CN113921835B - Preparation method of high-temperature proton exchange membrane fuel cell cathode catalyst - Google Patents
Preparation method of high-temperature proton exchange membrane fuel cell cathode catalyst Download PDFInfo
- Publication number
- CN113921835B CN113921835B CN202110988396.5A CN202110988396A CN113921835B CN 113921835 B CN113921835 B CN 113921835B CN 202110988396 A CN202110988396 A CN 202110988396A CN 113921835 B CN113921835 B CN 113921835B
- Authority
- CN
- China
- Prior art keywords
- black phosphorus
- activated
- fuel cell
- exchange membrane
- graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of a cathode catalyst of a high-temperature proton exchange membrane fuel cell, which comprises the steps of firstly preparing a black phosphorus nano sheet material, further carrying out mechanical ball milling on the black phosphorus nano sheet material and an alkali liquid activated graphene sheet material, heating in a reaction kettle to effectively form a heterostructure between black phosphorus and activated graphene, and finally adding a metal precursor and a reducing agent according to a certain proportion to obtain noble metal particles loaded by the black phosphorus-activated graphene composite material, thereby effectively improving the electrochemical activity, the utilization rate and the stability of the noble metal catalyst.
Description
Technical Field
The invention belongs to the field of materialy, relates to a cathode catalyst material of a high-temperature proton exchange membrane fuel cell, and particularly relates to a preparation method of a black phosphorus-activated graphene composite material supported noble metal nanoparticle.
Background
Compared with a low-temperature proton exchange membrane fuel cell working at 60-80 ℃, the phosphoric acid doped PBI-based high-temperature proton exchange membrane fuel cell (HT-PEMFC) generally works at 160-180 ℃, has the advantages of fast electrode reaction dynamics process, strong carbon monoxide resistance, simple water heat management and the like, and has wide application prospect in the fields of military special power supplies, portable power supplies, fixed power stations and auxiliary power supplies. However, the conventional catalyst of the HT-PEMFC cathode is carbon-supported platinum or carbon-supported platinum alloy, and the problems of low noble metal catalyst utilization rate, high loading capacity and poor stability exist, which severely limit the application of the HT-PEMFC.
Disclosure of Invention
The invention aims to overcome the defects, and provides a preparation method of a high-temperature proton exchange membrane fuel cell (HT-PEMFC) cathode catalyst, which comprises the steps of firstly preparing a black phosphorus nano sheet material, further carrying out mechanical ball milling on the black phosphorus nano sheet material and an alkali activated graphene sheet material, heating in a reaction kettle to effectively form a heterostructure between the black phosphorus and the activated graphene, and finally adding a metal precursor and a reducing agent according to a certain proportion to obtain noble metal particles loaded by the black phosphorus-activated graphene composite material, thereby effectively improving the electrochemical activity, the utilization rate and the stability of the noble metal catalyst.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the preparation method of the cathode catalyst of the high-temperature proton exchange membrane fuel cell comprises the following steps:
(1) Removing the surface oxide layer of the blocky red phosphorus, and grinding to obtain red phosphorus powder;
(2) Mixing red phosphorus powder, sn, and SnI 4 Heating under vacuum condition, cooling and washing to obtain block black phosphorus, and grinding to obtain black phosphorus powder;
(3) Adding black phosphorus powder into NMP solution, carrying out ultrasonic stripping under the condition of inert gas, taking supernatant, further carrying out continuous ice bath ultrasonic treatment, and centrifuging to obtain black phosphorus nano lamellar material;
(4) Performing mechanical ball milling on the black phosphorus nano lamellar material and the graphene lamellar material activated by alkali liquor under the condition of inert gas to obtain a composite material precursor;
(5) Dispersing the composite material precursor in ethylenediamine, heating in a reaction kettle, cooling, washing and vacuum drying to obtain a black phosphorus-activated graphene composite material;
(6) Dispersing the black phosphorus-activated graphene composite material in isopropanol, and adding a noble metal precursor for stirring;
(7) And (3) regulating the pH value of the dispersion liquid obtained in the step (6), slowly dripping a reducing agent, stirring for 2 hours, centrifugally washing the obtained product, and drying in vacuum to obtain the black phosphorus-activated graphene composite material loaded noble metal nano particles.
In the step (1), the method for removing the surface oxide layer of the red phosphorus is that the red phosphorus and deionized water are placed in a reaction kettle together, and the red phosphorus and the deionized water are subjected to hydrothermal treatment at 160-180 ℃ for more than 15 hours.
Further, in the step (2), red phosphorus powder, sn, and SnI 4 The mass ratio of (2) is 1: (0.02-0.08): (0.01-0.06); in the step (2), the vacuum heating method is to heat red phosphorus powder, sn and SnI 4 Adding the mixture into a quartz tube, vacuumizing and sealing, and sequentially heating, preserving heat, cooling and preserving heat; in step (2), washing is performed using toluene and acetone washing.
Further, in the step (2), the vacuum heating method is to heat red phosphorus powder, sn and SnI 4 Vacuum-pumping and sealing in quartz tube at 3-10 deg.C for 3 min -1 Heating to 600-700 ℃ for 2-3h, then cooling to 450-500 ℃ and preserving heat for 5-7h.
Further, in the step (3), the NMP solution is a NMP solution of saturated NaOH, and the inert gas is argon; in the step (3), the ultrasonic stripping method is that the ultrasonic stripping is carried out for 12-16 hours in a cell grinder under the condition of 400-600W.
Further, in the step (4), the graphene activated by alkali liquor is graphene activated by a potassium hydroxide solution of 6-7 mol/L, and the activation method comprises the steps of stirring the graphene in the potassium hydroxide solution for 8-10 hours, respectively centrifugally washing the graphene with isopropanol, absolute ethyl alcohol and deionized water for 3-5 times, drying and grinding the obtained sample, heating the sample to 600 ℃ at 5 ℃/min in nitrogen, preserving heat for 30min, and heating the sample to 800 ℃ at 2 ℃/min, and preserving heat for 2h.
Further, in the step (4), the mass ratio of the black phosphorus nano lamellar material to the alkali liquid activated graphene lamellar material is 1:0.5-2; in the step (4), a ball mill is used for mechanical ball milling under the argon condition, the rotating speed of the ball mill is 500-700 rpm, and the mechanical ball milling time is 45-60h.
Further, in the step (5), the precursor of the composite material is dispersed in ethylenediamine, heated to 140 ℃ in a reaction kettle, reacted for 12 hours, naturally cooled, and then respectively centrifugally washed for 3-5 times by isopropanol, absolute ethanol and deionized water, and vacuum-dried at the temperature of 50-60 ℃ to obtain the black phosphorus-activated graphene composite material.
Further, in step (6), the noble metal precursor is a chloride of platinum, palladium or gold.
Further, in the step (7), after adjusting the pH of the dispersion liquid obtained in the step (6) to 8-11, adding a reducing agent sodium borohydride or hydrazine hydrate; the mass ratio of the metal precursor added in the step (6) to the reducing agent added in the step (7) is 1:1-80.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the preparation method of the high-temperature proton exchange membrane fuel cell cathode catalyst, the heating condition of red phosphorus is designed to ensure that the red phosphorus is stably and efficiently converted into black phosphorus, and the black phosphorus is ultrasonically stripped in NMP solution to obtain a black phosphorus nano sheet material with a stable structure;
(2) In the preparation method of the high-temperature proton exchange membrane fuel cell cathode catalyst, the black phosphorus nano sheet layer and the alkali liquor activated graphene sheet layer are utilized for mechanical ball milling, and a heterostructure is effectively formed between the black phosphorus and the activated graphene by heating in a reaction kettle, so that electron transfer in the reaction process is facilitated; the invention further designs the proportion of the black phosphorus nano-sheet and the alkali liquor activated graphene sheet, so that the heterostructure has optimal performance;
(3) According to the preparation method of the high-temperature proton exchange membrane fuel cell cathode catalyst, the black phosphorus nano sheet layer and the graphene sheet layer activated by alkali liquor are utilized for mechanical ball milling, and the black phosphorus and the activated graphene are heated in a reaction kettle to form a black phosphorus-activated graphene composite material which is used as a base material loaded by noble metal, so that the black phosphorus-activated graphene composite material has more defects, the metal active site of the catalyst material obtained after loading is better exposed, and the oxygen reduction activity and electrochemical stability of the catalyst are improved;
(4) According to the preparation method of the high-temperature proton exchange membrane fuel cell cathode catalyst, the loading and uniform dispersion of the noble metal nano particles are realized, and the electrochemical activity, the utilization rate and the stability of the noble metal catalyst are effectively improved.
(5) In the preparation method of the high-temperature proton exchange membrane fuel cell cathode catalyst, the prepared catalyst is prepared by adopting the black phosphorus-activated graphene heterojunction as a matrix material, and the graphene plays a certain role in protecting the black phosphorus after forming a heterostructure, so that the stability of the material is greatly enhanced, and the catalyst can be used in a high-temperature environment.
Drawings
FIG. 1 is a TEM image of a black phosphorus-activated graphene composite obtained in example 1 of the present invention;
FIG. 2 shows that the black phosphorus-activated graphene composite material obtained in example 1 of the present invention has platinum nanoparticles supported on 0.1M HClO 4 Cyclic voltammograms in solution;
FIG. 3 shows the Pt nanoparticle supported on the black phosphorus-activated graphene composite material obtained in example 1 of the present invention and a commercial catalyst Pt/C at 0.1M HClO 4 Linear scanning voltammograms in solution;
FIG. 4 shows the loading of platinum nanoparticles on 0.1M HClO in the black phosphorus-activated graphene composite material obtained in example 1 of the present invention 4 Results of stability test in solution.
Detailed Description
The features and advantages of the present invention will become more apparent and clear from the following detailed description of the invention.
The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. Although various aspects of the embodiments are illustrated in the accompanying drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
The invention provides a preparation method of a high-temperature proton exchange membrane fuel cell (HT-PEMFC) cathode catalyst, in particular to a preparation method of a black phosphorus-activated graphene composite material loaded noble metal nanoparticle, which comprises the steps of preparing black phosphorus through high-temperature calcination, and then preparing the black phosphorus-activated graphene composite material: ball milling the stripped black phosphorus nano lamellar material and the graphene lamellar material activated by alkali liquor according to a certain proportion under the protection of argon, and then centrifugally washing for a plurality of times by using isopropanol, absolute ethyl alcohol and deionized water, and vacuum drying and collecting; and finally dispersing the composite material in isopropanol, adding a metal precursor (the metal in the metal precursor is platinum, palladium or gold), adjusting the pH value, adding a reducing agent, stirring and drying in vacuum to obtain the black phosphorus-activated graphene composite material loaded noble metal nano particles. The black phosphorus-activated graphene heterojunction provides a stable substrate for the composite material, has more defects on the substrate, is favorable for full exposure of metal active sites, provides a good channel for electron transfer to the metal active sites, and effectively improves the electrocatalytic oxygen reduction activity and stability of the catalyst.
The invention provides a preparation method of a cathode catalyst of a high-temperature proton exchange membrane fuel cell, which comprises the following steps:
1) Preparation of black phosphorus nano-sheets: weighing 1-3g of Red Phosphorus (RP), placing the Red Phosphorus (RP) and 15-25mL of deionized water in a reaction kettle, and removing a surface oxide layer by hydrothermal treatment at 160-180 ℃ for more than 15 h. Drying, grinding into powder, mixing 400-600mg RP,18-24mg Sn and 10-15mg SnI 4 Vacuum-pumping in quartz tube, sealing, and standing at 5deg.C for min -1 Heating to 650 ℃ for 2-3h, then cooling to 450-500 ℃, preserving heat for 5-7h, and cooling to room temperature. The resulting Black Phosphorus (BP) crystals were washed several times with hot toluene and acetone and placed in a glove box filled with Ar for use. 200mg of the bulk BP crystals were weighed in a glove box filled with argon, ground into powder with an agate mortar, added to 50-70mL of NMP (N-methylpyrrolidone) solution, and sonicated in a cell pulverizer at 400-600W for 12h. After centrifugation at 4000rpm and collection of the supernatant, the supernatant was further sonicated in batch ice bath, centrifuged at 10000rpm and dried in vacuo to give black phosphorus nanoplatelets.
2) Preparation of black phosphorus-activated graphene composite material: mechanically ball-milling black phosphorus nano sheets and graphene activated by alkali liquor for 45-60 hours under the protection of argon, wherein the mass ratio of the black phosphorus to the graphene is 1:1-2, the ball mill is set at 600 revolutions per minute, the obtained precursor is placed in 30-40mL of ethylenediamine, stirred for 0.5 hour, then transferred to a reaction kettle, reacted for 12 hours at 140 ℃, and then naturally cooled. And then, respectively centrifugally washing with isopropanol, absolute ethyl alcohol and deionized water for 3-5 times, and then, vacuum drying the product at 50-60 ℃ to obtain the black phosphorus-activated graphene composite material.
3) Preparation of a black phosphorus-activated graphene composite material loaded noble metal nanoparticle: dispersing the black phosphorus-activated graphene composite material in isopropanol, adding a metal precursor after ultrasonic treatment, wherein the metal in the metal precursor is platinum, palladium or gold, and continuously stirring for 10-14h. And (3) after the pH value is regulated, adding a reducing agent which is sodium borohydride or hydrazine hydrate, wherein the mass ratio of the metal precursor to the reducing agent is 1:1-80, and vacuum drying to obtain the black phosphorus-activated graphene heterojunction loaded noble metal nanoparticle.
Further, the NMP solution used for dispersing and preserving the black phosphorus in the step 1) is a NMP solution of saturated NaOH.
Further, the alkali solution used for activating the graphene in the step 2) is 7mol/L potassium hydroxide solution.
Further, in the step 2), the mass ratio of the black phosphorus nano-sheet to the alkali liquor activated graphene is 1:1-2.
Further, the reducing agent in the step 3) is sodium borohydride or hydrazine hydrate.
Further, the reaction in step 3) is carried out in an environment having a pH of 8 to 11.
The method comprises the steps of ball-milling the stripped black phosphorus nano lamellar material and the graphene lamellar material activated by alkali liquor according to a certain proportion under the protection of argon, performing hydrothermal treatment in ethylenediamine, centrifugally washing for a plurality of times by isopropanol, absolute ethyl alcohol and deionized water, and vacuum drying and collecting; and carrying out ultrasonic treatment on the black phosphorus-activated graphene dispersed in isopropanol, adding a metal precursor and a reducing agent according to a certain proportion, stirring, drying and collecting to obtain noble metal particles loaded by the black phosphorus-activated graphene composite material.
The TEM test characterization shows that the black phosphorus and the activated graphene effectively form a heterostructure, and the noble metal nano particles are loaded and uniformly dispersed. The formation of the heterostructure is beneficial to electron transfer in the reaction process, and the substrate material has more defects, so that the metal active site is better exposed, and the oxygen reduction activity and electrochemical stability of the catalyst are improved. Compared with the prior art, the invention effectively improves the electrochemical activity, the utilization rate and the stability of the noble metal catalyst.
Example 1
The preparation method of the black phosphorus-activated graphene composite material loaded platinum nano particle specifically comprises the following steps:
(1) Preparation of black phosphorus-activated graphene composite material
(1) Preparation of black phosphorus nano-sheets: weighing 2g of Red Phosphorus (RP), placing the Red Phosphorus (RP) and 25mL of deionized water in a reaction kettle, and removing a surface oxide layer by hydrothermal treatment at 160-180 ℃ for more than 15 h. Drying, grinding into powder, mixing 400-600mg RP,18-24mg Sn and 10-15mg SnI 4 Vacuum-pumping in quartz tube, sealing, and standing at 5deg.C for min -1 Heating to 650 ℃ for 3 hours, then cooling to 500 ℃, preserving heat for 6 hours, and cooling to room temperature. The resulting Black Phosphorus (BP) crystals were washed several times with hot toluene and acetone at 70 ℃ and placed in a glove box filled with Ar for use. 200mg of the bulk BP crystals were weighed in a glove box filled with argon, ground into powder with an agate mortar, added to 50-70mL of NMP solution, and sonicated in a cell pulverizer at 400-600W for 12h. Centrifuge at 4000rpm and collect the supernatant to obtain supernatant of BP nanoflakes dispersed in NMP solution.
(2) Activation of graphene: stirring graphene in a 6M potassium hydroxide solution for 8-10 h, centrifugally washing the obtained sample with isopropanol, absolute ethyl alcohol and deionized water for 3-5 times respectively, then drying the sample in an oven at 70 ℃ for 24h, taking out, grinding the sample with an agate mortar for 30min, heating to 600 ℃ at 5 ℃/min in nitrogen and preserving heat for 30min, and heating to 800 ℃ at 2 ℃/min and preserving heat for 2h. And collecting the graphene after naturally cooling to room temperature to obtain the activated graphene.
(3) Preparation of black phosphorus-activated graphene heterojunction material: mechanically ball-milling a black phosphorus nano lamellar material and a graphene lamellar material activated by alkali liquor for 40-50h under the protection of argon, wherein the mass ratio of the black phosphorus nano lamellar material to the graphene nano lamellar material is 1:0.5-1.5, the ball mill is set at 600 revolutions per minute, the obtained precursor is placed in 40mL of ethylenediamine, stirred for 0.5h, then transferred into a reaction kettle, reacted for 12h at 140 ℃, and then naturally cooled. And then, respectively centrifugally washing for 5 times by using isopropanol, absolute ethyl alcohol and deionized water, and then, vacuum drying the product at 60 ℃ to obtain the black phosphorus-activated graphene heterojunction material.
(2) Preparation of black phosphorus-activated graphene composite material loaded platinum nano particles
Dispersing the black phosphorus-activated graphene composite material in isopropanol, adding sodium chloroplatinate after ultrasonic treatment, and continuously stirring for 10-14h. And regulating the pH value to be 10-11, slowly adding a reducing agent sodium borohydride by using a peristaltic pump, wherein the mass ratio of the metal precursor to the reducing agent is 1:1-80, and vacuum drying to obtain the black phosphorus-activated graphene composite material loaded platinum nano particles.
A TEM image of the black phosphorus-activated graphene composite obtained above is shown in fig. 1. From the figure, it can be seen that the black phosphorus and the graphene are both lamellar structures, and the black phosphorus and the graphene form a heterostructure.
FIG. 2 corresponds to a black phosphorus-activated graphene composite loaded with platinum nanoparticles at 0.1M HClO 4 Cyclic voltammogram in solution, the catalyst showed a reduction peak at about 0.55V.
FIG. 3 is a graph of black phosphorus-activated graphene composite loaded with platinum nanoparticles at 0.1M HClO 4 Linear sweep voltammogram in solution, it can be seen from the figure that the starting potential of the catalyst is about-0.07V, slightly below 0V for Pt/C. The limiting current density of the catalyst was 6.24mAcm -2 4.93mAcm higher than Pt/C -2 . And the half-wave potential of the catalyst is 0.82V, which is similar to 0.86V of Pt/C. The catalyst has better ORR activity under acidic conditions.
FIG. 4 corresponds to a platinum nanoparticle loaded on a black phosphorus-activated graphene composite at 0.1M HClO 4 Cycling stability test in solution. After 2000 cycles, the catalyst has performance similar to that of Pt/C, and has smaller decay of half-wave potential compared with Pt/C, which indicates that the catalyst has better electrochemical stability.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
What is not described in detail in the present specification is a well known technology to those skilled in the art.
Claims (7)
1. The preparation method of the cathode catalyst of the high-temperature proton exchange membrane fuel cell is characterized by comprising the following steps of:
(1) Removing the surface oxide layer of the blocky red phosphorus, and grinding to obtain red phosphorus powder;
(2) Mixing red phosphorus powder, sn, and SnI 4 Heating under vacuum condition, cooling and washing to obtain block black phosphorus, and grinding to obtain black phosphorus powder;
(3) Adding black phosphorus powder into NMP solution, carrying out ultrasonic stripping under the condition of inert gas, taking supernatant, further carrying out continuous ice bath ultrasonic treatment, and centrifuging to obtain black phosphorus nano lamellar material;
(4) Performing mechanical ball milling on the black phosphorus nano lamellar material and the graphene lamellar material activated by alkali liquor under the condition of inert gas to obtain a composite material precursor;
(5) Dispersing the composite material precursor in ethylenediamine, heating in a reaction kettle, cooling, washing and vacuum drying to obtain a black phosphorus-activated graphene composite material;
(6) Dispersing the black phosphorus-activated graphene composite material in isopropanol, and adding a noble metal precursor for stirring;
(7) Regulating the pH value of the dispersion liquid obtained in the step (6), then dripping a reducing agent, stirring, centrifugally washing, and vacuum drying to obtain the black phosphorus-activated graphene composite material loaded noble metal nano particles;
in the step (3), the NMP solution is saturated NaOH NMP solution, and the inert gas is argon; in the step (3), the ultrasonic stripping method is that the ultrasonic stripping is carried out for 12 to 16 hours in a cell grinder under the condition of 400 to 600W;
in the step (4), the mass ratio of the black phosphorus nano lamellar material to the alkali liquor activated graphene lamellar material is 1:0.5-2; in the step (4), a ball mill is used for mechanical ball milling under the argon condition, the rotating speed of the ball mill is 500-700 rpm, and the mechanical ball milling time is 45-60h;
in the step (5), the precursor of the composite material is dispersed in ethylenediamine, heated to 140 ℃ in a reaction kettle, reacted for 12 hours, naturally cooled, and then respectively centrifugally washed for 3-5 times by isopropanol, absolute ethanol and deionized water, and vacuum dried at the temperature of 50-60 ℃ to obtain the black phosphorus-activated graphene composite material.
2. The method for preparing the cathode catalyst of the high-temperature proton exchange membrane fuel cell according to claim 1, wherein in the step (1), the red phosphorus is removed from the surface oxide layer by placing the red phosphorus and deionized water together in a reaction kettle, and carrying out hydrothermal treatment at 160-180 ℃ for more than 15 hours.
3. The method for preparing a cathode catalyst for a high temperature proton exchange membrane fuel cell as claimed in claim 1, wherein in the step (2), red phosphorus powder, sn, and SnI are mixed with each other 4 The mass ratio of (2) is 1: (0.02-0.08): (0.01-0.06); in the step (2), the vacuum heating method is to heat red phosphorus powder, sn and SnI 4 Adding the mixture into a quartz tube, vacuumizing and sealing, and sequentially heating, preserving heat, cooling and preserving heat; in step (2), washing is performed using toluene and acetone washing.
4. A method according to claim 3The preparation method of the cathode catalyst of the high-temperature proton exchange membrane fuel cell is characterized in that in the step (2), the vacuum heating method comprises the steps of mixing red phosphorus powder, sn and SnI 4 Vacuum-pumping and sealing in quartz tube at 3-10 deg.C for 3 min -1 Heating to 600-700 ℃ for 2-3h, then cooling to 450-500 ℃ and preserving heat for 5-7h.
5. The method for preparing the cathode catalyst of the high-temperature proton exchange membrane fuel cell according to claim 1, wherein in the step (4), the graphene activated by alkali liquor is graphene activated by a potassium hydroxide solution of 6-7 mol/L, the activation method is that after the graphene is stirred in the potassium hydroxide solution for 8-10 hours, the graphene is centrifugally washed for 3-5 times by isopropanol, absolute ethyl alcohol and deionized water respectively, the obtained sample is dried and ground, and then the temperature is raised to 600 ℃ at 5 ℃/min in nitrogen and kept for 30min, and then the temperature is raised to 800 ℃ at 2 ℃/min and kept for 2 hours.
6. The method for preparing a cathode catalyst for a high-temperature proton exchange membrane fuel cell according to claim 1, wherein in the step (6), the noble metal precursor is a chloride of platinum, palladium or gold.
7. The method for preparing a cathode catalyst for a high-temperature proton exchange membrane fuel cell according to claim 1, wherein in the step (7), after adjusting the pH of the dispersion obtained in the step (6) to 8-11, a reducing agent sodium borohydride or hydrazine hydrate is added; the mass ratio of the metal precursor added in the step (6) to the reducing agent added in the step (7) is 1:1-80.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110988396.5A CN113921835B (en) | 2021-08-26 | 2021-08-26 | Preparation method of high-temperature proton exchange membrane fuel cell cathode catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110988396.5A CN113921835B (en) | 2021-08-26 | 2021-08-26 | Preparation method of high-temperature proton exchange membrane fuel cell cathode catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113921835A CN113921835A (en) | 2022-01-11 |
| CN113921835B true CN113921835B (en) | 2023-06-06 |
Family
ID=79233147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110988396.5A Active CN113921835B (en) | 2021-08-26 | 2021-08-26 | Preparation method of high-temperature proton exchange membrane fuel cell cathode catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113921835B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115498165A (en) * | 2022-10-12 | 2022-12-20 | 哈尔滨工业大学 | Black phosphorus-based composite electrode and preparation method and application thereof |
| CN116022765A (en) * | 2022-12-27 | 2023-04-28 | 武汉中科先进材料科技有限公司 | Preparation method of carbon-coated black phosphorus nano-sheet derived from organic metal framework |
| CN116463518A (en) * | 2023-04-10 | 2023-07-21 | 陕西省军工（集团）陕铜有限责任公司 | High-conductivity phosphorus copper alloy material and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106711408B (en) * | 2015-11-13 | 2019-05-10 | 中国科学院金属研究所 | Flexible lithium ion battery black phosphorus nanometer sheet-graphene composite film cathode and preparation |
| CN106185849B (en) * | 2016-07-08 | 2017-11-10 | 深圳先进技术研究院 | A kind of nanoscale black phosphorus and preparation method and application |
| CN107170998B (en) * | 2017-05-15 | 2019-06-28 | 上海电力学院 | A kind of preparation method of black phosphorus graphene composite material supported precious metal nano-particle |
| CN110327961A (en) * | 2019-07-12 | 2019-10-15 | 上海电力大学 | Preparation method of black phosphorus-activated graphene heterojunction loaded nickel nitride particles |
-
2021
- 2021-08-26 CN CN202110988396.5A patent/CN113921835B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113921835A (en) | 2022-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113921835B (en) | Preparation method of high-temperature proton exchange membrane fuel cell cathode catalyst | |
| CN111952572B (en) | Cobalt-nickel bimetallic nitrogen-doped carbon composite material containing single-atom active sites | |
| CN109286012B (en) | Preparation method of high-rate silica-based lithium battery negative electrode material | |
| CN112421048A (en) | Method for preparing graphite-coated nano-silicon lithium battery negative electrode material at low cost | |
| CN107579227A (en) | Preparation method, silicon-carbon cathode piece and the lithium ion battery of silicon-carbon cathode piece | |
| CN103078087B (en) | A kind of preparation method of lithium titanate/carbon nano tube composite cathode material | |
| CN104319366B (en) | Silicon/graphite/lithium titanate composite anode material and preparation method thereof | |
| CN111952570A (en) | Cobalt-nitrogen-carbon composite material containing single-atom active site and preparation method and application thereof | |
| CN112038614B (en) | Negative electrode material for sodium ion battery and preparation method thereof | |
| CN109713294A (en) | A kind of lithium ion battery oxidation Asia silicon based anode material and preparation method thereof | |
| WO2020147295A1 (en) | Se-doped mxene battery cathode material and preparation method and use thereof | |
| CN108598405B (en) | Preparation method of three-dimensional graphene tin oxide carbon composite negative electrode material | |
| WO2023155333A1 (en) | Piezoelectric effect-based method for preparing high-performance lithium ion silicon-based negative electrode material and application thereof | |
| CN108695509B (en) | Composite lithium battery positive electrode with high energy storage efficiency, preparation method thereof and lithium battery | |
| CN113851647A (en) | Solid electrolyte coated cathode for solid battery and preparation method thereof | |
| CN116722131A (en) | Low-entropy antimony-based binary superfine nanocrystalline oxide negative electrode material and preparation method thereof | |
| WO2023130671A1 (en) | Composite solid electrolyte material, and preparation method therefor and use thereof | |
| CN111313004A (en) | Silicon monoxide-lithium titanate-based composite negative electrode material for lithium ion battery and preparation method thereof | |
| CN111129455A (en) | High-first-efficiency silicon-based negative electrode material and preparation method thereof | |
| CN112234218B (en) | Oxygen reduction catalyst, preparation process thereof, battery positive electrode, preparation process thereof and battery | |
| CN108807983B (en) | Preparation method of magnesium and tin doped porous lithium nickelate positive electrode material | |
| CN114068869B (en) | Core-shell structure silicon @ silicon oxide/carbon anode material and preparation method and application thereof | |
| CN118173790B (en) | Solid-state battery anode material and preparation method and application thereof | |
| CN118650162B (en) | Alloy frame silicon composite material and preparation method and application thereof | |
| CN103700826A (en) | Pre-lithiated ultrathin V6O13 nanosheet as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |