CN105789634A - Self-humidifying membrane electrode of proton exchange membrane fuel cell and preparation method for self-humidifying membrane electrode - Google Patents
Self-humidifying membrane electrode of proton exchange membrane fuel cell and preparation method for self-humidifying membrane electrode Download PDFInfo
- Publication number
- CN105789634A CN105789634A CN201410794877.2A CN201410794877A CN105789634A CN 105789634 A CN105789634 A CN 105789634A CN 201410794877 A CN201410794877 A CN 201410794877A CN 105789634 A CN105789634 A CN 105789634A
- Authority
- CN
- China
- Prior art keywords
- inorganic oxide
- catalyst
- membrane electrode
- pem
- self
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a self-humidifying membrane electrode of a proton exchange membrane fuel cell and a preparation method for the self-humidifying membrane electrode. The membrane electrode comprises a proton exchange membrane, an anode catalyst layer, a cathode catalyst layer and two gas diffusion layers, wherein the anode catalyst layer and the cathode catalyst layer are arranged on the two sides of the proton exchange membrane, or the anode catalyst layer and the cathode catalyst layer are arranged on the two gas diffusion layers respectively; the anode catalyst layer is prepared by the steps of mixing an inorganic oxide hydrolysis precursor, an organic solvent and water, and carrying out hydrolysis on the mixture by an acid solution to obtain acid sol; uniformly mixing a catalyst, a perfluorosulfonic acid resin solution and an organic solvent to obtain catalyst slurry; mixing the catalyst slurry with the acid sol, adding an alkali solution and forming a hydrophilic inorganic oxide in an in-situ reaction manner to obtain inorganic oxide turbid liquid; and spraying the inorganic oxide turbid liquid on one side of the proton exchange membrane or the gas diffusion layers to form the anode catalyst layer. The membrane electrode is simple in preparation, and the water retention capability is greatly improved, so that the normal operation of the fuel cell is ensured under a non-humidifying condition.
Description
Technical field
The invention belongs to Proton Exchange Membrane Fuel Cells technical field, be specifically related to a kind of self-humidifying proton exchange film fuel cell membrane electrode and preparation method thereof.
Background technology
Fuel cell is a kind of device that chemical energy is converted into electric energy.Wherein, Proton Exchange Membrane Fuel Cells has that start-up temperature is low, energy conversion efficiency is high, energy density is high and the advantage such as non-pollutant discharge, it is believed that be future portable power supply and the desirable power source of electric automobile.
Membrane electrode is the core component of Proton Exchange Membrane Fuel Cells, is generally made up of PEM, anode catalyst, cathod catalyst, cathode diffusion layer and anode diffusion layer.PEM needs to ensure that good wettability just can have good proton conductivity in the course of the work, if PEM overdrying, proton conductivity meeting dramatic drop-off, affects the properly functioning of Proton Exchange Membrane Fuel Cells.Therefore, for ensureing the normal operation of Proton Exchange Membrane Fuel Cells, it is necessary to assure PEM has enough water contents.
Although Proton Exchange Membrane Fuel Cells work process also can produce water, but current conventional membrane electrode structure is poor due to water holding capacity, gas must be carried out the properly functioning of humidification guarantee pile, but no matter be interior humidification or outer humidification mode, all need to use humidification auxiliary device, can substantially increase the cost of battery system, quality and volume, cause the volume of pile and quality to reduce than power.
Self-humidification is the main flow of research at present, but current self-humidification mostly is and hydrophilic powder or Organic substance such as perfluorinated sulfonic resin etc. are directly added into Catalytic Layer, and dispersing uniformity is poor, poor from moisturization effect.
Summary of the invention
It is an object of the invention to the deficiency for current self-humidifying method, hydrophilic nanoparticles is prepared by in-situ synthetic method, thus realizing hydrophilic granules being uniformly distributed in catalyst layer, be obviously improved membrane electrode from humidifying capacity, and by adjusting the component in solution, can conveniently regulate the hydrophilic ability adding hydrophilic granules, it is simple to from the adjustment of humidifying capacity.
