CN111342061B - Core-shell fiber structure electrode and preparation method and application thereof - Google Patents
Core-shell fiber structure electrode and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a core-shell structure electrode, wherein the electrode material is a core-shell fiber structure which takes fiber yarns as a core and takes a film wrapped on the outer surface of the fiber yarns as a shell, the diameter size range of the core-shell fiber structure is 20-5000nm, and the ratio of the thickness of the shell to the radius of the core layer is 10: 1-1: 10; the surface of the shell layer structure also comprises an array structure formed by nano-scale columnar crystals vertical to the surface of the shell layer film, the diameter range of the columnar crystals is 2-20nm, and the length range of the columnar crystals is 2-1000 nm. The electrode with the structure has adjustable inner layer fiber diameter and shell layer thickness, and adjustable core-shell proportion and shell composition, and can be used in electrodes of proton exchange membrane fuel cells, direct liquid fuel cells, metal air cells, high-temperature polymer electrolyte membrane fuel cells and the like.
Description
Technical Field
The invention relates to a novel core-shell structure electrode and a preparation method thereof, in particular to the core-shell structure electrode which has adjustable inner layer fiber diameter and shell thickness, adjustable core-shell proportion and adjustable shell composition and can be used in electrodes of proton exchange membrane fuel cells, direct liquid fuel cells, metal air cells, high-temperature polymer electrolyte membrane fuel cells and the like.
The invention also relates to a preparation method of the composite material.
Background
The porous nanofiber is a novel nano-structure material developed in recent years, and has the advantages of high electrochemical surface area, small density, flexible and adjustable structure and the like, so that the porous nanofiber has wide application prospects in the aspects of catalysis, medicines, sensing and the like.
The electrospinning process is one of the most convenient, straightforward and economical methods for producing porous nanofiber materials, and many polymers and melts can be used as raw materials. Fuel cell electrodes are the site of electrochemical reactions that directly determine fuel cell performance. The electrochemical reaction occurs in the three-phase interface region, i.e., electrons, protons, gas. The electrode structure is reasonably designed, the mass transfer of reactants to a reaction area with low mass transfer resistance is ensured, and good electron and proton channels are provided, so that the electrode structure becomes the design key point of the fuel cell electrode.
The porous fiber has the advantages of large electrochemical specific surface area, good pore structure and the like, and becomes a hot point for research on fuel cell electrodes. The porous fiber preparation method reported in the literature at present is to prepare the porous carbon paper catalyst by electrospinning a catalyst precursor salt and a polymer into filaments and then removing the polymer at high temperature or to adopt a method for regulating and controlling an electrostatic spinning solvent and spinning conditions, but few literatures relate to porous composite nanofibers, namely metal and ionic polymer nanofibers. Therefore, the preparation of the metal composite porous nanofiber has challenges and application prospects. Meanwhile, the electrode active substance is fully exposed in the interface area of the electrode substance transfer channel, which is an important means for ensuring the utilization rate of the electrode active substance, and the preparation of the electrode with the core-shell structure has important application prospect.
The invention adopts an electrostatic spinning method combined with a magnetron sputtering method to prepare the metal composite nano fiber with the porous structure core-shell structure.
Disclosure of Invention
The invention prepares an electrode material with a core-shell structure, the electrode with the core-shell structure has a nanofiber structure in microscopic morphology, and the shell structure also has the morphology characteristic of a crystal array, the core-layer structure of the structure is prepared by an electrostatic spinning technology, and the shell structure is prepared by a magnetron sputtering technology and can be used as a porous electrode of devices such as a fuel cell, a metal air cell, a high-temperature polymer electrolyte membrane fuel cell and the like. In order to achieve the purpose, the invention adopts the following specific scheme to realize:
an electrode material with a core-shell structure is a fiber structure with the diameter of micron, submicron or nanometer, the diameter size range is 20-5000nm, a fiber yarn is taken as a core and called as a core layer, a film wrapped on the outer surface of the fiber yarn is taken as a shell layer, the ratio of the thickness of the shell layer to the radius of the core layer is 10: 1-1: 10, the shell layer structure further comprises an array structure formed by nano-scale columnar crystals, the diameter range of the columnar crystals is 2-20nm, and the length range of the columnar crystals is 2-1000 nm.
The core-shell structure electrode material is composed of an ion conductor material, an electronic conductor material or a semiconductor material, and comprises one or more than two of perfluorosulfonic acid polymer, polybenzimidazole, polyether ether ketone, carbon nano tubes, activated carbon, nano silicon dioxide and nano ferroferric oxide.
The shell structure of the electrode material with the core-shell structure is made of a metal catalytic active material, wherein the metal catalytic active material comprises one or more than two of platinum, gold, silver, ruthenium and palladium or an alloy of any two or more than five of platinum, gold, silver, ruthenium and palladium, and one or more than two of transition metals of iron, nickel, cobalt and copper are not added or can be added as an alloy.
The generation template of the porous structure in the shell layer structure of the electrode material with the core-shell structure comprises one or more than two of polyacrylic acid, polyethylene oxide and polyvinylpyrrolidone.
The preparation method of the core-shell structure electrode material comprises the following preparation steps and is shown in figure 1.
a. Preparation of core layer material spinning solution
Dissolving one or more than two of perfluorinated sulfonic acid polyions, polybenzimidazole and polyether ether ketone in a certain mass in one or more than two solvents of water, dimethylformamide, methanol or ethanol, wherein the mass concentration is 1-20%, then adding one or more than two of polyacrylic acid, polyethylene oxide and polyvinylpyrrolidone, wherein the mass concentration is 0-10%, stirring for 2-48 h at the temperature of room temperature to 80 ℃, and fully and uniformly dissolving for later use.
b. Electrostatic spinning preparation of core-layer structure
And c, placing the spinning solution prepared in the step a in a spinning injection device, wherein the feeding speed is 0.1-2 mL/min, the distance between a needle and a receiver is 5-20 cm, the spinning potential is 10-30 kV, the environmental temperature is controlled to be 10-50 ℃, and the humidity is 20-80%. The resulting fibrous structure material is ready for use.
c. Magnetron sputtering preparation of shell structure
Adding one or more than two of chloroplatinic acid, chloroauric acid, silver nitrate, ruthenium chloride and chloropalladic acid or one or more than two of chloroplatinic acid, chloroauric acid, silver nitrate, ruthenium chloride and chloropalladic acid and one or more than two of ferric nitrate, nickel nitrate, cobalt nitrate and copper nitrate into one or more than two solvents of water, dimethylformamide, methanol or ethanol according to the mass ratio of 5:1 to 1:5 to ensure that the mass concentration of the noble metal is 1 to 10 percent, and fully dissolving the noble metal for later use; soaking the fiber structure material prepared in the step into the solution, and keeping the temperature at 12-48 ℃ at 50-80 ℃; taking out and washing with deionized water, drying and then placing in a tubular furnace, carrying out heat treatment for 2-8 hours in hydrogen-argon mixed gas containing 5% of hydrogen at the temperature of 150 ℃ and 400 ℃; a metal shell structure is prepared on the surface of the material by a magnetron sputtering method, the sputtering target material is one or more than two of platinum, gold, silver, ruthenium, palladium or an alloy of any two or more than two of platinum, gold, silver, ruthenium and palladium, the sputtering power is 1-10kW, and the sputtering time is 20-180 minutes. Thus obtaining the electrode material with the core-shell structure.
The components and proportion of the solvent adopted for dipping in the step c are key steps for realizing effective loading of the metal nanoparticle nucleation sites, and the aim is to enable the base part of the nano-fiber to be dissolved and fully cross-linked with the metal precursor salt;
the time and temperature adopted for dipping in the step c are also key conditions for realizing effective loading of metal nanoparticle nucleation sites, and the sufficient metal loading density is difficult to form at too low temperature and for too short time; the electrode material with the core-shell structure can be used in a proton exchange membrane fuel cell, a metal air cell or a high-temperature polymer electrolyte membrane fuel cell.
Compared with the prior art, the invention has the following advantages:
1. the structure is orderly and controllable: the fiber diameter and the pore density of the electrode material with the core-shell structure prepared by the method can be controlled by the parameters of the preparation process.
2. The mass transfer performance is good: the electrode material with the core-shell structure prepared by the method has the advantages of improved porosity, ordered pores and better mass transfer performance;
3. the utilization rate of the noble metal is high: the core-shell structure electrode material prepared by the method has the advantages that the surface of the noble metal can be mostly exposed in a mass transfer channel, so that the utilization rate is high;
4. the ion transmission efficiency is high: the core-shell structure electrode material prepared by the method has ordered and controllable ion transmission channels, and the one-dimensional structure of the core-shell structure electrode material can greatly strengthen the ion transmission process;
5. the electrode interface compatibility is good: the interface impedance of the electrode in contact with an electrolyte membrane is smaller and the ohmic polarization loss of the electrode is smaller by adopting the core-shell structure electrode material prepared by the method;
6. the practicability is strong: compared with other preparation methods, the electrostatic spinning method has the advantages that the preparation process is high in controllability, uncontrollable factors caused by other methods are reduced, and the practicability is high.
Description of the drawings:
FIG. 1 is a schematic flow chart of the synthesis route of the core-shell fiber structure electrode of the present invention.
FIG. 2 is a transmission electron micrograph of a core-shell fiber structure electrode prepared by the method of the present invention (example 1). As shown, the fiber material exhibits a core-shell structure characterized by a core diameter of about 200 nm and a shell thickness of about 80 nm, which is microscopically an array structure of nano-sized columnar crystals perpendicular to the core surface, the diameter of the columnar crystals ranging about 10 nm.
Fig. 3 is a graph showing the results of applying the core-shell fiber structure electrode prepared by the method of the present invention to a direct methanol fuel cell cathode (example 1, comparative example 1 and commercial catalyst). As can be seen from the figure, the performance of the core-shell fiber structure electrode prepared by the method is obviously improved.
Detailed Description
The present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples.
Example 1:
a. preparation of core layer material spinning solution
Dissolving a certain mass of perfluorinated sulfonic acid polyion in a mixed solvent of water and methanol in a volume ratio of 1:1, wherein the mass concentration is 5%, then adding polyacrylic acid, the mass concentration is 5%, stirring for 12h at room temperature, and fully and uniformly dissolving for later use.
b. Electrostatic spinning preparation of core-layer structure
And c, placing the spinning solution prepared in the step a in a spinning injection device, wherein the feeding speed is 2mL/min, the distance between a needle head and a receiver is 10cm, the spinning potential is 20kV, the environmental temperature is controlled to be 25 ℃, and the humidity is 50%. The resulting fibrous structure material is ready for use.
c. Magnetron sputtering preparation of shell structure
Adding chloroplatinic acid with a certain mass into a mixed solvent of deionized water and dimethylformamide according to the volume ratio of 5:1 to ensure that the mass concentration of noble metal is 8%, and fully dissolving for later use; soaking the fiber structure material prepared in the step into the solution, and keeping the solution at the temperature of 80 ℃ for 24 hours; taking out, washing with deionized water, drying, placing in a tubular furnace, and performing heat treatment for 4 hours in hydrogen-argon mixed gas containing 5% of hydrogen gas by volume at the temperature of 250 ℃; a metal shell structure is prepared on the surface of the material by a magnetron sputtering method, the sputtering target material is platinum, the sputtering power is 10kW, and the sputtering time is 30 minutes. Thereby producing a core-shell fibrous structure material. As can be seen from the results of the transmission electron microscope (FIG. 2), the prepared material exhibited excellent core-shell structural characteristics, wherein the core diameter was about 200 nm and the shell thickness was about 80 nm.
Comparative example 1:
preparing a fiber porous structure electrode with a non-core-shell structure. Dissolving a certain mass of perfluorinated sulfonic acid polyion in a mixed solvent of water and methanol in a ratio of 1:1, wherein the mass concentration is 5%, then adding polyacrylic acid, the mass concentration is 5%, stirring for 12h at room temperature, and fully and uniformly dissolving for later use. Adding chloroplatinic acid with a certain mass into deionized water to enable the mass concentration of noble metal to be 8%, fully dissolving, adding the spinning solution, and fully stirring and mixing for 4 hours; and (3) placing the spinning solution prepared in the step into a spinning injection device, wherein the feeding speed is 2mL/min, the distance between a needle head and a receiver is 10cm, the spinning potential is 20kV, the environmental temperature is controlled to be 25 ℃, and the humidity is 50%. And preparing the fiber porous structure with the non-core-shell structure.
Comparative example 2:
a. preparation of core layer material spinning solution
Dissolving a certain mass of perfluorinated sulfonic acid polyion in a mixed solvent of water and methanol in a ratio of 1:1, wherein the mass concentration is 5%, then adding polyacrylic acid, the mass concentration is 5%, stirring for 12h at room temperature, and fully and uniformly dissolving for later use.
b. Electrostatic spinning preparation of core-layer structure
And c, placing the spinning solution prepared in the step a in a spinning injection device, wherein the feeding speed is 2mL/min, the distance between a needle head and a receiver is 10cm, the spinning potential is 20kV, the environmental temperature is controlled to be 25 ℃, and the humidity is 50%. The resulting fibrous structure material is ready for use.
c. Magnetron sputtering preparation of shell structure
Adding chloroplatinic acid with a certain mass into deionized water to ensure that the mass concentration of the noble metal is 8 percent, and fully dissolving the noble metal for later use; soaking the fiber structure material prepared in the step into the solution, and keeping the solution at the temperature of 80 ℃ for 24 hours; taking out, washing with deionized water, drying, placing in a tubular furnace, and performing heat treatment in a hydrogen-argon mixed gas containing 5% of hydrogen for 4 hours at the temperature of 250 ℃; a metal shell structure is prepared on the surface of the material by a magnetron sputtering method, the sputtering target material is platinum, the sputtering power is 10kW, and the sputtering time is 30 minutes. The core-shell fiber structure material is prepared, the shell layer of the prepared material is sparse, and a compact shell layer structure is difficult to form.
And c, adopting water as an impregnation solvent to difficultly enable the metal precursor salt to be effectively adsorbed on the surface of the nanofiber structure, so that effective loading of metal nanoparticle nucleation sites and growth of a sputtered metal layer are difficultly realized. Comparative example 3:
a. preparation of core layer material spinning solution
Dissolving a certain mass of perfluorinated sulfonic acid polyion in a mixed solvent of water and methanol in a ratio of 1:1, wherein the mass concentration is 5%, then adding polyacrylic acid, the mass concentration is 5%, stirring for 12h at room temperature, and fully and uniformly dissolving for later use.
b. Electrostatic spinning preparation of core-layer structure
And c, placing the spinning solution prepared in the step a in a spinning injection device, wherein the feeding speed is 2mL/min, the distance between a needle head and a receiver is 10cm, the spinning potential is 20kV, the environmental temperature is controlled to be 25 ℃, and the humidity is 50%. The resulting fibrous structure material is ready for use.
c. Magnetron sputtering preparation of shell structure
Adding chloroplatinic acid with a certain mass into a mixed solvent of deionized water and dimethylformamide in a ratio of 5:1 to ensure that the mass concentration of noble metal is 8%, and fully dissolving for later use; soaking the fiber structure material prepared in the step into the solution, and keeping the solution at room temperature for 2 hours; taking out, washing with deionized water, drying, placing in a tubular furnace, and performing heat treatment in a hydrogen-argon mixed gas containing 5% of hydrogen for 4 hours at the temperature of 250 ℃; a metal shell structure is prepared on the surface of the material by a magnetron sputtering method, the sputtering target material is platinum, the sputtering power is 10kW, and the sputtering time is 30 minutes. Thereby producing a core-shell fibrous structure material. As can be seen by a transmission electron microscope, the shell layer of the prepared material is sparse, and a compact shell layer structure is difficult to form.
The lower dipping temperature and the shorter dipping time adopted in the step c can not ensure the effective load of the metal nanoparticle nucleation sites, and directly influence the growth of the sputtered metal shell layer structure.
Example 2:
a. preparation of core layer material spinning solution
Dissolving a certain mass of polybenzimidazole in dimethylformamide with the mass concentration of 10%, then adding the polybenzimidazole into polyvinylpyrrolidone with the mass concentration of 6%, stirring for 48 hours at the temperature of 50 ℃, and fully and uniformly dissolving for later use.
b. Electrostatic spinning preparation of core-layer structure
And c, placing the spinning solution prepared in the step a in a spinning injection device, wherein the feeding speed is 0.5mL/min, the distance between a needle head and a receiver is 5cm, the spinning potential is 10kV, the environmental temperature is controlled to be 40 ℃, and the humidity is 80%. The resulting fibrous structure material is ready for use.
c. Magnetron sputtering preparation of shell structure
Mixing chloroplatinic acid and nickel nitrate according to the mass ratio of 1:1, adding the mixture into a mixed solvent of water and methanol in a ratio of 1:1 to ensure that the mass concentration of noble metal is 5%, and fully dissolving the noble metal for later use; soaking the fiber structure material prepared in the step into the solution, and keeping the solution at the temperature of 80 ℃ for 48 hours; taking out, washing with deionized water, drying, placing in a tubular furnace, and performing heat treatment in a hydrogen-argon mixed gas containing 5% of hydrogen for 8 hours at the temperature of 400 ℃; a metal shell structure is prepared on the surface of the material by a magnetron sputtering method, the sputtering target material is platinum and palladium alloy (the molar ratio is 1:1), the sputtering power is 5kW, and the sputtering time is 60 minutes. The prepared material is in a core-shell structure, wherein the film of the shell layer is in a sparse array structure formed by nanoscale columnar crystals vertical to the surface of the core microscopically.
Claims (10)
1. An electrode material having a core-shell structure, characterized in that: the electrode material is a core-shell fiber structure which takes fiber yarns as a core and takes a film wrapped on the outer surfaces of the fiber yarns as a shell, the diameter size range of the core-shell fiber structure is 20-5000nm, and the ratio of the thickness of the shell to the radius of the core is 10: 1-1: 10; the film is microscopically in an array structure formed by nano-scale columnar crystals vertical to the surface of the core, the diameter range of the columnar crystals is 2-20nm, and the length range of the columnar crystals is 2-1000 nm;
comprises the following steps of (a) carrying out,
a. preparation of core material spinning solution:
dissolving one or more of an ionic conductor material, an electronic conductor material or a semiconductor material in a solvent, wherein the solvent is one or more of water, dimethylformamide, methanol or ethanol, the mass concentration of the solution is 1-20%, then adding one or more of polyacrylic acid, polyethylene oxide and polyvinylpyrrolidone, the mass concentration is 0.1-10%, stirring for 2-48 h at the temperature of room temperature to 80 ℃, and fully and uniformly dissolving for later use;
the ion conductor is one or more than two of perfluorosulfonic acid polymer, polybenzimidazole and polyether-ether-ketone; the electronic conductor is one or more of carbon nano tube and active carbon; the semiconductor material is one or more than two of nano silicon dioxide and nano ferroferric oxide;
b. electrostatic spinning preparation of core structure: b, placing the spinning solution prepared in the step a in a spinning injection device for spinning to prepare a fiber structure material;
c. magnetron sputtering preparation of the core-shell structure:
b, adding a noble metal catalyst precursor or a mixture of the noble metal catalyst precursor and a doping alloy precursor into a solvent to ensure that the mass concentration of noble metal is 1-10%, fully dissolving, soaking the fiber structure material prepared in the step b into the solution, taking out, washing, drying, and then placing into hydrogen-argon mixed gas containing hydrogen for heat treatment;
and preparing a metal shell structure on the surface of the obtained heat treatment material by a magnetron sputtering method, wherein the sputtering target material is one or more than two of platinum, gold, silver, ruthenium and palladium or an alloy of any two of the platinum, the gold, the silver, the ruthenium and the palladium.
2. The electrode material as set forth in claim 1, wherein: the core of the core-shell structure electrode material is made of one or more than two of ion conductor materials, electronic conductor materials or semiconductor materials, and simultaneously comprises one or more than two of polyacrylic acid, polyethylene oxide and polyvinylpyrrolidone.
3. The electrode material as claimed in claim 1 or 2, wherein: when the ion conductor material is arranged in the core of the core-shell structure electrode material, the core is one or more than two of perfluorosulfonic acid polymer, polybenzimidazole and polyether-ether-ketone; when the material is an electronic conductor material, the material is one or more than two of carbon nano tubes and activated carbon; when the material is a semiconductor material, the material is one or more than two of nano silicon dioxide and nano ferroferric oxide; the mass content of one or more than two of polyacrylic acid, polyethylene oxide and polyvinylpyrrolidone in the core is 5-50%.
4. The electrode material as set forth in claim 1, wherein: the shell layer of the electrode material with the core-shell structure is made of a noble metal catalytic active material, wherein transition metal is not added or is also added to serve as a doping alloy.
5. The electrode material as set forth in claim 4, wherein: the noble metal catalytic active material is one or more than two of platinum, gold, silver, ruthenium, palladium or an alloy of any two or more than five of the platinum, the gold, the silver, the ruthenium and the palladium; the doped alloy transition metal is one or more of iron, nickel, cobalt and copper, and the mass ratio of the noble metal to the transition metal is 5:1 to 1: 5.
6. A method for preparing the electrode material according to any one of claims 1 to 5, wherein: comprises the following steps of (a) carrying out,
a. preparation of core material spinning solution:
dissolving one or more of an ionic conductor material, an electronic conductor material or a semiconductor material in a solvent, wherein the solvent is one or more of water, dimethylformamide, methanol or ethanol, the mass concentration of the solution is 1-20%, then adding one or more of polyacrylic acid, polyethylene oxide and polyvinylpyrrolidone, the mass concentration is 0.1-10%, stirring for 2-48 h at the temperature of room temperature to 80 ℃, and fully and uniformly dissolving for later use;
the ion conductor is one or more than two of perfluorosulfonic acid polymer, polybenzimidazole and polyether-ether-ketone; the electronic conductor is one or more of carbon nano tube and active carbon; the semiconductor material is one or more than two of nano silicon dioxide and nano ferroferric oxide;
b. electrostatic spinning preparation of core structure: b, placing the spinning solution prepared in the step a in a spinning injection device for spinning to prepare a fiber structure material;
c. magnetron sputtering preparation of the core-shell structure:
b, adding a noble metal catalyst precursor or a mixture of the noble metal catalyst precursor and a doping alloy precursor into a solvent to ensure that the mass concentration of noble metal is 1-10%, fully dissolving, soaking the fiber structure material prepared in the step b into the solution, taking out, washing, drying, and then placing into hydrogen-argon mixed gas containing hydrogen for heat treatment;
and preparing a metal shell structure on the surface of the obtained heat treatment material by a magnetron sputtering method, wherein the sputtering target material is one or more than two of platinum, gold, silver, ruthenium and palladium or an alloy of any two of the platinum, the gold, the silver, the ruthenium and the palladium.
7. The method for producing an electrode material according to claim 6, wherein:
the electrostatic spinning preparation conditions in the step b are as follows: the feeding speed of the spinning solution is 0.1-2 mL/min, the distance between a needle and a receiver is 5-20 cm, the spinning potential is 10-30 kV, the environmental temperature is controlled to be 10-50 ℃, and the humidity is 20-80%.
8. The method for producing an electrode material according to claim 6, wherein:
the precious metal catalyst precursor in the step c is one or more than two of chloroplatinic acid, chloroauric acid, silver nitrate, ruthenium chloride and chloropalladic acid, and the electrocatalyst precursor is one or more than two of ferric nitrate, nickel nitrate, cobalt nitrate and copper nitrate; in the mixture of the noble metal catalyst precursor and the electrocatalyst precursor, the ratio of the amounts of the noble metal catalyst precursor and the electrocatalyst precursor is from 5:1 to 1: 5; the solvent is one or more of water, dimethylformamide, methanol or ethanol.
9. The method for producing an electrode material according to claim 6, wherein:
in the step c, the fiber structure material is soaked in the solution under the condition that the temperature is kept between 12 and 48 ℃ at 50 and 80 ℃;
in the step c, the volume concentration of the hydrogen in the hydrogen-argon mixed gas is 3-10%, the heat treatment time is 2-8 hours, and the heat treatment temperature is 150-;
the sputtering condition in the step c is that the sputtering power is 1-10kW, and the sputtering time is 20-180 minutes.
10. Use of an electrode material according to any of claims 1-5, characterized in that:
the core-shell structure electrode material is used in proton exchange membrane fuel cells, or metal air cells, or high-temperature polymer electrolyte membrane fuel cells.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4239488B2 (en) * | 2002-06-25 | 2009-03-18 | 東洋紡績株式会社 | Activated carbon carrier, catalyst-supported activated carbon and method for producing them |
| CN102517604A (en) * | 2011-12-15 | 2012-06-27 | 昆明理工大学 | Carbon-carrying core-shell type platinoid-platinum catalyst for indirect electrolytic hydrogen production and preparation method thereof |
| CN102738478A (en) * | 2012-06-15 | 2012-10-17 | 武汉理工大学 | Three-dimensional proton conductor based single electrode and fuel cell membrane electrode as well as preparation methods |
| CN103259023A (en) * | 2012-11-13 | 2013-08-21 | 山东省科学院新材料研究所 | Preparation method of hydrogen cell electrode material |
| WO2018187782A1 (en) * | 2017-04-07 | 2018-10-11 | The Board Of Trustees Of The University Of Illinois | Nanostructured polymer-based compositions and methods to fabricate the same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100599799B1 (en) * | 2004-06-30 | 2006-07-12 | 삼성에스디아이 주식회사 | Polymer electrolyte membrane, membrane-electrode assembly, fuel cell, and method for preparing the membrane-electrode assembly |
| US7838165B2 (en) * | 2004-07-02 | 2010-11-23 | Kabushiki Kaisha Toshiba | Carbon fiber synthesizing catalyst and method of making thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4239488B2 (en) * | 2002-06-25 | 2009-03-18 | 東洋紡績株式会社 | Activated carbon carrier, catalyst-supported activated carbon and method for producing them |
| CN102517604A (en) * | 2011-12-15 | 2012-06-27 | 昆明理工大学 | Carbon-carrying core-shell type platinoid-platinum catalyst for indirect electrolytic hydrogen production and preparation method thereof |
| CN102738478A (en) * | 2012-06-15 | 2012-10-17 | 武汉理工大学 | Three-dimensional proton conductor based single electrode and fuel cell membrane electrode as well as preparation methods |
| CN103259023A (en) * | 2012-11-13 | 2013-08-21 | 山东省科学院新材料研究所 | Preparation method of hydrogen cell electrode material |
| WO2018187782A1 (en) * | 2017-04-07 | 2018-10-11 | The Board Of Trustees Of The University Of Illinois | Nanostructured polymer-based compositions and methods to fabricate the same |
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