CN112072120B - Hydrophilic/hydrophobic membrane electrode relating to ionic liquid - Google Patents
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Abstract
The invention belongs to the technical field of membrane electrode preparation, in particular to a hydrophilic/hydrophobic membrane electrode of ionic liquid, which relates to a hydrophilic/hydrophobic membrane electrode of ionic liquid, wherein an anode catalyst layer is prepared from hydrophilic proton type ionic liquid and a catalyst, and a cathode catalyst layer is prepared from hydrophobic and hydrophilic proton type ionic liquid and a catalyst, the invention uses ionic liquid with special physicochemical characteristics as a raw material for preparing the catalyst layer to prepare a self-humidifying membrane electrode, effectively solves the problem of charge transfer resistance increase caused by inorganic oxide as an additive for preparing the self-humidifying membrane electrode, because the ionic liquid selected by the invention has negligible volatility, the ionic transmission capability and the stability of the membrane electrode are greatly improved, and meanwhile, the hydrophobic ionic liquid can be adsorbed into a catalyst pore channel under the high vacuum condition through a continuous vacuum pumping process, so that the ionic liquid can be uniformly dispersed on all surfaces of the catalyst.
Description
Technical Field
The invention belongs to the technical field of membrane electrode preparation, and particularly relates to a hydrophilic/hydrophobic membrane electrode relating to ionic liquid.
Background
The membrane electrode is used as a key component in the hydrogen-oxygen fuel cell stack and plays a decisive role in the performance of the fuel cell stack, the membrane electrode consists of a cathode catalyst layer and an anode catalyst layer and a proton exchange membrane, the catalyst layer and the proton exchange membrane are key composition materials of the membrane electrode, the catalyst layer plays a role in accelerating oxygen reduction reaction, the proton exchange membrane plays a role in isolating electrons and transmitting protons, the proton exchange membrane is used as a proton-conducting perfluorosulfonic acid polymer, the proton transmission capability of the proton exchange membrane depends on the hydration degree of the proton exchange membrane seriously, therefore, reaction gas needs to be humidified to keep a good hydration state of the proton exchange membrane, so that the high proton transmission efficiency of the membrane and the electrode is maintained, generally humidification equipment is adopted to humidify the reaction gas, but the humidification equipment increases the complexity, the quality, the volume and the cost of the system. This therefore makes the use of self-humidifying membrane electrodes essential in hydrogen-oxygen fuel cells.
Currently, most of the self-humidifying membrane electrode preparation technologies adopt hydrophilic inorganic oxide mixed with catalyst as an anode catalytic layer of a proton exchange membrane, and hydrophobic inorganic oxide or PTFE mixed with catalyst as a cathode catalytic layer of the proton exchange membrane on a cathode side, such as TiO in the patents of publication Nos. CN104716351A, CN103078122A and CN1750301A2、SnO2Or W2O3Inorganic oxides are used as hydrophilic materials, but the addition of the inorganic oxides brings another serious problem, because the inorganic oxides are non-conducting and proton, the addition of the inorganic oxides seriously influences the proton transmission performance of the membrane electrode, increases the charge transfer resistance and ohmic resistance, influences the performance of the battery, and simultaneously, the addition of the hydrophilic inorganic oxides in the proton exchange membrane also seriously influences the mechanical performance of the proton exchange membrane.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hydrophilic/hydrophobic membrane electrode related to ionic liquid, aiming at solving the problem that the performance of the membrane electrode is seriously influenced by the fact that the charge transfer resistance and the ohmic resistance of the membrane electrode are greatly increased by adopting an inorganic oxide additive.
The method is realized by the following technical scheme:
the invention aims to provide a hydrophilic/hydrophobic membrane electrode related to ionic liquid, wherein an anode catalyst layer is made of hydrophilic proton type ionic liquid and a catalyst, and a cathode catalyst layer is made of hydrophobic and hydrophilic proton type ionic liquid and a catalyst.
The hydrophilic ionic liquid is [ MTBD ]][BF4]、[MTBD][HSO4]、[MTBD][H2PO4]Any one or more of them.
The hydrophobic ionic liquid is [ MTBD ]][NTf2]、[MTBD][PF6]Either one or a combination of both.