For achieving the above object, the present invention is by the following technical solutions:
A kind of self-humidifying proton exchange film fuel cell membrane electrode, it is made up of PEM, anode catalyst layer, cathode catalysis layer and two gas diffusion layers, PEM is folded between two gas diffusion layers, is respectively arranged with anode catalyst layer and cathode catalysis layer between the both sides and gas diffusion layers of PEM；Described anode catalyst layer and cathode catalysis layer are separately positioned on the both sides on PEM, or described anode catalyst layer and cathode catalysis layer are separately positioned on two gas diffusion layers；
Wherein, described anode catalyst layer is prepared by following methods: inorganic oxide is hydrolyzed presoma, organic solvent and water mixing, it is 1:1～100:1～8 that described inorganic oxide is hydrolyzed the mol ratio of presoma, organic solvent and water, regulates pH to 1～3 hydrolysis with acid solution and obtains acid-sol in 1～48 hour；Catalyst, perfluor sulfoacid resin solution and organic solvent are obtained catalyst pulp according to the quality of 1:2～5:50～100 than mix homogeneously；Catalyst pulp is mixed with acid-sol, it is dispersed into suspension through ultrasonic wave concussion, in suspension, add aqueous slkali regulate pH to 9～13, in-situ preparation hydrophilic inorganic oxide, obtain inorganic oxide suspension, inorganic oxide suspension being sprayed at PEM side or gas diffusion layers forms anode catalyst layer, wherein the carrying capacity of anode catalyst layer platinum is 0.1～10mg cm-1；
Described cathode catalysis layer is prepared by following methods: inorganic oxide is hydrolyzed presoma, organic solvent and water mixing, it is 1:1～100:1～8 that described inorganic oxide is hydrolyzed the mol ratio of presoma, organic solvent and water, regulates pH to 1～3 hydrolysis with acid solution and obtains acid-sol in 1～48 hour；Catalyst, perfluor sulfoacid resin solution and organic solvent are obtained catalyst pulp according to the quality of 1:2～5:50～100 than mix homogeneously；Catalyst pulp is mixed with acid-sol, it is dispersed into suspension through ultrasonic wave concussion, in suspension, add aqueous slkali regulate pH to 9～13, in-situ preparation hydrophilic inorganic oxide, obtain inorganic oxide suspension, inorganic oxide suspension is sprayed at PEM side or gas diffusion layers forms anode catalyst layer；Or catalyst pulp is sprayed at PEM opposite side or gas diffusion layers forms cathode catalysis layer；Wherein the carrying capacity of cathode catalysis layer platinum is 0.1～10mg cm-1。
Described inorganic oxide is hydrolyzed the mol ratio of presoma, organic solvent and water and is preferably 1:30～36:2～5.
Described inorganic oxide hydrolysis presoma is one or more mixing in tetraethyl orthosilicate, Silicon chloride. or butyl titanate.
Described acid solution is dust technology, dilute sulfuric acid or dilute hydrochloric acid, it is preferred to 0.05mol/L salpeter solution.
Described catalyst is carbon supported platinum catalyst, and described carbon supported platinum catalyst is the carbon supported platinum catalyst of platinum loading 50～70%.Described perfluor sulfoacid resin solution is the perfluor sulfoacid resin solution of mass fraction 5%.
Described catalyst pulp mixes with acid-sol equal-volume.
Described aqueous slkali is ammonia or sodium hydroxide solution, and the mass percent of described ammonia is 1～10%, the concentration 0.1～5mol/L of described sodium hydroxide solution.
Described organic solvent is dehydrated alcohol or isopropanol.
The preparation method that it is a further object to provide self-humidifying proton exchange film fuel cell membrane electrode, comprises the following steps:
(1), by PEM washes clean, flatten standby after drying；
(2), inorganic oxide is hydrolyzed presoma, organic solvent and water mixing, it is 1:1～100:1～8 that described inorganic oxide is hydrolyzed the mol ratio of presoma, organic solvent and water, regulates pH to 1～3 hydrolysis with acid solution and obtains acid-sol in 1～48 hour；
(3), catalyst, perfluor sulfoacid resin solution and organic solvent are obtained catalyst pulp according to the quality of 1:2～5:50～100 than mix homogeneously；
(4), the acid-sol that the catalyst pulp that step (3) prepares is prepared with step (2) is mixed, it is dispersed into suspension through ultrasonic wave concussion, in suspension, add aqueous slkali regulate pH to 9～13, in-situ preparation hydrophilic inorganic oxide, obtain inorganic oxide suspension, inorganic oxide suspension being sprayed at PEM side or gas diffusion layers forms anode catalyst layer, wherein the carrying capacity of anode catalyst layer platinum is 0.1～10mg cm-1；
(5), the catalyst pulp that step (3) prepares is sprayed at PEM opposite side or gas diffusion layers forms cathode catalysis layer；Or the inorganic oxide suspension that step (4) prepares is sprayed at PEM opposite side or gas diffusion layers formation cathode catalysis layer；Wherein the carrying capacity of cathode catalysis layer platinum is 0.1～10mg cm-1
(6), by two ready made gas diffusion layers being pressed together on respectively sprays by the PEM both sides of cathode and anode Catalytic Layer, prepares membrane electrode；
Or the gas diffusion layers being coated with cathode and anode Catalytic Layer respectively is pressed together on PEM both sides, prepares membrane electrode.
In step (1), described PEM is Nafion212, Nafion211 film or the Nafion117 film of DuPont's production.Preferably employing distilled water or dilute acid soln washing PEM, described dilute acid soln can be 0.1mol.L-1Sulfuric acid solution.
In step (2), described inorganic oxide is hydrolyzed the mol ratio of presoma, organic solvent and water and is preferably 1:30～36:2～5.
Described inorganic oxide hydrolysis presoma is one or more mixing in tetraethyl orthosilicate, Silicon chloride. or butyl titanate；Described inorganic oxide is SiO2Or TiO2；Described acid solution is dust technology, dilute sulfuric acid or dilute hydrochloric acid, it is preferred to 0.05mol/L salpeter solution.
In step (3), described catalyst is carbon supported platinum catalyst, and described carbon supported platinum catalyst is the carbon supported platinum catalyst of platinum loading 50～70%.Described perfluor sulfoacid resin solution is the perfluor sulfoacid resin solution of mass fraction 5%.
In step (4), described catalyst pulp mixes with acid-sol equal-volume.
Described aqueous slkali is ammonia or sodium hydroxide solution, and the mass percent of described ammonia is 1～10%, the concentration 0.1～5mol/L of described sodium hydroxide solution.
Heretofore described organic solvent is dehydrated alcohol or isopropanol.
Compared to the prior art, beneficial effects of the present invention:
Self-humidifying proton exchange film fuel cell membrane electrode of the present invention preparation is simple, inorganic oxide hydrolysis precursor generates through hydrolysis and in-situ synthetic method and forms hydrophilic inorganic oxide (silicon dioxide, titanium dioxide) nano-particle, inorganic oxide nanoparticles is uniformly distributed between catalyst granules and catalyst granules internal void place, keep moisture ability be obviously improved, thereby may be ensured that without humidification when fuel cell properly functioning.
Accompanying drawing explanation
Fig. 1 illustrates the broken away view of first embodiment of the self-humidifying proton exchange film fuel cell membrane electrode in the present invention；
Fig. 2 illustrates the broken away view of second embodiment of the self-humidifying proton exchange film fuel cell membrane electrode in the present invention；
In figure, 1-PEM, 2-gas diffusion layers, 3-anode catalyst layer, 4-cathode catalysis layer.
Detailed description of the invention
Below by way of detailed description of the invention, technical scheme is described further.
Embodiment 1
A kind of self-humidifying proton exchange film fuel cell membrane electrode, is prepared by following preparation method, comprises the following steps:
(1), with distilled water by nafion211 PEM washes clean, flatten standby after drying；
(2), by 2.08g tetraethyl orthosilicate and 13.8g dehydrated alcohol, the mixing of 0.72ml distilled water, regulating pH to 2 with 0.05mol/L sulfuric acid solution, place 24 hours after stirring, hydrolysis obtains acid-sol；
(3), taking 1g carbon supported platinum catalyst (platinum loading of carbon supported platinum catalyst is 70%), 5g mass fraction 5% perfluor sulfoacid resin solution and 60g isopropanol, mix homogeneously obtains catalyst pulp；
(4), the acid-sol equal-volume that the catalyst pulp that step (3) prepares is prepared with step (2) is mixed, it is dispersed into suspension through ultrasonic wave concussion, in suspension, add 10% ammonia regulate pH to 9, in-situ preparation hydrophilic inorganic oxide S iO2, it is thus achieved that inorganic oxide suspension, under infrared lamp irradiates, inorganic oxide suspension is sprayed at PEM side, forms anode catalyst layer, wherein the carrying capacity of Pt is 0.5mg cm-1；
(5), taking the catalyst pulp that step (3) prepares, under infrared lamp irradiates, be sprayed at the PEM opposite side that step (4) has sprayed, form cathode catalysis layer, wherein the carrying capacity of Pt is 0.5mg cm-1；
(6), two ready made gas diffusion layers are pressed together on by the PEM both sides of cathode and anode Catalytic Layer respectively, prepare membrane electrode.
The anode catalyst layer that step (4) prepares, observes with transmission electron microscope, and inorganic oxide particles mean diameter is 12nm, and inorganic oxide particles is evenly distributed on Catalytic Layer catalyst neutralisation granule internal void.
The membrane electrode assembly prepared dresses up monocell, (battery performance test condition is as follows: fuel gas is hydrogen, and oxidant is that air, hydrogen and air are not humidified for air cooling condition, battery temperature is 50 DEG C) under carry out IV curve test, electric current density 300mA/cm2Under condition, cell voltage is 0.67V.
