulfate, Ferrous ammonium sulfate, double second
Acyl Ferrocene, benzoyl ferrocene, vinyl ferrocene, normal-butyl ferrocene, trifluoromethanesulfonic acid ferrum, Butyrylferrocene
In one or more mixing composition.
The method utilizing straw to prepare Proton Exchange Membrane Fuel Cells gas-diffusion electrode the most according to claim 1 and 2,
It is characterized in that: described protective gas is one or more mixing compositions in nitrogen, argon, helium.
The method utilizing straw to prepare Proton Exchange Membrane Fuel Cells gas-diffusion electrode the most according to claim 2, its
It is characterised by: it is braiding or compressing that straw billet is made the method for straw net by described step (2).
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