The catalyst is any one or more of Pt/C, Pt-Co/C, Pt-Ni/C and non-noble metal carbon-based catalysts.
The mass fraction of the hydrophilic ionic liquid in the anode catalyst layer is 10-50%.
The mass fraction of the hydrophobic ionic liquid in the cathode catalyst layer is 10-50%.
The Pt loading capacity in the anode catalyst layer is 0.02mg/cm2～0.09mg/cm2。
The Pt loading capacity in the cathode catalyst layer is 0.1mg/cm2～0.25mg/cm2。
Another object of the present invention is to provide a method for preparing a hydrophilic/hydrophobic membrane electrode involving ionic liquids, comprising the steps of:
1) preparing anode catalyst layer slurry: the preparation method comprises the following steps of (1) carrying out ultrasonic dispersion on hydrophilic ionic liquid, a catalyst, a solvent and a Nafion solution to obtain the catalyst;
2) preparing cathode catalyst layer slurry: performing ultrasonic dispersion on hydrophobic ionic liquid, a catalyst and a solvent, evaporating to remove the solvent, performing continuous vacuum-pumping treatment under an oil bath condition, and then adding deionized water, the solvent and a Nafion solution for ultrasonic dispersion to obtain the catalyst;
3) the anode catalyst layer slurry is attached to one side of the proton exchange membrane by any one of coating, thermal transfer printing and spraying, and the cathode catalyst layer slurry is attached to the other side of the proton exchange membrane.
And vacuumizing, wherein the vacuum degree is 0-150 pa.
TABLE 1 Pt/C and Ionic liquids [ MTBD ]][NTf2]Nitrogen desorption specific surface area of mixture processed under different vacuum degrees
| Vacuum degree treatment | Specific surface area for nitrogen desorption |
| ≤ |
0～25m2/g |
| ＞150pa | 25～100m2/g |
As can be seen from Table 1, when the mixture of the cathode catalyst and the hydrophobic ionic liquid is treated under the condition that the vacuum degree is less than or equal to 150pa, the specific surface area is less than 25m2The reason is that the hydrophobic ionic liquid can be effectively adsorbed into the inside of the pore channel of the catalyst in the vacuum degree range so as to block the pore channel of the catalyst, and nitrogen can not be filled into the inside of the pore channel of the catalyst in a nitrogen desorption test, so that the apparent specific surface area can be ignored. When the catalyst is treated in a low vacuum environment, the ionic liquid can not be ensured to fully enter the pores of the catalystThe coating effect is poor due to the inner part, and the performance of the membrane electrode is affected.
In this patent, the ionic liquid that negative pole and anode catalysis layer used all is proton type ionic liquid, the ability that has the rapid transfer hydrogen proton, the ionic liquid that the negative pole used still has the characteristics of high hydrophobicity and hydrophilic, can rapid transfer oxygen and hydrogen proton, the reaction of discharging simultaneously generates water fast, avoid the emergence of waterlogging caused by excessive rainfall phenomenon, the ionic liquid that the positive pole used still has high hydrophilicity, keep that membrane electrode anode side is abundant moist and does not influence hydrogen proton transmission, the addition of negative and positive pole ionic liquid improves and has huge effect to membrane electrode performance, make membrane electrode have excellent performance under low humidity and high humid environment.
In the invention, the hydrophilic ionic liquid is added into the anode and is directly mixed with the catalyst in a solvent, and the ultrasonic dispersion treatment is included, so that the catalyst can be rapidly and uniformly dispersed on each surface of the catalyst; the method has the advantages that the hydrophobic ionic liquid added to the cathode needs to be adsorbed in the catalyst pore channel under the condition of continuous vacuum pumping, high vacuum treatment is more critical, the hydrophobic ionic liquid can be adsorbed in the catalyst pore channel only under the condition of continuous vacuum pumping, and the ionic liquid can be uniformly dispersed on all surfaces of the catalyst, so that the coating effect is better than that of the coating effects of the coating methods of the patent publication No. CN111403756A (the ionic liquid and the catalyst are directly mixed in a solvent, and the ionic liquid is difficult to ensure to be uniformly coated on all surfaces of the catalyst) and the patent publication No. CN110197906A (the ionic liquid is directly permeated into an electrode layer, and the ionic liquid is difficult to ensure to be uniformly coated on all surfaces of the catalyst).