Embodiment 2
A kind of self-humidifying proton exchange film fuel cell membrane electrode, is prepared by following preparation method, comprises the following steps:
(1), with 0.05mol/L dilute sulfuric acid by nafion211 PEM washes clean, flatten standby after drying；
(2), by 2.08g tetraethyl orthosilicate and 13.8g dehydrated alcohol, the mixing of 0.72ml distilled water, regulating pH to 2 with 0.05mol/L sulfuric acid solution, place 24 hours after stirring, hydrolysis obtains acid-sol；
(3), taking 1g carbon supported platinum catalyst (platinum loading of carbon supported platinum catalyst is 70%), the perfluorinated sulfonic resin of 5g mass fraction 5% and 60g isopropanol, mix homogeneously obtains catalyst pulp；
(4), the acid-sol equal-volume that the catalyst pulp that step (3) prepares is prepared with step (2) is mixed, it is dispersed into suspension through ultrasonic wave concussion, in suspension, add 10% ammonia regulate pH to 9, in-situ preparation hydrophilic inorganic oxide S iO2, it is thus achieved that inorganic oxide suspension, under infrared lamp irradiates, inorganic oxide suspension is sprayed at PEM side, forms anode catalyst layer, wherein the carrying capacity of Pt is 0.5mg cm-1；
(5), taking the catalyst pulp that step (3) prepares, under infrared lamp irradiates, be sprayed at the PEM opposite side that step (4) has sprayed, form cathode catalysis layer, wherein the carrying capacity of Pt is 0.4mg cm-1；
(6), two ready made gas diffusion layers are pressed together on by the PEM both sides of cathode and anode Catalytic Layer respectively, prepare membrane electrode.
The anode catalyst layer that step (4) prepares, observes with transmission electron microscope, and inorganic oxide particles mean diameter is 12nm, and inorganic oxide particles is evenly distributed on Catalytic Layer catalyst neutralisation granule internal void.
The membrane electrode assembly prepared dresses up monocell, (battery performance test condition is as follows: fuel gas is hydrogen, and oxidant is that air, hydrogen and air are not humidified for air cooling condition, battery temperature is 50 DEG C) under carry out IV curve test, electric current density 300mA/cm2Under condition, cell voltage is 0.66V.
Embodiment 3
A kind of self-humidifying proton exchange film fuel cell membrane electrode, is prepared by following preparation method, comprises the following steps:
(1), with distilled water by nafion211 PEM washes clean, flatten standby after drying；
(2), by 1.42g Silicon chloride. and 13.8g dehydrated alcohol, the mixing of 0.72ml distilled water, regulating pH to 2 with 0.05mol/L sulfuric acid solution, place 24 hours after stirring, hydrolysis obtains acid-sol；
(3), taking 1g carbon supported platinum catalyst (platinum loading of carbon supported platinum catalyst is 70%), the perfluorinated sulfonic resin of 5g mass fraction 5% and 60g isopropanol, mix homogeneously obtains catalyst pulp；
(4), the acid-sol equal-volume that the catalyst pulp that step (3) prepares is prepared with step (2) is mixed, it is dispersed into suspension through ultrasonic wave concussion, in suspension, add 1mol/L sodium hydroxide solution regulate pH to 11, in-situ preparation hydrophilic inorganic oxide S iO2, it is thus achieved that inorganic oxide suspension, under infrared lamp irradiates, inorganic oxide suspension is sprayed at PEM side, forms anode catalyst layer, wherein the carrying capacity of Pt is 0.5mg cm-1；
(5), taking the catalyst pulp that step (3) prepares, under infrared lamp irradiates, be sprayed at the PEM opposite side that step (4) has sprayed, form cathode catalysis layer, wherein the carrying capacity of Pt is 0.4mg cm-1；
(6), two ready made gas diffusion layers are pressed together on by the PEM both sides of cathode and anode Catalytic Layer respectively, prepare membrane electrode.
The anode catalyst layer that step (4) prepares, observes with transmission electron microscope, and inorganic oxide particles mean diameter is 14nm, and inorganic oxide particles is evenly distributed on Catalytic Layer catalyst neutralisation granule internal void.
The membrane electrode assembly prepared dresses up monocell, (battery performance test condition is as follows: fuel gas is hydrogen, and oxidant is that air, hydrogen and air are not humidified for air cooling condition, battery temperature is 50 DEG C) under carry out IV curve test, electric current density 300mA/cm2Under condition, cell voltage is 0.65V.
Embodiment 4
A kind of self-humidifying proton exchange film fuel cell membrane electrode, is prepared by following preparation method, comprises the following steps:
(1), with distilled water by nafion211 PEM washes clean, flatten standby after drying；
(2), by 1.42g Silicon chloride. and 13.8g dehydrated alcohol, the mixing of 0.72ml distilled water, regulating pH to 2 with 0.05mol/L sulfuric acid solution, place 24 hours after stirring, hydrolysis obtains acid-sol；
(3), taking 1g carbon supported platinum catalyst (platinum loading of carbon supported platinum catalyst is 70%), the perfluorinated sulfonic resin of 5g mass fraction 5% and 60g isopropanol, mix homogeneously obtains catalyst pulp；
(4), the acid-sol equal-volume that the catalyst pulp that step (3) prepares is prepared with step (2) is mixed, it is dispersed into suspension through ultrasonic wave concussion, in suspension, add 1mol/L sodium hydroxide solution regulate pH to 11, in-situ preparation hydrophilic inorganic oxide S iO2, it is thus achieved that inorganic oxide suspension, under infrared lamp irradiates, inorganic oxide suspension is sprayed at PEM side, forms anode catalyst layer, wherein the carrying capacity of Pt is 0.5mg cm-1；
(5), take the acid-sol equal-volume prepared with step (2) of catalyst pulp that step (3) prepares to mix, it is dispersed into suspension through ultrasonic wave concussion, in suspension, add 1mol/L sodium hydroxide solution regulate pH to 11, in-situ preparation hydrophilic inorganic oxide S iO2, it is thus achieved that inorganic oxide suspension, under infrared lamp irradiates, it is sprayed at the PEM opposite side that step (4) has sprayed, forms cathode catalysis layer, wherein the carrying capacity of Pt is 0.4mg cm-1；
(6), two ready made gas diffusion layers are pressed together on by the PEM both sides of cathode and anode Catalytic Layer respectively, prepare membrane electrode.
Step (4) prepare anode catalyst layer and step (5) prepare cathode catalysis layer transmission electron microscope observe, inorganic oxide particles mean diameter is 13nm, and inorganic oxide particles is evenly distributed on Catalytic Layer catalyst neutralisation granule internal void.
The membrane electrode assembly prepared dresses up monocell, (battery performance test condition is as follows: fuel gas is hydrogen, and oxidant is that air, hydrogen and air are not humidified for air cooling condition, battery temperature is 50 DEG C) under carry out IV curve test, electric current density 300mA/cm2Under condition, cell voltage is 0.68V.
Comparative example 1
A kind of self-humidifying proton exchange film fuel cell membrane electrode, is prepared by following preparation method, comprises the following steps:
(1), with distilled water by PEM washes clean, flatten standby after drying；
(2), 0.6gSiO is taken2, 13.8g dehydrated alcohol, 0.72ml distilled water, prepare suspension, take 1g carbon supported platinum catalyst (platinum loading of carbon supported platinum catalyst is 70%), the perfluor sulfoacid resin solution of 5g mass fraction 5% and 60g isopropanol and be mixed with slurry, both equal-volume mixing, obtain Anode inks through ultrasonic wave concussion dispersion, under infrared lamp irradiates, catalyst pulp is sprayed at PEM side, forming anode catalyst layer, wherein the carrying capacity of Pt is 0.5mg cm-1；
(3) 1g carbon supported platinum catalyst (platinum loading of carbon supported platinum catalyst is 70%), the perfluor sulfoacid resin solution of mass fraction 5% and the mixing of 60g isopropanol, are taken, cathode inks is obtained through ultrasonic wave concussion dispersion, under infrared lamp irradiates, this catalyst pulp is sprayed at the PEM opposite side that step (2) has sprayed, forming cathode catalysis layer, wherein the carrying capacity of Pt is 0.5mg cm-1；
(4), two ready made gas diffusion layers are pressed together on by the PEM both sides of cathode and anode Catalytic Layer respectively, prepare membrane electrode.
The anode catalyst layer that step (4) prepares, observes with transmission electron microscope, and inorganic oxide particles mean diameter is 20nm, and inorganic oxide particles is evenly distributed in Catalytic Layer, and catalytic inner space is not generally visible.
The membrane electrode assembly prepared dresses up monocell, (battery performance test condition is as follows: fuel gas is hydrogen, and oxidant is that air, hydrogen and air are not humidified for air cooling condition, battery temperature is 50 DEG C) under carry out IV curve test, electric current density 300mA/cm2Under condition, battery value is 0.60V.
Not under humidification conditions, surveying large quantity of moisture due to air and scatter and disappear, PEM can become dry, and cell voltage can decline.When same test, according to different membrane electrode magnitudes of voltage under fixed current density, it can be seen that membrane electrode keeps the power of moisture ability, under air cooling condition, membrane electrode keeps moisture ability more good, and PEM exsiccation trend is more inconspicuous, and cell voltage is more high.By the IV curve test result of embodiment 1-4 and comparative example 1 it can be seen that at electric current density 300mA/cm2Under condition, the membrane electrode of embodiment 1-4 assembles the voltage (respectively 0.67V, 0.66V, 0.65V, 0.68V) of the battery obtained and assembles the voltage (0.60V) of the battery obtained higher than the membrane electrode of comparative example 1, at least improve 8%, illustrate that the water holding capacity of the membrane electrode of the present invention is substantially better than the membrane electrode conventionally prepared, it is ensured that fuel cell is properly functioning without humidification when.
Claims (10)
1. a self-humidifying proton exchange film fuel cell membrane electrode, it is made up of PEM, anode catalyst layer, cathode catalysis layer and two gas diffusion layers, PEM is folded between two gas diffusion layers, is respectively arranged with anode catalyst layer and cathode catalysis layer between the both sides and gas diffusion layers of PEM；Described anode catalyst layer and cathode catalysis layer are separately positioned on the both sides on PEM, or described anode catalyst layer and cathode catalysis layer are separately positioned on two gas diffusion layers；
It is characterized in that described anode catalyst layer is prepared by following methods: inorganic oxide is hydrolyzed presoma, organic solvent and water mixing, it is 1:1～100:1～8 that described inorganic oxide is hydrolyzed the mol ratio of presoma, organic solvent and water, regulates pH to 1～3 hydrolysis with acid solution and obtains acid-sol in 1～48 hour；Catalyst, perfluor sulfoacid resin solution and organic solvent are obtained catalyst pulp according to the quality of 1:2～5:50～100 than mix homogeneously；Catalyst pulp is mixed with acid-sol, it is dispersed into suspension through ultrasonic wave concussion, aqueous slkali is added in suspension, in-situ preparation hydrophilic inorganic oxide, obtain inorganic oxide suspension, inorganic oxide suspension being sprayed at PEM side or gas diffusion layers forms anode catalyst layer, wherein the carrying capacity of anode catalyst layer platinum is 0.1～10mg cm-2；
Described cathode catalysis layer is prepared by following methods: inorganic oxide is hydrolyzed presoma, organic solvent and water mixing, it is 1:1～100:1～8 that described inorganic oxide is hydrolyzed the mol ratio of presoma, organic solvent and water, regulates pH to 1～3 hydrolysis with acid solution and obtains acid-sol in 1～48 hour；Catalyst, perfluor sulfoacid resin solution and organic solvent are obtained catalyst pulp according to the quality of 1:2～5:50～100 than mix homogeneously；Catalyst pulp is mixed with acid-sol, it is dispersed into suspension through ultrasonic wave concussion, in suspension, add aqueous slkali regulate pH to 9～13, in-situ preparation hydrophilic inorganic oxide, obtain inorganic oxide suspension, inorganic oxide suspension is sprayed at PEM side or gas diffusion layers forms anode catalyst layer；Or catalyst pulp being sprayed at PEM opposite side or gas diffusion layers forms cathode catalysis layer, wherein the carrying capacity of cathode catalysis layer platinum is 0.1～10mg cm-1。
2. self-humidifying proton exchange film fuel cell membrane electrode according to claim 1, it is characterised in that it is 1:30～36:2～5 that described inorganic oxide is hydrolyzed the mol ratio of presoma, organic solvent and water.
3. self-humidifying proton exchange film fuel cell membrane electrode according to claim 1, it is characterised in that described inorganic oxide hydrolysis presoma is one or more mixing in tetraethyl orthosilicate, Silicon chloride. or butyl titanate；
Described acid solution is dust technology, dilute sulfuric acid or dilute hydrochloric acid, it is preferred to 0.05mol/L salpeter solution；
Described catalyst is carbon supported platinum catalyst, and described carbon supported platinum catalyst is the carbon supported platinum catalyst of platinum loading 50～70%；
Described perfluor sulfoacid resin solution is the perfluor sulfoacid resin solution of mass fraction 5%；
Described aqueous slkali is ammonia or sodium hydroxide solution, and the mass percent of described ammonia is 1～10%, the concentration 0.1～5mol/L of described sodium hydroxide solution；
Described organic solvent is dehydrated alcohol or isopropanol.
4. self-humidifying proton exchange film fuel cell membrane electrode according to claim 1, it is characterised in that described catalyst pulp mixes with acid-sol equal-volume.
5. the preparation method of the self-humidifying proton exchange film fuel cell membrane electrode described in claim 1, it is characterised in that it comprises the following steps:
(1), by PEM washes clean, flatten standby after drying；
(2), inorganic oxide is hydrolyzed presoma, organic solvent and water mixing, it is 1:1～100:1～8 that described inorganic oxide is hydrolyzed the mol ratio of presoma, organic solvent and water, regulates pH to 1～3 hydrolysis with acid solution and obtains acid-sol in 1～48 hour；
(3), catalyst, perfluor sulfoacid resin solution and organic solvent are obtained catalyst pulp according to the quality of 1:2～5:50～100 than mix homogeneously；
(4), the acid-sol that the catalyst pulp that step (3) prepares is prepared with step (2) is mixed, it is dispersed into suspension through ultrasonic wave concussion, in suspension, add aqueous slkali regulate pH to 9～13, in-situ preparation hydrophilic inorganic oxide, obtain inorganic oxide suspension, inorganic oxide suspension being sprayed at PEM side or gas diffusion layers forms anode catalyst layer, wherein the carrying capacity of anode catalyst layer platinum is 0.1～10mg cm-1；
(5), the catalyst pulp that step (3) prepares is sprayed at PEM opposite side or gas diffusion layers forms cathode catalysis layer；Or the inorganic oxide suspension that step (4) prepares is sprayed at PEM opposite side or gas diffusion layers formation cathode catalysis layer；Wherein the carrying capacity of cathode catalysis layer platinum is 0.1～10mg cm-1
(6), by two ready made gas diffusion layers being pressed together on respectively sprays by the PEM both sides of cathode and anode Catalytic Layer, prepares membrane electrode；
Or the gas diffusion layers being coated with cathode and anode Catalytic Layer respectively is pressed together on PEM both sides, prepares membrane electrode.
6. the preparation method of self-humidifying proton exchange film fuel cell membrane electrode according to claim 5, it is characterised in that the mol ratio of the inorganic oxide hydrolysis presoma described in step (2), organic solvent and water is 1:30～36:2～5.
7. the preparation method of self-humidifying proton exchange film fuel cell membrane electrode according to claim 5, it is characterised in that the inorganic oxide hydrolysis presoma described in step (2) is one or more mixing in tetraethyl orthosilicate, Silicon chloride. or butyl titanate；
Described acid solution is dust technology, dilute sulfuric acid or dilute hydrochloric acid, it is preferred to 0.05mol/L salpeter solution.
8. the preparation method of self-humidifying proton exchange film fuel cell membrane electrode according to claim 5, it is characterized in that the catalyst described in step (3) is carbon supported platinum catalyst, described carbon supported platinum catalyst is the carbon supported platinum catalyst of platinum loading 50～70%；
Described perfluor sulfoacid resin solution is the perfluor sulfoacid resin solution of mass fraction 5%；
Described aqueous slkali is ammonia or sodium hydroxide solution, and the mass percent of described ammonia is 1～10%, and the concentration of described sodium hydroxide solution is 0.1～5mol/L.
9. the preparation method of self-humidifying proton exchange film fuel cell membrane electrode according to claim 5, it is characterised in that in step (4), described catalyst pulp mixes with acid-sol equal-volume.
10. the preparation method of self-humidifying proton exchange film fuel cell membrane electrode according to claim 5, it is characterised in that described organic solvent is dehydrated alcohol or isopropanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410794877.2A CN105789634B (en) | 2014-12-18 | 2014-12-18 | A kind of self-humidifying proton exchange film fuel cell membrane electrode and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410794877.2A CN105789634B (en) | 2014-12-18 | 2014-12-18 | A kind of self-humidifying proton exchange film fuel cell membrane electrode and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105789634A true CN105789634A (en) | 2016-07-20 |
| CN105789634B CN105789634B (en) | 2018-09-14 |
Family
ID=56385521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410794877.2A Active CN105789634B (en) | 2014-12-18 | 2014-12-18 | A kind of self-humidifying proton exchange film fuel cell membrane electrode and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105789634B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111755725A (en) * | 2020-06-17 | 2020-10-09 | 鄂尔多斯市国科能源有限公司 | Membrane electrode assembly comprising self-crosslinking ionic polymer and method for preparing same |
| CN112786937A (en) * | 2021-01-27 | 2021-05-11 | 浙江高成绿能科技有限公司 | Fuel cell membrane electrode and preparation method thereof |
| CN113564633A (en) * | 2021-07-29 | 2021-10-29 | 阳光电源股份有限公司 | Water electrolysis membrane electrode, preparation method thereof and electrolytic cell |
| CN113851682A (en) * | 2021-09-24 | 2021-12-28 | 上海交通大学 | Preparation method of solid acid fuel cell supplied by general fuel |
| CN113851684A (en) * | 2021-09-24 | 2021-12-28 | 上海交通大学 | Solid acid salt, solid acid proton exchange membrane and preparation method |
| CN115029728A (en) * | 2022-07-01 | 2022-09-09 | 上海岚泽能源科技有限公司 | Catalyst slurry, preparation method and application thereof, and hydrogen electrochemical compressor |
| CN117577906A (en) * | 2023-12-16 | 2024-02-20 | 杭州质子动力有限公司 | Self-humidifying membrane electrode of air-cooled fuel cell and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1725536A (en) * | 2005-06-08 | 2006-01-25 | 广州市培源燃料电池有限公司 | Self-moist proton exchange film and its preparation method |
| CN101034748A (en) * | 2007-03-29 | 2007-09-12 | 武汉理工大学 | Making method for core component of water-reservation proton exchange film fuel battery |
-
2014
- 2014-12-18 CN CN201410794877.2A patent/CN105789634B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1725536A (en) * | 2005-06-08 | 2006-01-25 | 广州市培源燃料电池有限公司 | Self-moist proton exchange film and its preparation method |
| CN101034748A (en) * | 2007-03-29 | 2007-09-12 | 武汉理工大学 | Making method for core component of water-reservation proton exchange film fuel battery |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111755725A (en) * | 2020-06-17 | 2020-10-09 | 鄂尔多斯市国科能源有限公司 | Membrane electrode assembly comprising self-crosslinking ionic polymer and method for preparing same |
| CN111755725B (en) * | 2020-06-17 | 2021-11-26 | 鄂尔多斯市国科能源有限公司 | Membrane electrode assembly comprising self-crosslinking ionic polymer and method for preparing same |
| CN112786937A (en) * | 2021-01-27 | 2021-05-11 | 浙江高成绿能科技有限公司 | Fuel cell membrane electrode and preparation method thereof |
| CN112786937B (en) * | 2021-01-27 | 2022-03-15 | 浙江高成绿能科技有限公司 | Fuel cell membrane electrode and preparation method thereof |
| CN113564633A (en) * | 2021-07-29 | 2021-10-29 | 阳光电源股份有限公司 | Water electrolysis membrane electrode, preparation method thereof and electrolytic cell |
| CN113851682A (en) * | 2021-09-24 | 2021-12-28 | 上海交通大学 | Preparation method of solid acid fuel cell supplied by general fuel |
| CN113851684A (en) * | 2021-09-24 | 2021-12-28 | 上海交通大学 | Solid acid salt, solid acid proton exchange membrane and preparation method |
| CN115029728A (en) * | 2022-07-01 | 2022-09-09 | 上海岚泽能源科技有限公司 | Catalyst slurry, preparation method and application thereof, and hydrogen electrochemical compressor |
| CN117577906A (en) * | 2023-12-16 | 2024-02-20 | 杭州质子动力有限公司 | Self-humidifying membrane electrode of air-cooled fuel cell and preparation method thereof |
| CN117577906B (en) * | 2023-12-16 | 2024-05-03 | 杭州质子动力有限公司 | Self-humidifying membrane electrode of air-cooled fuel cell and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105789634B (en) | 2018-09-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105789634A (en) | Self-humidifying membrane electrode of proton exchange membrane fuel cell and preparation method for self-humidifying membrane electrode | |
| CN106784943B (en) | A kind of membrane electrode of fuel batter with proton exchange film of high power density and preparation method thereof | |
| CN103050661B (en) | Lithium ion battery cathode material compounded with graphene and preparation method thereof | |
| US20120107719A1 (en) | Electrode catalyst for membrane electrode of fuel cell and its method of preparation and fuel cell membrane electrode | |
| CN103441287A (en) | Preparation method of membrane electrode of direct methanol fuel cell | |
| CN108579818B (en) | Preparation method of solid polymer electrolyte water electrolysis membrane electrode catalyst slurry | |
| CN105118977B (en) | V with the three-dimensional winding arrangement of nano wire2O5Hollow micron thread ball and its preparation method and application | |
| CN103657648A (en) | Preparation method of fuel-cell catalyst Pt/WO3/C | |
| CN104787799B (en) | Web-type three-dimensional perforated macroporous-mesoporous-structure titanium dioxide material, and preparation method and application thereof | |
| CN106058276A (en) | Preparation method of silica-modified multi-spherical-cavity carbon material and application of carbon material to fuel cell membrane electrode | |
| Bao et al. | Effects of nano-SiO2 doped PbO2 as the positive electrode on the performance of lead-carbon hybrid capacitor | |
| CN100454636C (en) | Making method for core component of water-reservation proton exchange film fuel battery | |
| CN105375008A (en) | Laminated Na3V2(PO4)3@rGo nanocomposite and preparation method and application therefor | |
| CN104538647A (en) | Lithium-air battery catalyst and preparation method thereof | |
| CN109273732A (en) | A kind of cobalt cladding carbon supported platinum catalyst and preparation method thereof with proton transport function | |
| CN100517841C (en) | Method for preparing water-keeping diffusion layer of high temperature proton exchange film fuel cell | |
| CN104393312A (en) | Preparation method of ultralow platinum-loading capacity Pt-CoP/C anode electrocatalyst for high-activity high-stability direct methanol fuel cell | |
| CN113871633B (en) | Method for efficiently activating membrane electrode of proton exchange membrane fuel cell in situ | |
| KR20130059343A (en) | Proton exchange membrane fuel cell electrode structuration | |
| CN103367768B (en) | A kind of method preparing double-catalyst-layestructure structure of proton exchange membrane fuel cell | |
| JP5428493B2 (en) | Method for producing polymer electrolyte fuel cell | |
| CN104815682A (en) | High-dispersion supported palladium/tungsten carbide catalyst and preparation method thereof | |
| JP4709477B2 (en) | Method for producing electrode catalyst for fuel cell | |
| CN100483814C (en) | Method for preparation of membrane electrode of water-keeping proton exchange film fuel cells | |
| CN107069049B (en) | A kind of mesoporous polypyrrole nano-rings loaded Pt catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |