CN113023686A - N-doped porous carbon loaded ZnSe electrode material applied to sodium-ion battery - Google Patents
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Abstract
The invention relates to the technical field of sodium ion batteries, in particular to an N-doped porous carbon loaded ZnSe electrode material, wherein the porous carbon provides a stable loading matrix for ZnSe, the agglomeration of nano ZnSe hollow spheres is inhibited, the ZnSe grows in pores and the surface of the porous carbon, a rapid ion transmission channel is provided by a pore structure rich in the surface, the transmission of electrolyte is promoted, the contact with electrolyte is enhanced, the improvement of electron transmission capability is facilitated, and the doping energy of N atoms canCan form adsorbed Na+Defect site of (3), in favor of Na+The emergence of desorption to reinforcing electrode material's electric conductive property, and N doping can improve the infiltration degree of porous carbon, thereby reinforcing and the contact interface of electrolyte, because the stable structure of porous carbon, the load of porous carbon and the three-dimensional hollow structure of ZnSe can alleviate ZnSe and produce the volume effect at the charge-discharge in-process, avoided electrode material's pulverization, thereby improved electrode material's circulation stability can.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to an N-doped porous carbon loaded ZnSe electrode material applied to a sodium ion battery.
Background
With the development of society, the continuous development and consumption of natural resources by human society, energy exhaustion and environmental pollution become important problems hindering the development of the current society, electric energy is the most widely used secondary energy at present, and is more and more concerned and valued by researchers, as is well known, a lithium ion battery is reformed for several generations and becomes the mainstream electrochemical energy storage equipment at present, but metallic lithium is used as a strategic resource with relatively limited reserve capacity to limit the development of the lithium ion battery, and a sodium ion battery has the advantages of environmental friendliness, low redox potential and the like due to the very abundant reserve capacity of sodium element in the earth crust and the ocean, so the sodium ion battery is an electrochemical energy storage equipment with great development potential.
At present, the negative electrode material of the sodium ion battery can be divided into carbon-based and titanium-based materials with a de-intercalation mechanism, silicon-based and tin-based materials with an alloy mechanism, sulfide, selenide, oxide, nitride and the like with a conversion mechanism, wherein ZnSe is a metal selenide with high theoretical specific capacity, but ZnSe can generate larger volume expansion in the charging and discharging process when being used as the negative electrode material, so that electrode material pulverization is caused, and the cycle stable service life of the battery is influenced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides an N-doped porous carbon loaded ZnSe electrode material applied to a sodium ion battery, and solves the problems of poor battery circulation stability and poor ZnSe conductivity caused by large volume expansion of ZnSe when the ZnSe is used as the electrode material of the sodium ion battery.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of an N-doped porous carbon loaded ZnSe electrode material comprises the following steps:
(1) pyrrole is reacted with 4-nitrobenzaldehyde to give 5,10,15, 20-tetrakis (4-nitrophenyl) porphyrin, followed by SnCl in a strong acid solution2Reducing to obtain 5,10,15, 20-tetra (4-aminophenyl) porphyrin with the molecular formula of C44H34N8；
(2) Adding 5,10,15, 20-tetra (4-aminophenyl) porphyrin and 4,4' -biphenyldicarboxaldehyde into a toluene solvent, dropwise adding glacial acetic acid, performing ultrasonic treatment, vacuumizing, heating for Schiff base polymerization reaction, after the reaction is finished, performing suction filtration, acetone and tetrahydrofuran washing, and performing vacuum drying to obtain a Schiff base type porous organic polymer;
(3) grinding and mixing a Schiff base type porous organic polymer and KOH, placing the mixture in a tubular furnace, heating the mixture in a nitrogen atmosphere to perform a carbonization process, naturally cooling the mixture, and washing the mixture to be neutral to obtain N-doped porous carbon;
(4) ZnSO is added4With Na2SeO3Adding the mixture into NaOH solution, stirring and dissolving, adding N-doped porous carbon, carrying out ultrasonic treatment, pouring the dispersion liquid into a high-pressure kettle, adding hydrazine hydrate solution, carrying out hydrothermal reaction, washing with deionized water after the reaction is finished, and carrying out vacuum drying to obtain the N-doped porous carbon loaded ZnSe material.
