CN106890676A - A kind of porous electro-catalysis membrane and its preparation and application - Google Patents
A kind of porous electro-catalysis membrane and its preparation and application Download PDFInfo
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- CN106890676A CN106890676A CN201510961119.XA CN201510961119A CN106890676A CN 106890676 A CN106890676 A CN 106890676A CN 201510961119 A CN201510961119 A CN 201510961119A CN 106890676 A CN106890676 A CN 106890676A
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- 239000012528 membrane Substances 0.000 title claims abstract description 58
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 230000003197 catalytic effect Effects 0.000 claims abstract description 16
- 239000000446 fuel Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 229910000510 noble metal Inorganic materials 0.000 claims description 11
- 239000003575 carbonaceous material Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 230000005611 electricity Effects 0.000 claims description 9
- 238000006722 reduction reaction Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000012018 catalyst precursor Substances 0.000 claims description 8
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920002521 macromolecule Polymers 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 230000000903 blocking effect Effects 0.000 claims description 4
- 239000002134 carbon nanofiber Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 230000005518 electrochemistry Effects 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000012798 spherical particle Substances 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims 2
- 239000006229 carbon black Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 239000010970 precious metal Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 12
- 239000011943 nanocatalyst Substances 0.000 abstract description 10
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 210000004379 membrane Anatomy 0.000 description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000009467 reduction Effects 0.000 description 7
- 229920000557 Nafion® Polymers 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 229910002849 PtRu Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 210000002469 basement membrane Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006253 efflorescence Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 206010037844 rash Diseases 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 229910017939 Ag-MnO2 Inorganic materials 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008827 biological function Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Inert Electrodes (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of Polymer/nano catalyst composite membrane with conductive and catalysis, by high molecular polymer-nanometer electrical catalyst composite, the multiple roll-in on roll squeezer is obtained the Polymer/nano catalyst composite membrane, with flexility is good, light weight, catalysis activity it is high, and preparation process is simple is convenient, low cost, it is easy to large-scale production.In conductive catalytic high molecular polymer/nanocatalyst composite membrane that the present invention is provided, high molecular polymer and nanocatalyst are uniformly distributed on nanoscale, with excellent electrocatalysis characteristic and mechanical performance, long service life, electrochemical device is can be applied to, such as in fuel cell, metal-air battery, electrolytic cell, electrochemical sensor.
Description
Technical field
Constructed the invention belongs to high molecular polymer/nanocatalyst functional composite material and application field, especially
Ground is related to a kind of preparation method of the Polymer/nano catalyst composite membrane with conductive and catalysis, is applicable
In electrochemical device, such as in fuel cell, metal-air battery, electrolytic cell, electrochemical sensor.
Background technology
The catalyst of the relatively conventional size of nanocatalyst is smaller due to size, with surface atom ratio higher and
Specific surface area, therefore its catalysis activity and selectivity are much higher than the catalyst material of stock size.Polyphosphazene polymer
Compound is a class relative molecular mass 102-106Macromolecular substances above, based on high molecular polymer
Derivative obtains macromolecular material has preferable mechanical performance and chemical resistance.High molecular polymer/nanometer is urged
Agent composite can be by the dimensional stability of nanocatalyst and heat endurance, catalysis and macromolecule material
The toughness of material, machinability and corrosion resistance combine, while deriving new functional characteristic.Macromolecule is received
The functional characteristic of nano composite material be mainly shown as mechanics, calorifics, barrier property, biological function, optical photoconductor,
The field such as electricity magnetics, catalysis, anticorrosive, friction resistant, separating and filtering.
Wu and Sun etc. is by nano-TiO2Or fired as direct methanol in Pd nano-particles filleds to Nafion membrane
Material cell electrolyte film when, can effectively reduce methanol fuel from anode to negative electrode infiltration (Zhimu Wu et al.,
J.Mem.Sci.,2008,313,336-343；Hai Sun et al.,Journal of Membrane Science,2005,
259,27-33)；B Scrosati et al. are dispersed in polyethylene glycol-lithium salts by by the potter's clay powder of nano-scale
One kind polyelectrolyte containing lithium of acquisition, with good mechanical stability and ionic conductivity higher, can use
(F Croce, R Curini, the A Martinelli et al.Physical and chemical in lithium ion battery
Properties of nanocomposite polymer electrolytes, J Phys Chem
B,1999,103:10632-10638)。
But up to the present, high molecular polymer/inorganic nano composite material is generally used as the material that is electrically insulated
Expect to use, its range of application also more is limited to the fields such as engineering plastics and UF membrane, is rarely applied to electrochemistry
Catalytic field.By the content for reducing high molecular polymer in high molecular polymer/nanocatalyst composite
Electric conductivity with inorganic additive is improved, can effectively improve its electric conductivity, expand its answering in electro-catalysis field
With.Such as in fuel cell field, by will be with catalysis activity Pt and other nanometer electrical catalysts and mass ratio
After 10-30%Nafion resins uniformly mixing, spraying or brush in the conductive substrates as on carbon paper or carbon cloth,
Can serve as the Electrocatalytic Layer of fuel cell.In fuel cell Electrocatalytic Layer, one of Nafion resin functions are
Used as electrolyte conducts proton, second function is used as binding agent, and powdered nanometer electrical catalyst is bonded
Together.However, because the content of high molecular polymer Nafion in the Electrocatalytic Layer is relatively low
(10%-30%Nafion), therefore its cohesive force is small, causes the bad mechanical property of Catalytic Layer, structural stability
The phenomenons such as difference, easy chipping, scaling-off, efflorescence, the service life of battery is short.Improving polymer content can have
Effect improves its mechanical performance, however, improving Nafion contents can significantly affect the electric conductivity and electricity of Catalytic Layer
Catalysis activity, loses practical value.
The content of the invention
In view of the shortcomings of the prior art and shortcoming, the present invention proposes that one kind has good mechanical, electric conductivity concurrently and urges
Change the compound porous electro-catalysis membrane of polymer/catalyst and preparation method of function.The present invention is using side in detail below
Case is realized：
A kind of porous electro-catalysis membrane, is supported by carbon material C and hydrophobicity high molecular polymer M complex carriers C-M
Catalyst A constitute, i.e. A/C-M；Mass content with catalyst A in the porous electro-catalysis membrane for being formed is
10%-90%；The mass content of high molecular polymer M is 90%-10% in complex carrier C-M；Wherein C and M
Mass ratio be 4:1~1:4.
The catalyst A is one or two or more kinds composition in Pt, Pd, Ru, Au, Ag noble metal, or
The catalyst A be Pt, Pd, Ru, Au, Ag noble metal in one kind or two kinds with Mn, Co, Fe, Ni,
The mol ratio of one or two or more kinds composition in In non-noble metal oxides, noble metal and non-noble metal oxide
9：1~1:9；
The thickness of the porous electro-catalysis membrane is 100-1000 μm；Porosity is 5-80%.If electro-catalysis membrane mistake
Thick, porosity, is unfavorable for the infiltration of electrolyte, it is impossible to set up effective three-phase reaction interface, hinders electricity
The carrying out of catalytic reaction；It is catalyzed lepthymenia, porosity big, although be conducive to the foundation of three phase boundary, but simultaneously
A large amount of liquid electrolytes can be caused too to infiltrate catalytic membrane, flood covering catalytic active site, can equally reduce catalysis
Activity.
The electrical conductivity of the porous electro-catalysis membrane is 0.001~100S/cm.Too high electrical conductivity needs further drop
Mass content of the low high molecular polymer in film, but macromolecule content is too low, in follow-up roller membrane process hardly
Can film forming；Resistivity is too high, and the electronics conduction resistance of film is excessive, reduces the electro catalytic activity of film.
The maximum tensile strength of the porous electro-catalysis membrane is 1Mpa~5Mpa；Elongation at break is
5%-80%.If the bad mechanical property of porous electro-catalysis membrane, the easy efflorescence fracture of subsequent applications process.
The porous electro-catalysis membrane, it is characterised in that：The hydrophobicity high molecular polymer be polytetrafluoroethylene (PTFE),
One or more mixture in Kynoar, polyethylene, polystyrene；The carbon material C is work
In property charcoal, Graphene, CNT, graphene oxide, carbon nano-fiber, conductive black, electrically conductive graphite
One or more；Catalyst A is the spherical particle of particle diameter 5-50nm, catalyst A in the electro-catalysis membrane
It is uniformly distributed on complex carrier C-M.
The preparation method of the porous electro-catalysis membrane, comprises the following steps,
(1) preparation of solidliquid mixture：
Carbon material and hydrophobicity macromolecule are added in the precursor compound aqueous solution of the metal of composition catalyst
Polymer, makes it be uniformly dispersed；Reducing agent is introduced in gained mixed solution；Enter under liter high-temperature stirring condition
Row reduction reaction obtains solidliquid mixture；
The catalyst precursor compound be water-soluble nitrate, chloride, sulfate in one or two
More than；
The molar concentration of catalyst precursor compound is in the catalyst precursor compound aqueous solution
1mmoL/L-50mmoL/L；
(2) preparation of catalytic membrane base substrate：
Separation of solid and liquid carried out to above-mentioned steps (1) gained solidliquid mixture, and gained solid is dried successively,
Milled processed, obtains powdered solid substance；Solvent is added in pulverulent solids, is catalyzed through kneading roll-in
Film base substrate；
(3) preparation of porous electro-catalysis membrane：
Roll-in film forming is carried out to step (2) gained catalytic membrane base substrate, to gained roll-in film through solvent soaking after inertia
Or it is heat-treated in reducing atmosphere, obtain porous electro-catalysis membrane.
Hydrophobicity high molecular polymer described in step (1) is polytetrafluoroethylene (PTFE), Kynoar, polyethylene, poly-
One or more mixture in styrene；The carbon material C is activated carbon, Graphene, carbon nanometer
One or more in pipe, graphene oxide, carbon nano-fiber, conductive black, electrically conductive graphite；
The quality of the carbon material and hydrophobicity high molecular polymer in catalyst precursor compound solution contains
Amount is respectively 1-20g/L and 0.15-5g/L；
The reducing agent is NaBH4The aqueous solution, KBH4One kind in the aqueous solution, ascorbic acid, hydrogen or two
More than, consumption is 1-10 times (being calculated with molar concentration) of noble metal；The temperature of reaction system is 25-90
Degree Celsius, mixing speed is 600-5000rpm, time 0.5-5 hours.
Solid content in step (2) drying gained solid is 85-99%；The solvent be ethanol, water, isopropanol,
One kind in acetone；The powdered object material is 1 with the mass ratio of solvent:1~1:3；
The die opening of step (2) described roller process is 1-3mm.
The die opening being rolled into step (3) between film, the roller is 0.07-1mm；It is described immersion solvent be acetone,
One or more in ethanol, isopropanol；The heat treatment temperature is 200-400 DEG C, time 10-60 points
Clock；The inert atmosphere or reducing atmosphere are one or more in nitrogen, argon gas, helium, hydrogen
Gaseous mixture.
The porous electro-catalysis membrane can as Electrocatalytic Layer be used for fuel cell, metal-air battery, water electrolytic cell,
In electrochemical sensor.
Compared with prior art, advantage of the invention is that using one-step liquid-phase reaction by catalyst reduction, support and
Slurry with hydrophobicity high molecular polymer is realized in one pot, is reduced by preferred catalyst and slurry reacts ginseng
Number, realize nanometer electrical catalyst, activity carbon carrier and hydrophobicity high molecular polymer receive see yardstick on uniformly divide
Cloth.The content for using high molecular polymer in the porous electro-catalysis membrane of the method preparation is 10-45%, the machine of film
Tool performance is good, and catalysis activity is high.
Brief description of the drawings
Fig. 1 is the XRD diffraction patterns of the electro-catalysis membrane after heat treatment obtained in embodiment 1.
Fig. 2 is that the electro-catalysis membrane obtained in embodiment 1 is lived in 7M KOH to the electrochemical reduction of air
Property.
Fig. 3 is that the electro-catalysis membrane obtained in embodiment 2 is lived in 7M KOH to the electrochemical reduction of air
Property.
Specific embodiment
With reference to specific embodiment, the present invention is further illustrated, to be better understood from the present invention.
Embodiment 1
A kind of Polymer/nano catalyst composite membrane of conductive and catalysis, its constituent includes：Quality
Fraction is 15% PTFE and the Ag-MnO of mass fraction 30%2/ carbon elctro-catalyst
The acetylene black powder of 10.063g is weighed in three mouthfuls of glass flasks of 2L, 500ml deionized waters will be dissolved in
In 4.738g silver nitrate solutiones add three mouthfuls of glass flasks in, after dispersed with stirring 10min, continuation will be dissolved in
The potassium permanganate solution of the 4.384g in 500ml deionized waters is added, and after dispersed with stirring is uniform, will dilute 100
PTFE solution after quality times is added, and after stirring 30min, it is the NaBH of 100mM to add 200mL concentration4
The aqueous solution, maintenance system temperature is 80 DEG C, mechanical agitation 2h, maintains mixing speed to be not less than 800rpm.Instead
After should terminating, water is removed in centrifugation, is then placed in air -oven further resulting solid dough
Drying to water content is not more than 1%.By the solid abrasive after drying into fine-powdered, the deionization of the quality such as addition
After water kneading 60 times, it is placed on twin rollers, roll shaft spacing is set to 3mm, roller film temperature maintains 25 DEG C,
Thick roller 10 times is into base；The roller spacing of twin rollers is turned down successively for 1mm, 0.75mm, 0.5mm, 0.25mm and
0.15mm and 0.08mm, thin roller obtains the basement membrane that thickness is 0.10mm；The basement membrane of gained after roll-in is existed
30min is heat-treated in 300 DEG C of nitrogen ovens, conductive catalytic composite membrane is obtained.Electro-catalysis membrane after heat treatment is carried out
XRD is characterized, as a result as shown in Figure 1.The catalytic membrane after heat treatment, nanometer Ag-MnO2Catalyst shows
Stronger diffraction maximum.The conductive catalytic composite membrane is to the catalysis activity of oxygen electrochemical reduction：In 7M KOH,
When polarization potential is -0.18V (relative to HgO/Hg reference electrode), its hydrogen reduction electricity electric current is up to 50
mA/cm2, as shown in Figure 2；The maximum tensile strength of the film is 2.4Mpa, and elongation at break is 40%.
Embodiment 2
The present embodiment is with the difference of embodiment 1, the composition of the ventilative blocking solution film of conduction of the present embodiment into
Dividing includes：The Ag-MnO that mass fraction is 15% PTFE and mass fraction is 85%2/ C elctro-catalysts, this is led
Electro-catalytic composite membrane is to the catalysis activity of oxygen electrochemical reducting reaction：In 7M KOH, polarization potential is
During -0.20V (relative to HgO/Hg reference electrodes), its hydrogen reduction electricity electric current is up to 100mA/cm2；The film
Maximum tensile strength is 1.4Mpa, and elongation at break is 5%.
Embodiment 3
The present embodiment is with the difference of embodiment 1, the composition of the ventilative blocking solution film of conduction of the present embodiment into
Dividing includes：The Pt/C elctro-catalysts that mass fraction is 20% PTFE and mass fraction is 80%, wherein Pt/C electricity
The mass ratio of Pt and C is 2 in catalyst:8.The catalysis of the conductive catalytic composite membrane to oxygen electrochemical reducting reaction
Activity is：0.1M HClO4In electrolyte, when polarization potential is 0.6V (relative to saturated calomel reference electrode),
Its hydrogen reduction electricity electric current is up to 50mA/cm2；The maximum tensile strength of the film is 1.2Mpa, elongation at break
It is 20%.
Embodiment 4
The present embodiment is with the difference of embodiment 1, the composition of the ventilative blocking solution film of conduction of the present embodiment into
Dividing includes：The PtRu/C elctro-catalysts that mass fraction is 20% PTFE and mass fraction is 80%, wherein
The mass ratio of Pt, Ru and C is 30 in PtRu/C elctro-catalysts:15:65.The conductive catalytic composite membrane is to methyl alcohol electricity
Chemical oxidation reaction with catalysis activity；The maximum tensile strength of the film is 1.2Mpa, elongation at break
It is 20%.
Specific embodiment of the invention has been described in detail above, but it is intended only as example, and the present invention is simultaneously
It is not restricted to particular embodiments described above.To those skilled in the art, it is any that the present invention is carried out
Equivalent modifications and substitute also all among scope of the invention.Therefore, spirit of the invention and model are not being departed from
Enclose lower made impartial conversion and change, all should be contained within the scope of the invention.
Claims (10)
1. a kind of porous electro-catalysis membrane, it is characterised in that：By carbon material C and hydrophobicity high molecular polymer M
The catalyst A that complex carrier C-M is supported is constituted, i.e. A/C-M；The catalyst A be Pt, Pd, Ru,
In Au, Ag noble metal one or two or more kinds composition, or the catalyst A be Pt, Pd, Ru, Au,
One kind in one kind in Ag noble metals or two kinds and Mn, Co, Fe, Ni, In non-noble metal oxide or
The mol ratio 9 of more than two kinds compositions, noble metal and non-noble metal oxide：1~1:9；The porous electro-catalysis membrane
In, the mass content of catalyst A is 10%-90%；The matter of high molecular polymer M in complex carrier C-M
Amount content is 90%-10%.
2. as claimed in claim 1 porous electro-catalysis membrane, it is characterised in that：The thickness of the porous electro-catalysis membrane
Spend is 100-1000 μm；Porosity is 5-80%.
3. as claimed in claim 1 porous electro-catalysis membrane, it is characterised in that：The electricity of the porous electro-catalysis membrane
Conductance is 0.001~100S/cm.
4. as claimed in claim 1 porous electro-catalysis membrane, it is characterised in that：The porous electro-catalysis membrane is most
Big tensile strength is 1Mpa~5Mpa；Elongation at break is 5%-80%.
5. as claimed in claim 1 porous electro-catalysis membrane, it is characterised in that：The hydrophobicity high molecular polymerization
Thing is one or more mixture in polytetrafluoroethylene (PTFE), Kynoar, polyethylene, polystyrene；
The carbon material C is activated carbon, Graphene, CNT, graphene oxide, carbon nano-fiber, conduction
One or more in carbon black, electrically conductive graphite；Catalyst A is the spherical particle of particle diameter 5-50nm, institute
Catalyst A is uniformly distributed on complex carrier C-M in stating electro-catalysis membrane；The mass ratio of wherein C and M is
4:1~1:4.
6. the preparation method of any porous electro-catalysis membranes of a kind of claim 1-5, it is characterised in that：Bag
Include following steps,
(1) preparation of solidliquid mixture：
Carbon material and hydrophobicity macromolecule are added in the precursor compound aqueous solution of the metal of composition catalyst
Polymer, makes it be uniformly dispersed；Reducing agent is introduced in gained mixed solution；Enter under liter high-temperature stirring condition
Row reduction reaction obtains solidliquid mixture；
The catalyst precursor compound be water-soluble nitrate, chloride, sulfate in one or two
More than；
The molar concentration of catalyst precursor compound is in the catalyst precursor compound aqueous solution
1mmoL/L-50mmoL/L；
(2) preparation of catalytic membrane base substrate：
Separation of solid and liquid carried out to above-mentioned steps (1) gained solidliquid mixture, and gained solid is dried successively,
Milled processed, obtains powdered solid substance；Solvent is added in pulverulent solids, is catalyzed through kneading roll-in
Film base substrate；
(3) preparation of porous electro-catalysis membrane：
Roll-in film forming is carried out to step (2) gained catalytic membrane base substrate, to gained roll-in film through solvent soaking after lazy
It is heat-treated in property or reducing atmosphere, obtains porous electro-catalysis membrane.
7. as claimed in claim 6 porous electro-catalysis membrane preparation method, it is characterised in that：
Hydrophobicity high molecular polymer described in step (1) be polytetrafluoroethylene (PTFE), Kynoar, polyethylene,
One or more mixture in polystyrene；The carbon material C is activated carbon, Graphene, carbon are received
One or more in mitron, graphene oxide, carbon nano-fiber, conductive black, electrically conductive graphite；
The quality of the carbon material and hydrophobicity high molecular polymer in catalyst precursor compound solution contains
Amount is respectively 1-20g/L and 0.15-5g/L；
The reducing agent is NaBH4The aqueous solution, KBH4One kind in the aqueous solution, ascorbic acid, hydrogen or two
More than, the amount of reducing agent material is 1-10 times of precious metals species amount；The temperature of reaction system is taken the photograph for 25-90
Family name's degree, mixing speed is 600-5000rpm, time 0.5-5 hours.
8. as claimed in claim 6 porous electro-catalysis membrane preparation method, it is characterised in that：
Solid content in step (2) drying gained solid is 85-99%；The solvent be ethanol, water, isopropanol,
One kind in acetone；The powdered object material is 1 with the mass ratio of solvent:1~1:3；
The die opening of step (2) described roller process is 1-3mm.
9. the preparation method of conductive ventilative blocking solution film as claimed in claim 6, it is characterised in that：
The die opening being rolled into step (3) between film, the roller is 0.07-1mm；It is described immersion solvent be acetone,
One or more in ethanol, isopropanol；The heat treatment temperature is 200-400 DEG C, time 10-60 points
Clock；The inert atmosphere or reducing atmosphere are one or more in nitrogen, argon gas, helium, hydrogen
Gaseous mixture.
10. the application of any porous electro-catalysis membranes of a kind of claim 1-5, it is characterised in that：It is described many
Hole electro-catalysis membrane can be used for fuel cell, metal-air battery, water electrolytic cell or electrochemistry and pass as Electrocatalytic Layer
In sensor.
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