Has the advantages that:
the invention uses ionic liquid with special physical and chemical properties as the raw material for preparing the catalyst layer to prepare the self-humidifying membrane electrode, effectively solves the problem of charge transfer resistance increase caused by inorganic oxide as the additive for preparing the self-humidifying membrane electrode, greatly improves the ion transmission capability and stability of the membrane electrode because the ionic liquid selected by the invention has negligible volatility, and simultaneously can lead the hydrophobic ionic liquid to be absorbed into the pore canal of the catalyst under the high vacuum condition through the continuous vacuum-pumping treatment process, so that the ionic liquid can be uniformly dispersed on each surface of the catalyst.
Selection of [ MTBD ] in accordance with the invention][BF4]、[MTBD][HSO4]、[MTBD][H2PO4]Any one or more of the hydrophilic ionic liquids is/are used for preparing the anode catalyst layer, and the anode catalyst layer has hydrophilicity and proton transmission capability, so that the anode side has good water retention capability, the membrane electrode self-humidifying capability can be greatly improved, and the good proton transmission capability can be maintained.
Selection of [ MTBD ] in accordance with the invention][NTf2]、[MTBD][PF6]One or two of the components are combined into hydrophobic ionic liquid to prepare a cathode catalyst layer, and the cathode catalyst layer has hydrophobicity, oxygen affinity and proton transmission capability, can improve the oxygen transmission capability of the cathode, quickly discharges water generated on the cathode side and prevents the cathode side from flooding.
The method continuously pumps vacuum under the oil bath condition, so that the ionic liquid is adsorbed into the pore channel structure of the catalyst under the high vacuum condition, and the ionic liquid is favorably and uniformly coated on the surface of the catalyst; meanwhile, the proportion of deionized water is controlled in the preparation process of the cathode catalyst layer slurry, so that ionic liquid entering a catalyst pore passage is effectively prevented from being separated out, and the stability and the self-humidifying capability of the membrane electrode are greatly improved.
Drawings
FIG. 1 is a polarization curve and a power density curve at a relative humidity of 45% for the membrane electrodes prepared in example 1, comparative example 1 and comparative example 2;
fig. 2 is a graph of the in-situ electrochemical impedance at 0.65V and 45% relative humidity for the membrane electrodes prepared in example 1, comparative example 1 and comparative example 2.
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
Example 1
A hydrophilic/hydrophobic membrane electrode relating to ionic liquid is prepared by the following steps:
(1) proton exchange membrane treatment
Placing the proton exchange membrane in 8% hydrogen peroxide solution, placing for 1h at 80 ℃, then placing in 1mol/L sulfuric acid solution, soaking for one hour at 80 ℃, finally washing away the sulfuric acid solution by deionized water, and placing in the deionized water for later use;
(2) anode catalyst slurry preparation
Mixing ionic liquid [ MTBD ]][BF4]Pt/C catalyst, isopropanol solvent, Nafion solution were placed in a glass bottle, in which an ionic liquid [ MTBD ]][BF4]The mass percentages of the Pt/C catalyst, the isopropanol solvent and the Nafion solution are respectively 0.3 percent, 1.7 percent, 95 percent and 3 percent, and the anode catalyst slurry with uniform dispersion is obtained after ultrasonic dispersion for 30 minutes;
(3) cathode catalyst slurry formulation
Firstly, ionic liquid [ MTBD ]][NTf2]Isopropanol solvent, Pt/C catalyst in a glass bottle, wherein the ionic liquid [ MTBD ]][NTf2]0.3 percent of isopropanol solvent and 98 percent of Pt/C catalyst by mass percent and 1.7 percent of Pt/C catalyst by mass percent respectively, carrying out ultrasonic treatment for 30 minutes to ensure that the catalyst and the ionic liquid are fully and uniformly mixed, and then removing the isopropanol solvent by using a rotary evaporator device to leave only the ionic liquid [ MTBD ]][NTf2]And a mixture of Pt/C catalysts;
② the obtained ionic liquid [ MTBD ]][NTf2]And the Pt/C catalyst mixture is continuously vacuumized for 24 hours by a vacuum oil pump under the condition of oil bath at the temperature of 80 ℃, the vacuum degree is maintained within the range of 0-150pa, so that the ionic liquid is adsorbed into the pore channel structure of the catalyst under the high vacuum condition, and the ionic liquid is favorably and uniformly coated on the surface of the catalyst;
fourthly, after the treatment of the first step and the second step, deionized water, isopropanol solvent and Nafion solution are added into the mixture of the treated ionic liquid and the catalyst, wherein the ionic liquid [ MTBD ]][NTf2]The mass percentages of the Pt/C catalyst, the isopropanol solvent, the Nafion solution and the deionized water are respectively 0.3 percent, 1.7 percent, 14 percent, 3 percent and 81 percent, and the larger proportion of the deionized water is to preventStopping separating out the hydrophobic ionic liquid entering the catalyst pore channel, and then performing ultrasonic dispersion for 30 minutes to obtain uniform cathode catalyst slurry;
(4) catalyst slurry coating
Uniformly coating the prepared anode catalyst slurry and cathode catalyst slurry on two sides of the treated proton exchange membrane at 80 ℃, wherein the Pt loading amount on the anode side is controlled at 0.08mgPt/cm2The amount of Pt supported on the cathode side was controlled to 0.2mgPt/cm2The mass percentage of the ionic liquid at the anode side and the cathode side is 15 percent.
Comparative example 1
A self-humidifying membrane electrode with inorganic oxide as a catalyst layer additive is prepared by the following steps:
(1) placing the proton exchange membrane in 8% hydrogen peroxide solution, placing for one hour at 80 ℃, then soaking for one hour in 1mol/L sulfuric acid solution at 80 ℃, finally washing away the sulfuric acid solution by deionized water, and placing in the deionized water for later use;
(2) adding inorganic oxide TiO2Pt/C catalyst, isopropanol solvent and Nafion solution are put in a glass bottle, wherein, inorganic oxide TiO2The mass percentages of the Pt/C catalyst, the isopropanol solvent and the Nafion solution are respectively 0.3 percent, 1.7 percent, 95 percent and 3 percent, the catalyst slurry is dispersed by ultrasonic for 30 minutes to obtain evenly dispersed catalyst slurry, the catalyst slurry is attached to one side of a treated proton exchange membrane by a coating method to obtain an anode catalyst layer, the coating temperature is 80 ℃, wherein the inorganic oxide TiO is2Accounts for 15 percent by mass, and the Pt loading amount is 0.08mgPt/cm2；
(3) Placing PTFE emulsion, a Pt/C catalyst, an isopropanol solvent and a Nafion solution in a glass bottle, wherein the mass percentages of the PTFE, the Pt/C catalyst, the isopropanol solvent and the Nafion solution are respectively 0.3%, 1.7%, 95% and 3%, performing ultrasonic dispersion for 30 minutes to obtain uniformly dispersed catalyst slurry, attaching the catalyst slurry to the other side of the treated proton exchange membrane by a coating method to obtain a cathode catalyst layer, and the coating temperature is 80 ℃, wherein the mass percentage of the PTFE emulsion is15% and the Pt supporting amount is 0.2mgPt/cm2；
Comparative example 2: blank membrane electrode
The specific steps of adding PTFE to the cathode catalyst layer without adding any hydrophilic substance in the anode catalyst layer were the same as in comparative example 1.
3. Membrane electrode Performance testing
The performance of the prepared membrane electrode (example 1, comparative example 1 and comparative example 2) is shown in fig. 1, and the ionic liquid as an electrode additive of a self-humidifying membrane shows the best electrochemical performance, because the proton type ionic liquid not only has good moisturizing capability, but also has proton conducting property which is beneficial to improving the charge transport capability of the membrane electrode and exerting the electrode performance of the membrane, and the inorganic oxidant without proton conducting is used as the electrode additive of the self-humidifying membrane, the electrochemical performance is relatively inferior, because the inorganic oxide only has moisturizing capability and has no proton transport property, and the charge transport capability is relatively poor. Meanwhile, the electrochemical impedance of each membrane electrode is tested in situ under the condition that the relative humidity is 45% and the voltage is 0.65V, and the impedance is shown in fig. 2, so that the ohmic resistance of the membrane electrode can be reduced by using the ionic liquid and the inorganic oxide as the electrode additives of the self-humidifying membrane, and the charge transfer resistance is reduced at the same time, because the hydrophilic ionic liquid and the inorganic oxide have the water retention capacity, the high-efficiency proton transfer capacity of the membrane electrode can be ensured, and because the ionic liquid is used as the electrode additives of the self-humidifying membrane, the ohmic resistance and the charge transfer resistance are minimum, because the ionic liquid has the proton transfer characteristic and the good moisture retention capacity, the ohmic resistance and the charge transfer resistance of the membrane electrode can be greatly reduced.
Example 2
A hydrophilic/hydrophobic membrane electrode relating to ionic liquid is prepared by the following steps:
(1) proton exchange membrane treatment
The same as example 1;
(2) anode catalyst slurry preparation
On the basis of example 1, the ionic liquid was replaced by [ MTBD ]][HSO4]The catalyst is replaced by Pt-Co/C;
(3) cathode catalyst slurry formulation
On the basis of example 1, the ionic liquid was replaced by [ MTBD ]][PF6]The catalyst was replaced with Pt-Co/C and the other steps were the same as in example 1;
(4) catalyst slurry coating
Uniformly coating the prepared anode catalyst slurry and cathode catalyst slurry on two sides of the treated proton exchange membrane at 80 ℃, wherein the Pt loading amount on the anode side is controlled at 0.02mgPt/cm2The amount of Pt supported on the cathode side was controlled to 0.1mgPt/cm2The mass percentage of the ionic liquid at the anode side and the cathode side is 20 percent.
Example 3
A hydrophilic/hydrophobic membrane electrode relating to ionic liquid is prepared by the following steps:
(1) proton exchange membrane treatment
The same as example 1;
(2) anode catalyst slurry preparation
On the basis of example 1, the ionic liquid was replaced by [ MTBD ]][H2PO4]The catalyst is replaced by Pt-Ni/C;
(3) cathode catalyst slurry formulation
On the basis of the example 1, the catalyst replaces Pt-Ni/C, and other steps are the same as the example 1;
(4) catalyst slurry coating
Uniformly coating the prepared anode catalyst slurry and cathode catalyst slurry on two sides of the treated proton exchange membrane at 80 ℃, wherein the Pt loading amount on the anode side is controlled at 0.05mgPt/cm2The amount of Pt supported on the cathode side was controlled to 0.15mgPt/cm2The mass percentage of the ionic liquid at the anode side and the cathode side is 50 percent.
Example 4
A hydrophilic/hydrophobic membrane electrode relating to ionic liquid is prepared by the following steps:
(1) proton exchange membrane treatment
The same as example 1;
(2) anode catalyst slurry preparation
On the basis of example 1Replacement of ionic liquid by [ MTBD ]][HSO4]And [ MTBD ]][H2PO4]The catalyst is replaced by Pt-Co/C;
(3) cathode catalyst slurry formulation
On the basis of example 1, the ionic liquid was replaced by [ MTBD ]][NTf2]And [ MTBD ]][PF6]The catalyst was replaced with Pt-Ni/C, and the other steps were the same as in example 1;
(4) catalyst slurry coating
Uniformly coating the prepared anode catalyst slurry and cathode catalyst slurry on two sides of the treated proton exchange membrane at 80 ℃, wherein the Pt loading amount on the anode side is controlled at 0.03mgPt/cm2The Pt loading amount on the cathode side was controlled to 0.18mgPt/cm2The mass percentage of the ionic liquid at the anode side and the cathode side is 30 percent.
Electrochemical tests were performed as in example 1, with the peak power densities for each set shown in table 2:
TABLE 2
| Item | Power density (W/cm)2) |
| Example 2 | 0.930 |
| Example 3 | 0.918 |
| Example 4 | 0.925 |
Each set of EIS curves shows: it has better proton conductivity, and the charge transfer resistance is shown in table 3:
TABLE 3
| Item | Charge transfer resistance (Ω · cm)2) |
| Example 2 | 0.215 |
| Example 3 | 0.185 |
| Example 4 | 0.195 |
Claims (9)
1. The hydrophilic/hydrophobic membrane electrode related to ionic liquid is characterized in that an anode catalyst layer is made of hydrophilic proton type ionic liquid and a catalyst, and a cathode catalyst layer is made of hydrophobic proton type ionic liquid and a catalyst.
2. The hydrophilic/hydrophobic membrane electrode assembly of claim 1, wherein the hydrophilic protic ionic liquid is [ MTBD ™][BF4]、[MTBD][HSO4]、[MTBD][H2PO4]Any one or more of them.
3. The hydrophilic/hydrophobic membrane electrode assembly of claim 1, wherein the hydrophobic protic ionic liquid is [ MTBD ™][NTf2]、[MTBD][PF6]Any one or two of them in combination。
4. The hydrophilic/hydrophobic membrane electrode assembly related to ionic liquid of claim 1, wherein the catalyst is any one or more of Pt/C, Pt-Co/C, Pt-Ni/C and non-noble metal carbon-based catalysts.
5. The hydrophilic/hydrophobic membrane electrode assembly related to ionic liquid according to claim 1, wherein the mass fraction of the ionic liquid with hydrophilic properties in the anode catalytic layer is 10-50%.
6. The hydrophilic/hydrophobic membrane electrode assembly related to ionic liquid according to claim 1, wherein the mass fraction of the ionic liquid with hydrophobic properties in the cathode catalyst layer is 10-50%.
7. The hydrophilic/hydrophobic membrane electrode assembly related to ionic liquid according to claim 1, wherein the Pt loading in the anode catalytic layer is 0.02mg/cm2～0.09mg/cm2。
8. The hydrophilic/hydrophobic membrane electrode assembly related to ionic liquid of claim 1, wherein the Pt loading in the cathode catalyst layer is 0.1mg/cm2～0.25mg/cm2。
9. The hydrophilic/hydrophobic membrane electrode assembly related to ionic liquid according to claim 1, wherein the preparation method comprises the following steps:
1) preparing anode catalyst layer slurry: the preparation method comprises the following steps of (1) carrying out ultrasonic dispersion on hydrophilic proton type ionic liquid, a catalyst, a solvent and a Nafion solution to obtain the product;
2) preparing cathode catalyst layer slurry: ultrasonically dispersing hydrophobic proton type ionic liquid, a catalyst and a solvent, evaporating to remove the solvent, continuously vacuumizing under the condition of oil bath, and then adding deionized water, an isopropanol solvent and a Nafion solution for ultrasonic dispersion to obtain the catalyst;
3) the anode catalyst layer slurry is attached to one side of the proton exchange membrane by any one of coating, thermal transfer printing and spraying, and the cathode catalyst layer slurry is attached to the other side of the proton exchange membrane.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5211984A (en) * | 1991-02-19 | 1993-05-18 | The Regents Of The University Of California | Membrane catalyst layer for fuel cells |
| CN1750301A (en) * | 2005-09-29 | 2006-03-22 | 华南理工大学 | Self humidifying film electrode and its preparing method |
| CN101557001A (en) * | 2008-04-10 | 2009-10-14 | 汉能科技有限公司 | Fuel cell film electrode and preparation method thereof |
| CN102017264A (en) * | 2008-02-29 | 2011-04-13 | 巴斯夫欧洲公司 | Ionic liquid-containing catalyst ink and the use thereof in the production of electrodes, CCMs, GDEs and MEAs |
| CN102437343A (en) * | 2011-11-17 | 2012-05-02 | 华南理工大学 | Membrane electrode containing hydrophilic high polymer in anode catalytic layer and preparation method thereof |
| CN105720274A (en) * | 2016-04-15 | 2016-06-29 | 厦门大学 | Method for preventing pore passages from being flooded with water in catalyst layer of fuel cell |
| CN105949367A (en) * | 2016-05-11 | 2016-09-21 | 常州大学 | Polymer electrolyte film adopting hydrophilic/hydrophobic interpenetrating network structure and preparation method of film |
| CN106229533A (en) * | 2016-08-24 | 2016-12-14 | 上海交通大学 | Compound Multilayer Film Electrode of hydrophilic/hydrophobic and preparation method thereof |
| CN106876758A (en) * | 2017-04-24 | 2017-06-20 | 常州大学 | A kind of preparation method of the PEM with hydrophilic/hydrophobic inierpeneirating network structure |
| CN107744836A (en) * | 2017-09-29 | 2018-03-02 | 浙江工业大学 | A kind of preparation method and applications of load-type ion liquid catalyst |
| CN110289438A (en) * | 2019-07-01 | 2019-09-27 | 江苏乾景新能源产业技术研究院有限公司 | A kind of preparation method of fuel cell self-humidifying membrane electrode |
| CN110323477A (en) * | 2019-04-19 | 2019-10-11 | 武汉理工大学 | A kind of hydrogen reduction Catalytic Layer and preparation method thereof based on poly ion liquid as proton conductor |
| CN111403756A (en) * | 2019-01-03 | 2020-07-10 | 丰田自动车工程及制造北美公司 | Novel catalyst layer compositions for improving performance of membrane-assembled electrodes with ionic liquids |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110189589A1 (en) * | 2010-01-29 | 2011-08-04 | The Johns Hopkins University | Composite porous catalysts |
| CN104190412B (en) * | 2014-08-29 | 2016-05-25 | 北京大学 | A kind of platinum/carbon-based nano composite and preparation method thereof and application |
| CN111490277A (en) * | 2020-04-20 | 2020-08-04 | 淄博火炬能源有限责任公司 | Membrane electrode of medium-temperature proton exchange membrane fuel cell and preparation method thereof |
-
2020
- 2020-09-07 CN CN202010928280.8A patent/CN112072120B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5211984A (en) * | 1991-02-19 | 1993-05-18 | The Regents Of The University Of California | Membrane catalyst layer for fuel cells |
| CN1750301A (en) * | 2005-09-29 | 2006-03-22 | 华南理工大学 | Self humidifying film electrode and its preparing method |
| CN102017264A (en) * | 2008-02-29 | 2011-04-13 | 巴斯夫欧洲公司 | Ionic liquid-containing catalyst ink and the use thereof in the production of electrodes, CCMs, GDEs and MEAs |
| CN101557001A (en) * | 2008-04-10 | 2009-10-14 | 汉能科技有限公司 | Fuel cell film electrode and preparation method thereof |
| CN102437343A (en) * | 2011-11-17 | 2012-05-02 | 华南理工大学 | Membrane electrode containing hydrophilic high polymer in anode catalytic layer and preparation method thereof |
| CN105720274A (en) * | 2016-04-15 | 2016-06-29 | 厦门大学 | Method for preventing pore passages from being flooded with water in catalyst layer of fuel cell |
| CN105949367A (en) * | 2016-05-11 | 2016-09-21 | 常州大学 | Polymer electrolyte film adopting hydrophilic/hydrophobic interpenetrating network structure and preparation method of film |
| CN106229533A (en) * | 2016-08-24 | 2016-12-14 | 上海交通大学 | Compound Multilayer Film Electrode of hydrophilic/hydrophobic and preparation method thereof |
| CN106876758A (en) * | 2017-04-24 | 2017-06-20 | 常州大学 | A kind of preparation method of the PEM with hydrophilic/hydrophobic inierpeneirating network structure |
| CN107744836A (en) * | 2017-09-29 | 2018-03-02 | 浙江工业大学 | A kind of preparation method and applications of load-type ion liquid catalyst |
| CN111403756A (en) * | 2019-01-03 | 2020-07-10 | 丰田自动车工程及制造北美公司 | Novel catalyst layer compositions for improving performance of membrane-assembled electrodes with ionic liquids |
| CN110323477A (en) * | 2019-04-19 | 2019-10-11 | 武汉理工大学 | A kind of hydrogen reduction Catalytic Layer and preparation method thereof based on poly ion liquid as proton conductor |
| CN110289438A (en) * | 2019-07-01 | 2019-09-27 | 江苏乾景新能源产业技术研究院有限公司 | A kind of preparation method of fuel cell self-humidifying membrane electrode |
Non-Patent Citations (2)
| Title |
|---|
| Morphology studies of high temperature proton conducting membranes containing hydrophilic/hydrophobic ionic liquids;S. S. Sekhon等;《Macromolecules》;20090226(第42期);第2054-2062页 * |
| 用于高温质子交换膜燃料电池的聚合物电解质膜研究进展;李英 等;《化工进展》;20180905;第37卷(第9期);第3446-3453页 * |
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