2. The N-doped porous carbon-loaded ZnSe electrode material according to claim 1, wherein: in the step (2), 5,10,15, 20-tetra (4-aminophenyl) porphyrin, 4' -biphenyldicarboxaldehyde and CH3The mass ratio of COOH is 100:55-75: 100-120.
Preferably, the temperature of the Schiff base polymerization reaction in the step (2) is 110-130 ℃, and the reaction time is 60-96 h.
Preferably, the mass ratio of the Schiff base type porous organic polymer to the KOH in the step (3) is 100: 40-80.
Preferably, the temperature rise rate of the carbonization process in the step (3) is 1-3 ℃/min, the carbonization temperature is 800-900 ℃, and the carbonization time is 3-5 h.
Preferably, in the step (4), the N is doped with porous carbon and ZnSO4With Na2SeO3The mass ratio of (A) to (B) is 10:60-90: 65-98.
Preferably, the temperature of the hydrothermal reaction in the step (4) is 130-150 ℃, and the reaction time is 24-36 h.
(III) advantageous technical effects
Compared with the prior art, the invention has the following experimental principles and beneficial technical effects:
the N-doped porous carbon loaded ZnSe electrode material is prepared by taking pyrrole and 4-nitrobenzaldehyde as raw materials, carrying out Alder-Longo reaction and reduction to obtain 5,10,15, 20-tetra (4-aminophenyl) porphyrin, polymerizing the 5,10,15, 20-tetra (4-aminophenyl) porphyrin and 4,4' -biphenyldialdehyde under the catalysis of glacial acetic acid to obtain a Schiff base type porous organic polymer, carbonizing the Schiff base type porous organic polymer and a KOH activator in a tubular furnace together, taking the Schiff base and the porphyrin as N sources, taking a rigid aromatic ring as a carbon skeleton to obtain N-doped porous carbon, finally adding the N-doped porous carbon in an alkaline solvent by taking hydrazine hydrate as a reduction aid when synthesizing hollow nano ZnSe, so that the hollow nano ZnSe grows on the N-doped porous carbon to obtain the N-doped porous carbon loaded ZnSe electrode material, wherein among a plurality of metal selenides, the ZnSe has the advantages of good thermal stability, low discharge platform, small polarization and the like, after the porous carbon is loaded, the agglomeration of the nano ZnSe hollow spheres is inhibited, the porous carbon also provides a stable loading matrix for ZnSe, the ZnSe grows in the pores and the surface of the porous carbon, and the porous structure rich in the surface of the porous carbon provides a quick ion transmission channel, so that the transmission of electrolyte is promoted, the contact with electrolyte is enhanced, the improvement of electron transmission capacity is facilitated, the conductivity of an electrode material is improved in a high-electron-conductivity carbon material loading mode, and the defect of poor electron conductivity of the ZnSe is overcome.
The N-doped porous carbon loaded ZnSe electrode material takes Schiff base and porphyrin in a Schiff base type porphyrin porous organic polymer as an N source and is carbonizedThen obtaining N-doped porous carbon, wherein N atoms doped into the carbon structure can form adsorbed Na+Defect site of (3), in favor of Na+The de-intercalation occurs, the ion transmission and charge transfer process of the carbon material can be obviously improved by the graphite type N generated by N doping, so that the conductivity of the electrode material is enhanced, and the wettability of porous carbon can be improved by the N doping, so that the contact interface with an electrolyte is enhanced, and the electrochemical activity of the electrode material is improved.
This N doping porous carbon load ZnSe electrode material, add N doping porous carbon at the in-process of hydrothermal preparation nanometer ZnSe clean shot, make nanometer ZnSe clean shot grow on porous carbon matrix, because the carbon material can keep stable structure at the in-process of charge-discharge and sodium ion deintercalation, consequently the load of porous carbon and the three-dimensional hollow structure of ZnSe can alleviate ZnSe and produce the volume effect at the charge-discharge in-process, electrode material's pulverization has been avoided, thereby very big improvement electrode material's circulation stability can, the life of sodium ion battery has been prolonged.
