CN115896981A - ATO (antimony tin oxide) nano-fiber and preparation method thereof - Google Patents
ATO (antimony tin oxide) nano-fiber and preparation method thereof Download PDFInfo
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 title description 85
- 238000010438 heat treatment Methods 0.000 claims abstract description 39
- IIQBISCKFGIEED-UHFFFAOYSA-K [OH-].[OH-].[OH-].[Sn].[Sb+3] Chemical compound [OH-].[OH-].[OH-].[Sn].[Sb+3] IIQBISCKFGIEED-UHFFFAOYSA-K 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000000975 co-precipitation Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 67
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 31
- 239000006185 dispersion Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000009987 spinning Methods 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 15
- 238000002347 injection Methods 0.000 claims description 15
- 239000007924 injection Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 239000012065 filter cake Substances 0.000 claims description 10
- 229910052741 iridium Inorganic materials 0.000 claims description 10
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 239000012876 carrier material Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 4
- 239000010411 electrocatalyst Substances 0.000 claims description 4
- 238000001523 electrospinning Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- 238000004448 titration Methods 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 28
- 230000014759 maintenance of location Effects 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract 1
- 230000000607 poisoning effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 208000012886 Vertigo Diseases 0.000 description 15
- 238000001704 evaporation Methods 0.000 description 7
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 description 6
- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- -1 tin chloride antimony chloride ethanol Chemical compound 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
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Classifications
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- 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
- Y02E60/10—Energy storage using batteries
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- Inorganic Fibers (AREA)
Abstract
The invention discloses an ATO nano fiber and a preparation method thereof, comprising the following steps: precursor preparation, electrostatic spinning and heat treatment. The method adopts a coprecipitation method to prepare the tin-antimony hydroxide, and impurities such as chloride ions in the raw materials are removed by filtering and washing, so that the method has lower resistivity compared with the traditional direct electrostatic spinning, and the pollution of the chloride ions to ATO and the poisoning effect of the chloride ions on the subsequent supported noble metal catalyst are eliminated; the ATO nano-fiber prepared by the two-step heat treatment method has good structure retention rate and large specific surface area, and the continuous structure can reduce the electron conduction resistance, is beneficial to improving the transmission resistance of reactants and products in the electrocatalytic reaction process, and improves the electrocatalytic reaction rate. The ATO nano-fiber prepared by the method has the advantages of high purity, high specific surface area, low resistivity, high structure retention rate, low cost and the like, and has a good application prospect in the field of electrocatalysis.
Description
Technical Field
The invention belongs to the technical field of proton exchange membrane fuel cell preparation technology and new energy, and relates to a method for preparing nanofibers by using an electrostatic spinning technology, in particular to ATO nanofibers and a preparation method thereof.
Background
In the field of electrocatalytic reactions, such as electrochemical reduction of oxygen, oxygen evolution by electrolysis and hydrogen evolution by electrolysis, the adopted catalyst and the carrier thereof are required to have good chemical stability, electrochemical stability, mechanical stability, higher conductivity, high specific surface area and lower impurity content in acid or alkali environment.
Antimony doped tin oxide (ATO) is a stable electrochemical catalyst support material with good conductivity under acid or alkaline conditions. The specific surface area of ATO can be effectively increased by preparing ATO nano-fiber through electrostatic spinning, and the nano-fiber structure can reduce and reduce electron conduction resistance and is beneficial to improving the transmission resistance of reactants and products in the electrocatalytic reaction process, thereby increasing the electrocatalytic reaction rate.
The existing ATO electrostatic spinning technologyThe preparation method comprises the steps of mixing Sn and Sb precursors containing chloride ions with a solvent and a polymer to prepare electrostatic spinning slurry, directly spinning and then roasting. For example, chinese application CN103290525B TiO of core-shell structure 2 ATO nano-fiber and preparation method thereof, and Chinese application CN103436991B nano-fiber capable of improving specific surface area. Although the preparation process is simple, the prepared ATO fibers contain a large amount of impurities, such as Cl elements, which can cause poor conductivity and structural order degree of the ATO nanofibers and low specific surface area, and limit the use of the ATO nanofibers in the fields of electrochemistry and chemical energy.
Disclosure of Invention
The invention discloses an ATO nano-fiber and a preparation method thereof according to the defects of the prior art. The preparation method disclosed by the invention can reduce the content of harmful impurity elements in the ATO nano-fibers, reduce the resistivity of the ATO fibers, improve the specific surface area and the structural retention rate of the ATO, and is beneficial to promoting the utilization of the ATO nano-fibers in the fields of electrochemistry and chemical energy.
The invention is realized by the following technical scheme:
a preparation method of ATO nano-fiber is characterized by comprising the following steps: preparing a precursor, electrostatic spinning and heat treatment; the method specifically comprises the following steps:
preparation of the S1 precursor: dissolving tin chloride and antimony chloride serving as metal sources in a hydrochloric acid solution by adopting a coprecipitation method, carrying out cotitration with an alkali liquor to prepare tin-antimony hydroxide, filtering and washing to remove impurities including chloride ions to obtain a tin-antimony hydroxide filter cake without impurities, and dispersing the tin-antimony hydroxide filter cake in a solvent to obtain a tin-antimony hydroxide dispersion liquid;
s2, electrostatic spinning: adding a polymer into the tin antimony hydroxide dispersion liquid obtained in the step S1 to prepare a spinning solution, and performing electrostatic spinning after uniform dispersion to prepare nano fibers with the diameter of 50-1000 nm;
s3, heat treatment: the heat treatment is divided into two stages; the first stage of pre-oxidation, heating from room temperature to 100-400 ℃ in air atmosphere, and keeping the temperature for 0.1-5 hours; and (3) performing high-temperature pyrolysis in the second stage, heating to 400-900 ℃ after heat preservation in the first stage, and preserving the heat for 0.1-5 hours to prepare the ATO nano-fiber.
In the further step S1, in the preparation of the precursor, the mass percentage of Sn to Sb is 100.
In the further step S1 of precursor preparation, chloride ions in the solution are removed by filtration and washing, and dispersed in a solvent; wherein the dispersing solvent is: at least one of water, ethanol, N-dimethylformamide, isopropanol and N-propanol.
In the further step S2 of electrospinning, the polymer is: at least one of polyacrylic acid, polyvinylpyrrolidone, polyacrylonitrile, polyamide, polystyrene, polyether sulfone and polyvinyl alcohol, wherein the mass ratio of the polymer to Sn and Sb is 10.
The preparation method of the ATO nano-fiber specifically comprises the following steps:
preparation of the S1 precursor:
weighing SnCl 4 And SbCl 3 Dissolving the mixture in 0.1-4M HCl solution, and performing ultrasonic dispersion to obtain clear solution, namely first solution; wherein the mass ratio of the transition metal Sn to Sb is 100;
preparing an alkali solution with the concentration of 0.1-4M;
respectively transferring the prepared first solution and alkali solution into a burette, slowly dripping the first solution and the alkali solution into the solution of the reactor, stirring, keeping the pH = X +/-0.2 of the mixture solution in the dripping process, and keeping X between 1 and 6;
after the titration is finished, stirring for 0.1 to 10 hours at the constant temperature of between 20 and 90 ℃ to obtain a tin-antimony hydroxide precipitate;
separating the precipitate from the liquid, washing with deionized water for several times until the conductivity of the filtrate is less than 10 μ S-cm, washing off impurities, and separating to obtain a tin-antimony hydroxide filter cake; dispersing the filter cake in a dispersion solvent to obtain a tin antimony hydroxide dispersion liquid, namely a second dispersion liquid;
s2, electrostatic spinning:
adding a polymer into the second dispersion liquid, and stirring for 0.1-10 hours under the condition of heating in a water bath at the temperature of 20-90 ℃ to obtain a spinning solution; wherein the solid content in the spinning solution is 1-10 wt%, and the mass content of the polymer is 1-70 wt%;
sucking the prepared spinning solution into an injector provided with a metal needle head, wherein the diameter of the metal needle head is 100-1000 mu m;
communicating the injector filled with the slurry with an injection pump, and moving the injection pump forwards at the injection speed of 0.1-2 mm/min;
applying positive high voltage of 2-50 kV on the needle head, applying negative high voltage of 1-20 kV on the spinning receiver, and enabling the distance between the receiver and the needle head to be 2-20 cm;
after spinning, taking out the spun nanofiber and putting the nanofiber into a vacuum oven for drying;
s3, heat treatment:
and (3) putting the dried nanofiber obtained in the step (S2) into a muffle furnace, heating to 100-400 ℃ in the air atmosphere, preserving the heat for 0.1-5 hours, continuing heating to 400-900 ℃, preserving the heat for 0.1-5 hours, and finally reducing the furnace temperature to room temperature to obtain the ATO nanofiber.
The ATO nano-fiber prepared by the invention can be used as an electrocatalyst carrier material for electrolytic water reaction or a catalyst carrier material for oxygen reduction reaction of a fuel cell, wherein the mass content of the ATO nano-fiber is 20-95%.
The catalyst comprises an ATO nanofiber supported iridium-based carrier material for an electrolytic water reaction electrocatalyst; or ATO nano-fiber supported platinum-based carrier materials for oxygen reduction reaction catalysts for fuel cells.
In the preparation of the precursor, a coprecipitation method is adopted, tin chloride and antimony chloride are used as metal sources to prepare tin-antimony hydroxide, impurities such as chloride ions in the solution are removed in a filtering and washing mode, and the tin-antimony hydroxide dispersion liquid is obtained by dispersing the impurities in the solvent again. The solvent is also the solvent of the spinning solution and is at least one of water, ethanol, N-dimethylformamide, isopropanol and N-propanol.
In electrostatic spinning, adding a certain amount of polymer into tin antimony hydroxide dispersion liquid, wherein the polymer is at least one of polyacrylic acid, polyvinylpyrrolidone, polyacrylonitrile, polyamide, polystyrene, polyether sulfone and polyvinyl alcohol, and performing electrostatic spinning after uniform dispersion; the method comprises the steps of preparing uniform nano-fibers with the diameter of 50-1000 nm by adjusting the content of tin-antimony hydroxide, the type and content of polymers, the type and content of solvents and parameters of electrostatic spinning, such as the diameter of a needle head, voltage and the distance between the needle head and a roller, and then putting the nano-fibers into an oven for drying.
The heat treatment is divided into two stages: the first stage is the pre-oxidation of the nanofibers: the stage is mainly evaporation of solvent and preoxidation of the nano-fibers, so that the stability of the nano-fibers is improved, and the structure of the fibers can still be maintained in the second stage of heat treatment. The temperature at this stage is relatively low, generally below the glass transition temperature of the polymer. The second stage is high temperature pyrolysis of the nanofibers: the stage is carbonization and oxidation of the polymer in air, the polymer is decomposed into CO 2 、CO、N 2 、H 2 And (3) waiting for gas, wherein the tin antimony hydroxide in the nanofiber is gradually dehydrated in the high-temperature pyrolysis process to be changed into oxide (ATO) along with the aggregation and growth of crystal grains, so that the ATO nanofiber is obtained.
The method adopts a coprecipitation method to prepare the tin-antimony hydroxide, and impurities such as chloride ions in the raw materials are removed by filtering and washing to obtain the impurity-free tin-antimony hydroxide precipitate.
The two-step heat treatment method adopted by the invention comprises the steps of pre-oxidizing the precursor of the ATO nano-fiber at a lower temperature, and then pyrolyzing the precursor of the ATO nano-fiber at a higher temperature, wherein the ATO nano-fiber prepared by the two-step heat treatment method has good retention rate and larger specific surface area, and the nano-fiber-shaped continuous structure can reduce the electron conduction resistance, is beneficial to improving the transmission resistance of reactants and products in the electrocatalytic reaction process, and improves the electrocatalytic reaction rate.
The ATO nano-fiber prepared by the method disclosed by the invention has the advantages of high purity, high specific surface area, low resistivity, high structure retention rate and low cost, and has a good application prospect in the field of electrocatalysis.
Drawings
FIG. 1 is a scanning electron microscope image of ATO nanofiber-1 prepared in the present invention before calcination;
FIG. 2 is a scanning electron microscope image of ATO nanofiber-1 prepared in the present invention;
FIG. 3 is a Linear Sweep Voltammetry (LSV) curve of an iridium-based catalyst prepared by using ATO nano-fibers prepared by the present invention as a carrier;
fig. 4 is a Linear Sweep Voltammetry (LSV) curve of a platinum-based catalyst prepared by using ATO nanofibers prepared by the present invention as a support.
Detailed Description
The present invention is further described below in conjunction with the following detailed description, which is intended to further illustrate the principles of the invention and is not intended to limit the invention in any way, but is equivalent or analogous to the present invention without departing from its scope.
Example 1:
s1 precursor preparation stage:
4.689g (1.8 mmol) of SnCl was weighed 4, And 0.456g (0.2 mmol) of SbCl 3 Dissolving the precipitate in 100mL of HCl (2M), and ultrasonically dispersing for 30min to obtain a clear solution (a first solution);
dissolving 12g of NaOH in 150mL of deionized water;
transferring the prepared first solution and NaOH solution into a burette, slowly dripping the first solution and NaOH solution into the solution in the reactor, and strictly controlling the pH value of the reaction to be 2 +/-0.1 and the rotating speed to be 700rpm;
after titration, stirring at the constant temperature of 50 ℃ for 2 hours at the rotating speed of 700rpm, and generating yellow precipitate which is tin-antimony hydroxide;
and carrying out vacuum filtration on the precipitate, and washing the precipitate for several times by using deionized water until the conductivity of the filtrate is less than 10 mu S-cm, wherein the impurities are mainly removed by washing. The filter cake was dispersed in 50mL of an anhydrous ethanol solution to obtain an ethanol dispersion of tin antimony hydroxide (second dispersion).
S2, electrostatic spinning stage:
taking 10mL of the second dispersion prepared in the step S1, adding 1g of polyacrylic acid (PAA) into the second dispersion, and stirring the mixture for 20min under the heating of a water bath at the temperature of 60 ℃ to obtain a spinning solution;
sucking the dispersed spinning solution into a 10mL syringe equipped with a No. 21 metal needle having a diameter of about 500 μm;
then communicating the injector filled with the slurry with an injection pump, and moving the injection pump forwards at the injection speed of 0.8 mm/min;
applying positive high voltage of 12kV on the needle head, applying negative high voltage of 5kV on the receiving rotary drum, and rotating at constant speed of 100r/min at a position 10cm away from the needle head;
after spinning, the spun nanofiber was taken out and put into a vacuum oven for drying at 80 ℃ for 6 hours, and the structure thereof is shown in fig. 1.
S3, a heat treatment stage:
and (3) putting the dried nano-fiber obtained in the step (S2) into a muffle furnace, heating to 200 ℃ in the air atmosphere, preserving the heat for 2 hours, continuing heating to 600 ℃, preserving the heat for 1 hour, heating at a rate of 2 ℃/min, and finally reducing the furnace temperature to room temperature to obtain the ATO nano-fiber, which is marked as ATO nano-fiber-1 and is shown in figure 2. It can be seen from the figure that the ATO nano-fiber prepared in the embodiment is composed of ATO nano-particles bonded with each other, the fiber diameter is about 100nm, and the retention rate of the fiber structure after heat treatment is good.
Example 2:
this example differs from example 1 only in the type of polymer used in the S2 electrospinning stage, the polymer used in this example being polyvinylpyrrolidone (PVP). The ATO nanofibers prepared in example 2, are designated as "ATO nanofiber-2".
Example 3:
the present example differs from example 1 only in the ratio of Sn to Sb precursors used in the S1 precursor preparation stage, and the specific steps are as follows:
s1 precursor preparation stage:
4.950g (1.9 mmol) of SnCl was weighed 4, And 0.228g (0.1 mmol) of SbCl 3 Dissolving the precipitate in 100mL of HCl (2M), and ultrasonically dispersing for 30min to obtain a clear solution (a first solution);
dissolving 12g of NaOH in 150mL of deionized water;
transferring the prepared first solution and NaOH solution into a burette, slowly dripping the first solution and NaOH solution into the solution in the reactor, and strictly controlling the pH value of the reaction to be 2 +/-0.1 and the rotating speed to be 700rpm;
after titration, stirring at the constant temperature of 50 ℃ for 2 hours at the rotating speed of 700rpm, and generating yellow precipitate which is tin-antimony hydroxide;
and (4) carrying out vacuum filtration on the precipitate, washing the precipitate for a plurality of times by using deionized water until the conductivity of the filtrate is less than 10 mu S-cm, and mainly removing impurities by washing. The filter cake was dispersed in 50mL of an anhydrous ethanol solution to obtain an ethanol dispersion of tin antimony hydroxide (second dispersion).
S2, electrostatic spinning stage:
taking 10mL of the second dispersion prepared in the step S1, adding 1g of polyacrylic acid (PAA) into the second dispersion, and stirring the mixture for 20min under the heating of a water bath at the temperature of 60 ℃ to obtain a spinning solution;
sucking the dispersed spinning solution into a 10mL syringe equipped with a No. 21 metal needle having a diameter of about 500 μm;
then communicating the injector filled with the slurry with an injection pump, and moving the injection pump forwards at the injection speed of 0.8 mm/min;
applying positive high voltage of 12kV on the needle head, applying negative high voltage of 5kV on the receiving rotary drum, and rotating at constant speed of 100r/min at a position 10cm away from the needle head;
and after spinning is finished, taking out the spun nanofiber, and putting the nanofiber into a vacuum oven for drying at 80 ℃ for 6 hours.
S3, a heat treatment stage:
and (3) putting the dried nano-fiber obtained in the step (S2) into a muffle furnace, heating to 200 ℃ in the air atmosphere, preserving the heat for 2 hours, continuing heating to 600 ℃, preserving the heat for 1 hour, heating at a speed of 2 ℃/min, and finally reducing the furnace temperature to room temperature to finally obtain the ATO nano-fiber which is marked as ATO nano-fiber-3.
Comparative example 1:
the comparative example has no precursor preparation stage, and specifically comprises the following steps from the electrospinning stage:
4.689g (1.8 mmol) of SnCl was weighed 4, And 0.456g (0.2 mmol) of SbCl 3 Dissolving it in 100mL of ethanol and addingDispersing by sound for 30min to obtain clear solution.
10mL of tin chloride antimony chloride ethanol solution is taken, 1g of polyacrylic acid (PAA) is added into the solution, and the solution is stirred for about 20min under the heating of a water bath at the temperature of 60 ℃.
Sucking the dispersed slurry into a 10mL syringe equipped with a 21-gauge metal needle having a diameter of about 500 μm;
then the injector filled with the slurry is communicated with an injection pump, and the injection pump moves forwards at the injection speed of 0.8 mm/min;
applying positive high voltage of 12kV on the needle head, applying negative high voltage of 5kV on the receiving rotary drum, and rotating at constant speed of 100r/min at a position 10cm away from the needle head;
after spinning is finished, taking out the spun nano-fiber, and drying the nano-fiber in a vacuum oven at the temperature of 80 ℃ for 6 hours;
the heat treatment stage specifically comprises the following steps:
and (3) putting the dried nanofiber into a muffle furnace, heating to 200 ℃ in the air atmosphere, preserving the heat for 2 hours, continuing heating to 600 ℃, preserving the heat for 1 hour, heating at a rate of 2 ℃/min, and finally reducing the furnace temperature to room temperature to finally obtain the ATO nanofiber, which is recorded as the ATO nanofiber-contrast.
As can be seen from Table 1, the comparative example prepared the "ATO nanofiber-comparative" having a resistivity of 3. Omega. Cm 100 times that of the "ATO nanofiber-1" prepared in example 1 and having a Cl content 63 times that of the "ATO nanofiber-1" prepared in example 1, compared to the examples. It can also be seen from the table that the ATO nanofibers produced using the process of the present invention all have much higher specific surface areas than the comparative examples, and that the specific surface area of the "ATO nanofiber-1" samples is as high as 150m 2 (ii) in terms of/g. In conclusion, the ATO nanofibers prepared by the inventive process are superior to the conventional process (comparative) in terms of resistivity, impurity content and specific surface area, and the "ATO nanofiber-1" sample prepared in example 1 is the best performing.
TABLE 1
Example 4: (Ir/ATO-1)
Preparing an ATO nanofiber-supported iridium-based catalyst by using an ATO nanofiber-1 as a carrier:
dissolving 1g of iridium acetylacetonate in 100mL of absolute ethanol, adding 5g of ATO nanofiber-1 carrier into the iridium acetylacetonate ethanol solution, evaporating the solvent in a water bath at 65 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 350 ℃ for 4h in an air atmosphere to obtain an ATO nanofiber supported iridium-based catalyst, which is marked as IrO 2 /ATO-1”。
Example 5: (Ir/ATO-2)
Preparing an ATO nanofiber-supported iridium-based catalyst by using an ATO nanofiber-2 as a carrier:
dissolving 1g of iridium acetylacetonate in 100mL of absolute ethanol, adding 5g of ATO nanofiber-1 carrier into the iridium acetylacetonate ethanol solution, evaporating the solvent in a water bath at 65 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 350 ℃ for 4h in an air atmosphere to obtain an ATO nanofiber supported iridium-based catalyst, which is marked as IrO 2 /ATO-2”。
Example 6: (Ir/ATO-comparison)
The ATO nanofiber-supported iridium-based catalyst was prepared using the "ATO nanofiber-comparative" as the support:
dissolving 1g of iridium acetylacetonate in 100mL of absolute ethanol, adding 5g of ATO nanofiber-1 carrier into the iridium acetylacetonate ethanol solution, evaporating the solvent in a water bath at 65 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 350 ℃ for 4h in an air atmosphere to obtain an ATO nanofiber supported iridium-based catalyst, which is marked as' IrO 2 ATO-comparison ".
The resistivity and the Oxygen Evolution Reaction (OER) catalytic activity of iridium-based catalysts prepared using different ATO nanofibers as carriers were respectively tested, and the results thereof are shown in table 2 and fig. 3. It can be seen from table 2 that the electrical resistivity of the catalysts prepared using the three supports "ATO nanofiber-1", "ATO nanofiber-2" and "ATO nanofiber-comparative" is greatly reduced with respect to the support thereof, wherein "IrO" is 2 /ATO-1”、“IrO 2 /ATO-2”The overpotential of the catalyst is lower than that of commercial IrO 2 The catalyst shows that the ATO nano-fiber is an excellent carrier of the OER reaction catalyst. In addition "IrO 2 [ ATO-1 ] and [ IrO ] 2 The resistivity and OER reaction overpotential of the/ATO-2' catalyst are far lower than that of IrO 2 The resistivity of the catalyst and the overpotential of the OER reaction are compared, so that the ATO nano-fiber with low resistivity, low impurity and high specific surface area prepared by the method is more suitable to be used as an OER catalyst carrier.
TABLE 2
Example 7: preparation of ATO-Supported platinum nanoparticles (Pt/ATO-1)
Selecting 'ATO nanofiber-1' as a carrier, and soaking the 'ATO nanofiber-1' into 128mL of 0.04mol/L platinum acetylacetonate solution by taking 0.04mol/L platinum acetylacetonate solution as soaking solution 4 g. And after 24 hours of dipping, evaporating the solvent in a water bath at 65 ℃, drying in a drying oven at 120 ℃ for 10 hours, and then roasting the solid substance in a hydrogen atmosphere at 300 ℃ for 4 hours to obtain the ATO nanofiber loaded platinum-based catalyst, which is marked as Pt/ATO-1.
Example 8: preparation of ATO-Supported platinum nanoparticles (Pt/ATO-2)
Selecting ATO nanofiber-2 as a carrier, and soaking the ATO nanofiber-2 in 128mL0.04mol/L platinum acetylacetonate solution by using 0.04mol/L platinum acetylacetonate solution as soaking solution 4 g. And after 24 hours of immersion, evaporating the solvent in a water bath at 65 ℃, drying in a drying oven at 120 ℃ for 10 hours, and roasting the solid matter in a hydrogen atmosphere at 300 ℃ for 4 hours to obtain the ATO nanofiber-supported platinum-based catalyst, which is marked as Pt/ATO-2.
Example 9: preparation of ATO-Supported platinum nanoparticles (Pt/ATO-comparative)
Selecting an ATO nano-fiber-contrast as a carrier and taking 0.04mol/L platinum acetylacetonate solution as impregnation liquid 4g, and immersing the ATO nano-fiber-contrast into 128mL0.04mol/L platinum acetylacetonate solution. And after 24 hours of dipping, evaporating the solvent in a water bath at 65 ℃, drying in a drying oven at 120 ℃ for 10 hours, and roasting the solid matter in a hydrogen atmosphere at 300 ℃ for 4 hours to obtain the ATO nanofiber loaded platinum-based catalyst, which is recorded as Pt/ATO-comparison.
TABLE 3
Platinum-based catalysts were prepared using different ATO nanofibers as carriers, and the resistivity and Oxygen Reduction Reaction (ORR) catalytic activity thereof were respectively tested, and the results thereof are shown in table 3 and fig. 4. It can be seen from table 3 that the electrical resistivity of the catalysts prepared using the three supports "ATO nanofiber-1", "ATO nanofiber-2" and "ATO nanofiber-comparative" is greatly reduced relative to the support. In addition, the resistivity and ORR reaction activity of the 'Pt/ATO-1' and 'Pt/ATO-2' catalysts are superior to those of the 'Pt/ATO-comparative' catalyst, so that the low-resistivity and low-impurity ATO nano-fiber prepared by the method can be used as a carrier of a platinum-based catalyst.
Claims (9)
1. A preparation method of ATO nano-fiber is characterized by comprising the following steps: preparing a precursor, electrostatic spinning and heat treatment; the method specifically comprises the following steps:
preparation of the S1 precursor: dissolving tin chloride and antimony chloride serving as metal sources in a hydrochloric acid solution by adopting a coprecipitation method, carrying out cotitration with an alkali liquor to prepare tin-antimony hydroxide, filtering and washing to remove impurities including chloride ions to obtain a tin-antimony hydroxide filter cake without impurities, and dispersing the tin-antimony hydroxide filter cake in a solvent to obtain a tin-antimony hydroxide dispersion liquid;
s2, electrostatic spinning: adding a polymer into the tin antimony hydroxide dispersion liquid obtained in the step S1 to prepare a spinning solution, and performing electrostatic spinning after uniform dispersion to prepare nano fibers with the diameter of 50-1000 nm;
s3, heat treatment: the heat treatment is divided into two stages; the first stage of pre-oxidation, heating from room temperature to 100-400 deg.c in air atmosphere and maintaining for 0.1-5 hr; and (3) performing high-temperature pyrolysis in the second stage, heating to 400-900 ℃ after heat preservation in the first stage, and preserving the heat for 0.1-5 hours to prepare the ATO nano-fiber.
2. The ATO nanofiber preparation method as claimed in claim 1, characterized in that: in the step S1, in the preparation of the precursor, the mass percentage of Sn to Sb is 100.
3. The ATO nanofiber preparation method as claimed in claim 1, characterized in that: in the step S1, in the preparation of the precursor, chloride ions in the solution are removed by filtration and washing, and the chloride ions are dispersed in a solvent; wherein the dispersing solvent is: at least one of water, ethanol, N-dimethylformamide, isopropanol and N-propanol.
4. The ATO nanofiber manufacturing method as claimed in claim 1, characterized in that: in step S2 of electrospinning, the polymer is: at least one of polyacrylic acid, polyvinylpyrrolidone, polyacrylonitrile, polyamide, polystyrene, polyether sulfone and polyvinyl alcohol, wherein the mass ratio of the polymer to Sn and Sb is 10.
5. The method for preparing ATO nanofibers according to any of claims 1 to 4, characterized in that it specifically comprises the following steps:
preparation of the S1 precursor:
weighing SnCl 4 And SbCl 3 Dissolving the mixture in 0.1-4M HCl solution, and performing ultrasonic dispersion to obtain clear solution, namely first solution; wherein the mass ratio of the transition metal Sn to Sb is 100;
preparing an alkali solution with the concentration of 0.1-4M;
respectively transferring the prepared first solution and aqueous alkali into a burette, slowly dripping the first solution and the aqueous alkali into the solution in the reactor, stirring, and keeping the pH = X +/-0.2 of the mixture solution in the dripping process, wherein X is 1-6;
after the titration is finished, stirring for 0.1 to 10 hours at the constant temperature of between 20 and 90 ℃ to obtain a tin-antimony hydroxide precipitate;
separating the precipitate from the liquid, washing with deionized water for several times until the conductivity of the filtrate is less than 10 μ S-cm, washing off impurities, and separating to obtain a tin-antimony hydroxide filter cake; dispersing the filter cake in a dispersion solvent to obtain a tin antimony hydroxide dispersion liquid, namely a second dispersion liquid;
s2, electrostatic spinning:
adding a polymer into the second dispersion liquid, and stirring for 0.1-10 hours under the condition of heating in a water bath at the temperature of 20-90 ℃ to obtain a spinning solution; wherein the solid content in the spinning solution is 1-10 wt%, and the mass content of the polymer is 1-70 wt%;
sucking the prepared spinning solution into an injector provided with a metal needle head, wherein the diameter of the metal needle head is 100-1000 mu m;
communicating the injector filled with the slurry with an injection pump, and moving the injection pump forwards at a push injection speed of 0.1-2 mm/min;
applying positive high voltage of 2-50 kV on the needle head, applying negative high voltage of 1-20 kV on the spinning receiver, and enabling the distance between the receiver and the needle head to be 2-20 cm;
after spinning, taking out the spun nanofiber and putting the nanofiber into a vacuum oven for drying;
s3, heat treatment:
and (3) putting the dried nano-fibers obtained in the step (S2) into a muffle furnace, heating to 100-400 ℃ in an air atmosphere, preserving the heat for 0.1-5 hours, continuing to heat to 400-900 ℃, preserving the heat for 0.1-5 hours, and finally reducing the furnace temperature to room temperature to obtain the ATO nano-fibers.
6. An ATO nanofiber characterized in that: the ATO nanofiber is the ATO nanofiber prepared in any one of claims 1 to 5.
7. A carrier material characterized by: the support material is made of the ATO nano-fiber of claim 6, an electrocatalyst support material for an electrolytic water reaction or a fuel cell oxygen reduction reaction catalyst support material, wherein the ATO nano-fiber is in a mass content of 20 to 95%.
8. The carrier material of claim 7, wherein: the carrier material is an ATO nanofiber supported iridium-based carrier material for an electrolytic water reaction electrocatalyst.
9. The carrier material of claim 7, wherein: the support material is an ATO nanofiber supported platinum-based support material for an oxygen reduction reaction catalyst for a fuel cell.
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1357509A (en) * | 2000-12-14 | 2002-07-10 | 成都亿安方博低维材料科技有限公司 | Transparent conductive nano Sb:SnO2 fine powder |
CN102695824A (en) * | 2009-11-04 | 2012-09-26 | 巴斯夫欧洲公司 | Process for producing nanofibres |
CN103641157A (en) * | 2013-12-04 | 2014-03-19 | 西南交通大学 | Method for preparing low-resistance nanometer powder |
CN104617314A (en) * | 2013-11-04 | 2015-05-13 | 中国科学院大连化学物理研究所 | Fuel cell catalyst Pt/ATO, and preparation method and application thereof |
CN104925853A (en) * | 2015-06-04 | 2015-09-23 | 天津市职业大学 | Stable nano antimony-doped tin dioxide hydrosol and preparation method thereof |
WO2020111710A1 (en) * | 2018-11-26 | 2020-06-04 | 고려대학교 산학협력단 | Electrode material for electrochemical water treatment, and manufacturing method therefor |
US20200335800A1 (en) * | 2019-04-19 | 2020-10-22 | Korea Institute Of Science And Technology | FLUORINE-DOPED TIN OXIDE SUPPORT AND Pt CATALYST FOR FUEL CELL COMPRISING THE SAME |
CN113620337A (en) * | 2021-09-02 | 2021-11-09 | 畅的新材料科技(上海)有限公司 | Preparation method of antimony-doped tin dioxide heat insulation material |
-
2022
- 2022-12-01 CN CN202211538569.4A patent/CN115896981A/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1357509A (en) * | 2000-12-14 | 2002-07-10 | 成都亿安方博低维材料科技有限公司 | Transparent conductive nano Sb:SnO2 fine powder |
CN102695824A (en) * | 2009-11-04 | 2012-09-26 | 巴斯夫欧洲公司 | Process for producing nanofibres |
CN104617314A (en) * | 2013-11-04 | 2015-05-13 | 中国科学院大连化学物理研究所 | Fuel cell catalyst Pt/ATO, and preparation method and application thereof |
CN103641157A (en) * | 2013-12-04 | 2014-03-19 | 西南交通大学 | Method for preparing low-resistance nanometer powder |
CN104925853A (en) * | 2015-06-04 | 2015-09-23 | 天津市职业大学 | Stable nano antimony-doped tin dioxide hydrosol and preparation method thereof |
WO2020111710A1 (en) * | 2018-11-26 | 2020-06-04 | 고려대학교 산학협력단 | Electrode material for electrochemical water treatment, and manufacturing method therefor |
US20200335800A1 (en) * | 2019-04-19 | 2020-10-22 | Korea Institute Of Science And Technology | FLUORINE-DOPED TIN OXIDE SUPPORT AND Pt CATALYST FOR FUEL CELL COMPRISING THE SAME |
CN113620337A (en) * | 2021-09-02 | 2021-11-09 | 畅的新材料科技(上海)有限公司 | Preparation method of antimony-doped tin dioxide heat insulation material |
Non-Patent Citations (2)
Title |
---|
刘述忠: "纳米掺锑氧化锡(ATO)粉体制备及其浆料稳定性", 中国博士学位论文全文数据库工程科技Ⅰ辑, 15 January 2012 (2012-01-15), pages 1 - 107 * |
闵祥萍 等: "高效铱基析氧催化剂及超低贵金属用量质子交换膜水电解器研究", 中国化学会第二十次全国电化学大会, 31 December 2019 (2019-12-31) * |
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