Detailed Description
FIG. 1 is a reaction diagram for synthesizing a Schiff base type porous organic polymer.
Detailed Description
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the N-doped porous carbon loaded ZnSe electrode material comprises the following steps:
(1) pyrrole is reacted with 4-nitrobenzaldehyde to give 5,10,15, 20-tetrakis (4-nitrophenyl) porphyrin, followed by SnCl in a strong acid solution2Reducing to obtain 5,10,15, 20-tetra (4-aminophenyl) porphyrin with the molecular formula of C44H34N8；
(2) Adding 5,10,15, 20-tetra (4-aminophenyl) porphyrin and 4,4 '-biphenyldicarboxaldehyde into a toluene solvent, and dropwise adding glacial acetic acid, wherein the 5,10,15, 20-tetra (4-aminophenyl) porphyrin, the 4,4' -biphenyldicarboxaldehyde and the CH3The mass ratio of COOH is 100:55-75:100-120, ultrasonic treatment, vacuum pumping, heating to 110-130 ℃ for polymerization for 60-96h, after the reaction is finished, suction filtration, acetone and tetrahydrofuran washing and vacuum drying are carried out to obtain the Schiff base type porous organic polymerA compound;
(3) grinding and mixing a Schiff base type porous organic polymer and KOH according to the mass ratio of 100:40-80, placing the mixture in a tubular furnace, heating the mixture in a nitrogen atmosphere to carry out a carbonization process, wherein the heating rate of the carbonization process is 1-3 ℃/min, the carbonization temperature is 800-900 ℃, the carbonization time is 3-5h, naturally cooling the mixture, and washing the mixture to be neutral to obtain N-doped porous carbon;
(4) ZnSO is added4With Na2SeO3Adding into NaOH solution, stirring for dissolving, adding N-doped porous carbon, wherein N-doped porous carbon and ZnSO4With Na2SeO3The mass ratio of the N-doped porous carbon loaded ZnSe material to the N-doped porous carbon loaded ZnSe material is 10:60-90:65-98, ultrasonic treatment is carried out, the dispersion liquid is poured into a high-pressure kettle, a hydrazine hydrate solution is added, hydrothermal reaction is carried out for 24-36h at the temperature of 130-150 ℃, and after the reaction is finished, deionized water washing and vacuum drying are carried out to obtain the N-doped porous carbon loaded ZnSe material.
Example 1
(1) Pyrrole is reacted with 4-nitrobenzaldehyde to give 5,10,15, 20-tetrakis (4-nitrophenyl) porphyrin, followed by SnCl in a strong acid solution2Reducing to obtain 5,10,15, 20-tetra (4-aminophenyl) porphyrin with the molecular formula of C44H34N8；
(2) Adding 5,10,15, 20-tetra (4-aminophenyl) porphyrin and 4,4 '-biphenyldicarboxaldehyde into a toluene solvent, and dropwise adding glacial acetic acid, wherein the 5,10,15, 20-tetra (4-aminophenyl) porphyrin, the 4,4' -biphenyldicarboxaldehyde and the CH3Performing ultrasonic treatment and vacuum pumping on COOH in a mass ratio of 100:55:100, heating to 110 ℃, polymerizing for 60 hours, after the reaction is finished, performing suction filtration, washing with acetone and tetrahydrofuran, and performing vacuum drying to obtain a Schiff base type porous organic polymer;
(3) grinding and mixing a Schiff base type porous organic polymer and KOH according to the mass ratio of 100:40, placing the mixture in a tubular furnace, heating the mixture in a nitrogen atmosphere to carry out a carbonization process, wherein the heating rate of the carbonization process is 1 ℃/min, the carbonization temperature is 800 ℃, the carbonization time is 3h, naturally cooling the mixture, and washing the mixture to be neutral to obtain N-doped porous carbon;
(4) ZnSO is added4With Na2SeO3Adding into NaOH solution, stirring to dissolve,adding N-doped porous carbon, wherein the N-doped porous carbon and ZnSO4With Na2SeO3The mass ratio of the N-doped porous carbon loaded ZnSe material to the reaction product is 10:60:65, carrying out ultrasonic treatment, pouring the dispersion liquid into a high-pressure kettle, adding a hydrazine hydrate solution, carrying out hydrothermal reaction for 24 hours at 130 ℃, washing with deionized water after the reaction is finished, and carrying out vacuum drying to obtain the N-doped porous carbon loaded ZnSe material.
Example 2
(1) Pyrrole is reacted with 4-nitrobenzaldehyde to give 5,10,15, 20-tetrakis (4-nitrophenyl) porphyrin, followed by SnCl in a strong acid solution2Reducing to obtain 5,10,15, 20-tetra (4-aminophenyl) porphyrin with the molecular formula of C44H34N8；
(2) Adding 5,10,15, 20-tetra (4-aminophenyl) porphyrin and 4,4 '-biphenyldicarboxaldehyde into a toluene solvent, and dropwise adding glacial acetic acid, wherein the 5,10,15, 20-tetra (4-aminophenyl) porphyrin, the 4,4' -biphenyldicarboxaldehyde and the CH3Performing ultrasonic treatment and vacuum pumping on COOH at the mass ratio of 100:60:105, heating to 115 ℃ for polymerization for 69 hours, after the reaction is finished, performing suction filtration, washing with acetone and tetrahydrofuran, and performing vacuum drying to obtain a Schiff base type porous organic polymer;
(3) grinding and mixing a Schiff base type porous organic polymer and KOH according to the mass ratio of 100:50, placing the mixture in a tubular furnace, heating the mixture in a nitrogen atmosphere to carry out a carbonization process, wherein the heating rate of the carbonization process is 2 ℃/min, the carbonization temperature is 850 ℃, the carbonization time is 3.5h, naturally cooling the mixture, and washing the mixture to be neutral to obtain N-doped porous carbon;
(4) ZnSO is added4With Na2SeO3Adding into NaOH solution, stirring for dissolving, adding N-doped porous carbon, wherein N-doped porous carbon and ZnSO4With Na2SeO3The mass ratio of the N-doped porous carbon loaded ZnSe material to the reaction product is 10:67:74, carrying out ultrasonic treatment, pouring the dispersion liquid into a high-pressure kettle, adding a hydrazine hydrate solution, carrying out hydrothermal reaction for 27 hours at 135 ℃, washing with deionized water after the reaction is finished, and carrying out vacuum drying to obtain the N-doped porous carbon loaded ZnSe material.
Example 3
(1) Pyrrole reacts with 4-nitrobenzaldehyde to obtain 5,10,15, 20-tetra (4-nitrophenyl) porphyrin,followed by SnCl in a strong acid solution2Reducing to obtain 5,10,15, 20-tetra (4-aminophenyl) porphyrin with the molecular formula of C44H34N8；
(2) Adding 5,10,15, 20-tetra (4-aminophenyl) porphyrin and 4,4 '-biphenyldicarboxaldehyde into a toluene solvent, and dropwise adding glacial acetic acid, wherein the 5,10,15, 20-tetra (4-aminophenyl) porphyrin, the 4,4' -biphenyldicarboxaldehyde and the CH3Performing ultrasonic treatment, vacuumizing and heating to 120 ℃ for polymerization for 78 hours at the mass ratio of COOH of 100:65:110, performing suction filtration, washing with acetone and tetrahydrofuran and performing vacuum drying after the reaction is finished to obtain a Schiff base type porous organic polymer;
(3) grinding and mixing a Schiff base type porous organic polymer and KOH according to the mass ratio of 100:60, placing the mixture in a tubular furnace, heating the mixture in a nitrogen atmosphere to carry out a carbonization process, wherein the heating rate of the carbonization process is 2 ℃/min, the carbonization temperature is 850 ℃, the carbonization time is 4h, naturally cooling the mixture, and washing the mixture to be neutral to obtain N-doped porous carbon;
(4) ZnSO is added4With Na2SeO3Adding into NaOH solution, stirring for dissolving, adding N-doped porous carbon, wherein N-doped porous carbon and ZnSO4With Na2SeO3The mass ratio of the N-doped porous carbon loaded ZnSe material to the reaction product is 10:74:83, carrying out ultrasonic treatment, pouring the dispersion liquid into a high-pressure kettle, adding a hydrazine hydrate solution, carrying out hydrothermal reaction for 30 hours at 140 ℃, washing with deionized water after the reaction is finished, and carrying out vacuum drying to obtain the N-doped porous carbon loaded ZnSe material.
Example 4
(1) Pyrrole is reacted with 4-nitrobenzaldehyde to give 5,10,15, 20-tetrakis (4-nitrophenyl) porphyrin, followed by SnCl in a strong acid solution2Reducing to obtain 5,10,15, 20-tetra (4-aminophenyl) porphyrin with the molecular formula of C44H34N8；
(2) Adding 5,10,15, 20-tetra (4-aminophenyl) porphyrin and 4,4 '-biphenyldicarboxaldehyde into a toluene solvent, and dropwise adding glacial acetic acid, wherein the 5,10,15, 20-tetra (4-aminophenyl) porphyrin, the 4,4' -biphenyldicarboxaldehyde and the CH3The mass ratio of COOH is 100:70:115, ultrasonic treatment is carried out, vacuum pumping is carried out, the mixture is heated to 125 ℃ for polymerization for 85 hours, and suction filtration is carried out after the reaction is finished,Washing with acetone and tetrahydrofuran, and vacuum drying to obtain Schiff base type porous organic polymer;
(3) grinding and mixing a Schiff base type porous organic polymer and KOH according to the mass ratio of 100:70, placing the mixture in a tubular furnace, heating the mixture in a nitrogen atmosphere to carry out a carbonization process, wherein the heating rate of the carbonization process is 2 ℃/min, the carbonization temperature is 850 ℃, the carbonization time is 4.5h, naturally cooling the mixture, and washing the mixture to be neutral to obtain N-doped porous carbon;
(4) ZnSO is added4With Na2SeO3Adding into NaOH solution, stirring for dissolving, adding N-doped porous carbon, wherein N-doped porous carbon and ZnSO4With Na2SeO3The mass ratio of the N-doped porous carbon loaded ZnSe material to the reaction product is 10:83:89, carrying out ultrasonic treatment, pouring the dispersion liquid into a high-pressure kettle, adding a hydrazine hydrate solution, carrying out hydrothermal reaction for 33 hours at 145 ℃, washing with deionized water after the reaction is finished, and carrying out vacuum drying to obtain the N-doped porous carbon loaded ZnSe material.
Example 5
(1) Pyrrole is reacted with 4-nitrobenzaldehyde to give 5,10,15, 20-tetrakis (4-nitrophenyl) porphyrin, followed by SnCl in a strong acid solution2Reducing to obtain 5,10,15, 20-tetra (4-aminophenyl) porphyrin with the molecular formula of C44H34N8；
(2) Adding 5,10,15, 20-tetra (4-aminophenyl) porphyrin and 4,4 '-biphenyldicarboxaldehyde into a toluene solvent, and dropwise adding glacial acetic acid, wherein the 5,10,15, 20-tetra (4-aminophenyl) porphyrin, the 4,4' -biphenyldicarboxaldehyde and the CH3Performing ultrasonic treatment, vacuumizing and heating to 130 ℃ for polymerization for 96 hours at the mass ratio of COOH of 100:75:120, performing suction filtration, washing with acetone and tetrahydrofuran and performing vacuum drying after the reaction is finished to obtain a Schiff base type porous organic polymer;
(3) grinding and mixing a Schiff base type porous organic polymer and KOH according to the mass ratio of 100:80, placing the mixture in a tubular furnace, heating the mixture in a nitrogen atmosphere to perform a carbonization process, wherein the heating rate of the carbonization process is 3 ℃/min, the carbonization temperature is 900 ℃, the carbonization time is 5h, naturally cooling the mixture, and washing the mixture to be neutral to obtain N-doped porous carbon;
(4) ZnSO is added4With Na2SeO3Adding into NaOH solution, stirring for dissolving, adding N-doped porous carbon, wherein N-doped porous carbon and ZnSO4With Na2SeO3The mass ratio of the N-doped porous carbon loaded ZnSe material to the reaction product is 10:90:98, carrying out ultrasonic treatment, pouring the dispersion liquid into a high-pressure kettle, adding a hydrazine hydrate solution, carrying out hydrothermal reaction for 36 hours at 150 ℃, washing with deionized water after the reaction is finished, and carrying out vacuum drying to obtain the N-doped porous carbon loaded ZnSe material.
Comparative example 1
(1) Pyrrole is reacted with 4-nitrobenzaldehyde to give 5,10,15, 20-tetrakis (4-nitrophenyl) porphyrin, followed by SnCl in a strong acid solution2Reducing to obtain 5,10,15, 20-tetra (4-aminophenyl) porphyrin with the molecular formula of C44H34N8；
(2) Adding 5,10,15, 20-tetra (4-aminophenyl) porphyrin and 4,4 '-biphenyldicarboxaldehyde into a toluene solvent, and dropwise adding glacial acetic acid, wherein the 5,10,15, 20-tetra (4-aminophenyl) porphyrin, the 4,4' -biphenyldicarboxaldehyde and the CH3Performing ultrasonic treatment, vacuumizing, heating to 110 ℃, polymerizing for 60 hours, filtering after the reaction is finished, washing with acetone and tetrahydrofuran, and drying in vacuum to obtain a Schiff base type porous organic polymer, wherein the mass ratio of COOH is 100:45: 80;
(3) grinding and mixing a Schiff base type porous organic polymer and KOH according to the mass ratio of 100:30, placing the mixture in a tubular furnace, heating the mixture in a nitrogen atmosphere to perform a carbonization process, wherein the heating rate of the carbonization process is 1 ℃/min, the carbonization temperature is 800 ℃, the carbonization time is 3h, naturally cooling the mixture, and washing the mixture to be neutral to obtain N-doped porous carbon;
(4) ZnSO is added4With Na2SeO3Adding into NaOH solution, stirring for dissolving, adding N-doped porous carbon, wherein N-doped porous carbon and ZnSO4With Na2SeO3The mass ratio of the N-doped porous carbon loaded ZnSe material to the reaction product is 10:50:54, carrying out ultrasonic treatment, pouring the dispersion liquid into a high-pressure kettle, adding a hydrazine hydrate solution, carrying out hydrothermal reaction for 24 hours at 130 ℃, washing with deionized water after the reaction is finished, and carrying out vacuum drying to obtain the N-doped porous carbon loaded ZnSe material.
ZnSe electrode materials of examples and comparative examples, conductive carbon black and sodium hydroxymethyl celluloseDeionized water is mixed and coated on an electrode sheet to prepare a working electrode, metallic sodium is used as a counter electrode and a reference electrode, and NaClO is used4The methyl carbonate and diethyl carbonate solution as electrolyte were assembled into button cells in a glove box, and the cell cycling stability was tested using RST5200F electrochemical workstation.
The ZnSe electrode materials of the examples and comparative examples were assembled into coin cells, and the cells were tested for rate at different current densities using the RST5200F electrochemical workstation.
Claims (7)
1. An N-doped porous carbon loaded ZnSe electrode material is characterized in that: the preparation method of the N-doped porous carbon loaded ZnSe electrode material comprises the following steps:
(1) pyrrole is reacted with 4-nitrobenzaldehyde to give 5,10,15, 20-tetrakis (4-nitrophenyl) porphyrin, followed by SnCl in a strong acid solution2Reducing to obtain 5,10,15, 20-tetra (4-aminophenyl) porphyrin with the molecular formula of C44H34N8；
(2) Adding 5,10,15, 20-tetra (4-aminophenyl) porphyrin and 4,4' -biphenyldicarboxaldehyde into a toluene solvent, dropwise adding glacial acetic acid, performing ultrasonic treatment, vacuumizing, heating for Schiff base polymerization reaction, after the reaction is finished, performing suction filtration, acetone and tetrahydrofuran washing, and performing vacuum drying to obtain a Schiff base type porous organic polymer;
(3) grinding and mixing a Schiff base type porous organic polymer and KOH, placing the mixture in a tubular furnace, heating the mixture in a nitrogen atmosphere to perform a carbonization process, naturally cooling the mixture, and washing the mixture to be neutral to obtain N-doped porous carbon;
(4) ZnSO is added4With Na2SeO3Adding the mixture into NaOH solution, stirring and dissolving, adding N-doped porous carbon, carrying out ultrasonic treatment, pouring the dispersion liquid into a high-pressure kettle, adding hydrazine hydrate solution, carrying out hydrothermal reaction, washing with deionized water after the reaction is finished, and carrying out vacuum drying to obtain the N-doped porous carbon loaded ZnSe material.
2. The N-doped porous carbon-loaded ZnSe electrode material according to claim 1, wherein: in the step (2), 5,10,15, 20-tetra (4-aminophenyl) porphyrin, 4' -biphenyldicarboxaldehyde and CH3The mass ratio of COOH is 100:55-75: 100-120.
3. The N-doped porous carbon-loaded ZnSe electrode material according to claim 1, wherein: the temperature of the Schiff base polymerization reaction in the step (2) is 110-130 ℃, and the reaction time is 60-96 h.
4. The N-doped porous carbon-loaded ZnSe electrode material according to claim 1, wherein: the mass ratio of the Schiff base type porous organic polymer to the KOH in the step (3) is 100: 40-80.
5. The N-doped porous carbon-loaded ZnSe electrode material according to claim 1, wherein: the heating rate of the carbonization process in the step (3) is 1-3 ℃/min, the carbonization temperature is 800-900 ℃, and the carbonization time is 3-5 h.
6. The N-doped porous carbon-loaded ZnSe electrode material according to claim 1, wherein: in the step (4), N is doped with porous carbon and ZnSO4With Na2SeO3The mass ratio of (A) to (B) is 10:60-90: 65-98.
7. The N-doped porous carbon-loaded ZnSe electrode material according to claim 1, wherein: the temperature of the hydrothermal reaction in the step (4) is 130-150 ℃, and the reaction time is 24-36 h.
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| CN116216709A (en) * | 2023-02-22 | 2023-06-06 | 三峡大学 | Preparation method and application of graphite carbon catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113912026A (en) * | 2021-09-13 | 2022-01-11 | 三峡大学 | Preparation method of double-carbon-modified zinc selenide layered multistage microspheres |
| CN113912026B (en) * | 2021-09-13 | 2022-12-20 | 三峡大学 | Preparation method of double-carbon-modified zinc selenide layered multistage microspheres |
| CN113991093A (en) * | 2021-10-27 | 2022-01-28 | 重庆硕盈峰新能源科技有限公司 | Preparation of heteroatom in-situ doped porous carbon and application of heteroatom in high-rate sodium ion battery |
| CN113991094A (en) * | 2021-10-27 | 2022-01-28 | 重庆硕盈峰新能源科技有限公司 | Heteroatom in-situ doped porous carbon composite lithium cathode and preparation method and application thereof |
| CN113991094B (en) * | 2021-10-27 | 2023-09-22 | 重庆硕盈峰新能源科技有限公司 | Heteroatom in-situ doped porous carbon composite lithium anode and preparation method and application thereof |
| CN113991093B (en) * | 2021-10-27 | 2023-09-22 | 重庆硕盈峰新能源科技有限公司 | Preparation of heteroatom in-situ doped porous carbon and application of heteroatom in high-rate sodium ion battery |
| CN116216709A (en) * | 2023-02-22 | 2023-06-06 | 三峡大学 | Preparation method and application of graphite carbon catalyst |
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