CN113460993B - Zinc-nitrogen modified dual-carbon catalytic material, preparation method thereof and application thereof in zinc-air battery - Google Patents
Zinc-nitrogen modified dual-carbon catalytic material, preparation method thereof and application thereof in zinc-air battery Download PDFInfo
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Abstract
The invention discloses a zinc-nitrogen modified dual-carbon catalytic material, a preparation method thereof and application thereof in a zinc-air battery. Synthesizing a metal framework ZIF-8 by using dimethyl imidazole and zinc salt as raw materials, carrying out first heat treatment on the metal framework ZIF-8 in a protective atmosphere to obtain a zinc-modified porous carbon material, ball-milling and mixing the zinc-modified porous carbon material, a saccharide compound and a nitrogen source compound, and carrying out second heat treatment in the protective atmosphere to obtain a zinc-nitrogen-modified dual-carbon catalytic material; the catalytic material has zinc-nitrogen double modification, is rich in defects and porous structures, has good conductivity and a 3D network structure, and is applied to a zinc-air battery to obtain high power density and specific capacity; the preparation method of the catalytic material has low cost and simple steps, and is beneficial to industrial production.
Description
Technical Field
The invention relates to a zinc-air battery electrode material, in particular to a zinc nitrogen modified dual-carbon catalytic material, a preparation method thereof and application of the zinc nitrogen modified dual-carbon catalytic material in a zinc-air battery, belonging to the technical field of zinc-air battery catalytic materials.
Background
Rechargeable zinc-air batteries are receiving increasing attention due to their high theoretical energy density, low cost, environmental friendliness, and high safety. Zinc-air batteries are driven by Oxygen Reduction Reactions (ORR) and Oxygen Evolution Reactions (OER) during discharge and charge, respectively. However, the kinetic lag of ORR and OER on air cathodes greatly limits the commercial application of zinc-air batteries.
Noble metal catalysts (e.g., platinum, ruthenium, iridium, etc.) are considered to be effective electrocatalysts for Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER), however, noble metal catalysts have scarce reserves, high cost, poor stability, poor methanol resistance, and severely hinder the large-scale application of zinc-air batteries. Based on the advantages of abundant resources, various structures, environmental friendliness and the like of carbon-based materials, the zinc-air battery catalyst gradually draws general attention, and particularly, nonmetal and metal are doped in the carbon material, so that the electron distribution around carbon atoms can be changed, the conductivity of the material is improved, and the electrochemical performance and the stability of the carbon material can be greatly improved. At present, partial studies on modifying carbon materials by heteroatoms have been made, in chinese patent (CN112397733A), a carbon source is dissolved in an organic solvent, an organic cobalt salt is added, a carbon source is also dissolved in an organic solvent in a second step, an inorganic iron salt is added, and an electrostatic spinning method is used to obtain an iron-cobalt-loaded nitrogen-doped carbon material, but the synthesis process is relatively complicated and the cost is high. In Chinese patent (CN111554945A), metal salt and nitrogen source (dopamine and urea) are uniformly stirred and distributed in an aqueous solution to further volatilize water, and the mixing process of the method is complex. In Chinese patent (CN111889114A), Co and Fe elements obtained by the method are highly dispersed in a bimetallic organic framework with a porous structure, so that the agglomeration of the nano CoFe alloy is avoided, and the full exposure of electrochemical active sites is facilitated, however, hydrogen is adopted for reduction in the process, and a high danger coefficient exists.
Disclosure of Invention
In view of the defects of the prior art, the first object of the present invention is to provide a zinc-nitrogen-modified dual-carbon catalytic material containing zinc atoms and heteroatom-nitrogen dual modification, having developed pores, having a dual-carbon structure with a three-dimensional carbon skeleton inside and a carbon shell outside, and being rich in defects.
The second purpose of the invention is to provide a method for modifying a dual-carbon catalytic material by zinc nitrogen, which has the advantages of simple steps and low cost, can controllably adjust the doping amount of heteroatoms by regulating and controlling the proportion of raw materials, can control and adjust the graphitization degree of a dual-carbon structure by heat treatment conditions, can realize the atomic doping of a zinc metal simple substance by adopting zinc coordination metal as the raw material, enables the distribution of active sites to be more uniform, and has obvious advantages compared with the prior art.
The third purpose of the invention is to provide the application of the zinc-nitrogen modified dual-carbon catalytic material in the zinc-air battery, and the zinc-air battery obtained by applying the zinc-nitrogen modified dual-carbon catalytic material to the cathode of the zinc-air battery shows excellent electrochemical performance, such as higher power density and specific capacity.
In order to achieve the technical purpose, the invention provides a preparation method of a zinc-nitrogen modified double-carbon catalytic material, which comprises the following steps:
1) synthesizing a metal framework ZIF-8 by using dimethyl imidazole and zinc salt as raw materials;
2) carrying out first heat treatment on the metal framework ZIF-8 under a protective atmosphere to obtain a zinc modified porous carbon material;
3) and (3) mixing the zinc modified porous carbon material with a carbohydrate compound and a nitrogen source compound by ball milling, and then carrying out secondary heat treatment under a protective atmosphere to obtain the zinc nitrogen modified dual-carbon catalytic material.
According to the technical scheme, the metal framework ZIF-8 with regular morphology and pores and metal zinc in the form of single metal ions in coordination and complexation can be obtained by taking dimethyl imidazole and zinc salt as raw materials, the three-dimensional zinc modified porous carbon material with regular morphology can be obtained after high-temperature carbonization, and zinc is highly dispersed and doped in the three-dimensional porous carbon material in situ in the form of metal zinc atoms, so that the distribution of active sites is more uniform; on the basis, nitrogen doping and a double-carbon structure are built on the zinc modified porous carbon material, a carbon skeleton surface of the zinc modified porous carbon material is coated with a uniform carbon coating layer which is rich in defects and has high catalytic activity by using a saccharide compound and a nitrogen source compound, and a nitrogen source is introduced to form zinc-nitrogen co-doping, so that the whole zinc-nitrogen modified double-carbon catalytic material can show higher ORR activity.
As a preferable scheme, dimethyl imidazole and zinc salt are dissolved in an alcohol solvent and react for 8-16 h at the temperature of 20-40 ℃ to obtain the metal framework ZIF-8. Under the preferable reaction condition, the metal framework ZIF-8 with uniform particle size, particle size within the range of 200-300 nm and shape of a regular dodecahedron can be obtained, and the metal framework ZIF-8 with the shape is most favorably used as a raw material of a zinc nitrogen modified double-carbon catalytic material. If the reaction temperature is not within the preferred range, the resulting metal framework ZIF-8 has an irregular spherical shape and poor size uniformity. In addition, the shape of the metal framework ZIF-8 can be influenced by the type of the zinc salt, and the zinc salt is preferably zinc nitrate, and the used alcohol solvents such as methanol, ethanol and the like.
In a preferred embodiment, the molar ratio of the dimethylimidazole to the zinc salt is (0.5-1): 1.
As a preferable mode, the conditions of the first heat treatment are as follows: and under the argon atmosphere, heating to 700-1000 ℃ at the heating rate of 3-5 ℃/min, and preserving heat for 1-4 h. Under the preferable heat treatment condition, high-temperature carbonization and partial graphitization of the metal framework ZIF-8 can be realized, the three-dimensional zinc modified porous carbon material with a regular morphology is formed, and simultaneously, zinc is reduced into atomic metal zinc which is doped in situ in the framework of the three-dimensional zinc modified porous carbon material. If the temperature condition of the heat treatment is too low, carbonization is not complete, and if the temperature is too high, the yield is lowered.
Preferably, the mass ratio of the zinc-modified porous carbon material to the carbohydrate compound and the nitrogen source compound is 1 (0.01-0.1) to (0.5-1). The carbohydrate compound and the nitrogen source compound mainly form a uniform nitrogen-doped carbon coating layer on the surface of a carbon skeleton of the three-dimensional zinc-modified porous carbon material, so that the proportion control of the carbohydrate compound, the nitrogen source compound and the three is important. Within the selected ratio range, the nitrogen source compound mainly controls the doping amount of nitrogen, and the doping amount of nitrogen shows an increasing trend as the nitrogen source compound is increased from low to high, but the doping amount of nitrogen does not change much when the ratio of the nitrogen source compound is increased to a certain amount. The carbohydrate is mainly used as a carbon source, if the proportion of the carbohydrate is too low, the carbon material can be unevenly coated on the surface of a carbon skeleton of the three-dimensional zinc modified porous carbon material, and if the proportion of the carbohydrate is too high, the porous structure of the three-dimensional zinc modified porous carbon material can be blocked.
In a preferred embodiment, the saccharide compound is at least one of sucrose and fructose. The selected micromolecule carbohydrate is rich in polar groups, can fully cover the surface of ZIF-8 to form a 3D interconnected porous network structure, and can effectively protect the volatilization of zinc atoms.
In a preferred embodiment, the nitrogen source compound is at least one of cyanamide, dimethyl cyanamide, and dibenzyl cyanamide.
As a preferable mode, the conditions of the second heat treatment are as follows: in the argon atmosphere, firstly heating to 400-650 ℃ at a heating rate of 3-5 ℃/min, preserving heat for 2-6 h, then heating to 900-1000 ℃ at a heating rate of 3-5 ℃/min, and preserving heat for 2-6 h. The second heat treatment needs to be carried out in a segmented mode, the first temperature rise is carried out at a lower temperature, the primary carbonization of the carbohydrate is achieved, ZIF-8 is covered, a 3D interconnected network structure is formed, the loss of Zn at a high temperature is reduced, and the second temperature rise enables partial carbon in the double-carbon structure to be graphitized to improve the conductivity of the material. If the heat treatment temperature is too high, the metallic zinc will volatilize, resulting in a decrease in the zinc modification amount and a decrease in the activity.
As a preferred scheme, the ball milling conditions are as follows: the rotating speed is 200 to 240r/min, and the time is 0.5 to 1.5 hours.
According to the technical scheme, after the second heat treatment process, the heat treatment product is subjected to conventional washing and drying treatment to obtain the zinc-nitrogen modified dual-carbon catalytic material. The washing process is preferably carried out to neutrality. The drying temperature adopted by the drying treatment is 50-80 ℃, and the time is 10-12 h.
The invention also provides a zinc-nitrogen modified double-carbon catalytic material which is prepared by the preparation method. The zinc-nitrogen modified dual-carbon catalytic material has a 3D interconnected porous network structure, the connection points of the network structure are irregular spherical structures, and the irregular spheres have a shell-core structure. The graphitized carbon degree is increased due to the carbonization frequency of the inner layer, the defect carbon accounts for most of the outer layer due to the volatilization of zinc atoms and the formation of a large number of active sites with nitrogen carbon, the ORR capacity can be obviously improved due to the double-carbon-layer structure, and the air electrode serving as the zinc-air battery has high power density and specific capacity.
The invention also provides an application of the zinc-nitrogen modified dual-carbon catalytic material as a zinc-air battery cathode catalytic material.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects;
(1) the zinc-nitrogen modified dual-carbon catalytic material has the characteristics of developed pore structure, good conductivity, more active sites and the like, can obviously improve the initial potential, quickens the kinetic reaction process and improves the ORR capacity when being applied as a zinc-air battery cathode catalytic material.
(2) The zinc nitrogen modified dual-carbon catalytic material has a dual-carbon structure, a carbon skeleton structure is provided by ZIF-8 pyrolytic carbon, a 3D network dual-carbon structure is formed beneficially, the graphitization degree of the ZIF-8 pyrolytic carbon is high, the composite material is endowed with good conductivity, and the carbohydrate mainly modifies the surface of the carbon skeleton structure, provides a defect-rich high-activity carbon modified layer, and endows high ORR catalytic activity.
(3) According to the zinc-nitrogen modified dual-carbon catalytic material, ZIF-8 is used as a zinc source, zinc is uniformly distributed in an ionic state, and in-situ reduction coordination zinc ions form atomic-level doping, so that active sites are distributed more uniformly, and the catalytic activity is promoted more beneficially.
(4) According to the zinc-nitrogen modified dual-carbon catalytic material, the doping amount of zinc and nitrogen can be effectively adjusted through adjusting and controlling the proportion, and the adjustment and control of reaction active sites can be controllably realized.
(5) The invention adopts the carbohydrate as the carbon source, has wide source and low cost, and can better cover the precursor in the process of converting the carbohydrate into the carbon material by heat treatment to form a 3D interconnected network structure.
(6) The zinc-nitrogen modified dual-carbon catalytic material prepared by the invention is used as an air cathode catalytic material of a zinc-air battery, and the prepared zinc-air battery has high power density and specific capacity.
Drawings
Fig. 1 is an SEM image of the zinc-nitrogen modified dual-carbon catalytic material prepared in example 3 of the present invention.
Fig. 2 is an XPS diagram of the zinc-nitrogen modified dual-carbon catalytic material prepared in example 3 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1
Respectively dissolving zinc nitrate hexahydrate (1.0g) and dimethylimidazole (0.7g) in 50mL of methanol, pouring the dissolved dimethylimidazole into the zinc nitrate hexahydrate, stirring for 5 minutes until white suspended matters appear, standing at 30 ℃ for 12 hours, centrifuging and washing to obtain ZIF-8. Placing prepared ZIF-8 in quartz boat, placing in tube furnace, introducing argon gas, and keeping at 5 deg.C for min-1Heating to 900 ℃ at the heating rate, preserving heat for 2 hours at 900 ℃, and finally naturally cooling to room temperature to obtain black solid powder; the powder (1g) was mixed with cyanamide (0.7g) and sucrose (0.05g) at 240 rpm for ball milling-1Ball milling for 0.5 hr, placing the mixed sample in quartz boat, placing in tube furnace, introducing argon gas, and heating at 5 deg.C for min-1Annealing at a temperature rise rate of 500 ℃ and keeping the temperature at 500 ℃ for 5h, and then keeping the temperature for 5 min-1Heating to 1000 ℃ at the heating rate, annealing, keeping the temperature at 1000 ℃ for 5 hours, naturally cooling to room temperature, washing to neutrality by using deionized water, and drying at 100 ℃ for 12 hours to obtain the zinc-nitrogen modified dual-carbon catalytic material.
The obtained zinc-nitrogen modified dual-carbon material catalyst is used as an air cathode to assemble a zinc-air battery, and the electrolyte is 6mol L- 1KOH, the maximum power density can reach 286.3mW cm-2。
Example 2
Respectively dissolving zinc nitrate hexahydrate (1.0g) and dimethylimidazole (0.5g) in 50mL of methanol, pouring the dissolved dimethylimidazole into the zinc nitrate hexahydrate, stirring for 5 minutes until white suspended matters appear, standing at 40 ℃ for 12 hours, centrifuging and washing to obtain ZIF-8. Placing prepared ZIF-8 in quartz boat, placing in tube furnace, introducing argon gas, and heating at 3 deg.C for min-1Heating to 700 ℃, keeping the temperature at 700 ℃ for 1h, and finally naturally cooling to room temperature to obtain black solid powder; this powder (1g) was mixed with dibenzylcyanamide (0.5g) and fructose (0.03 g)g) The mixing speed of ball milling is 220 rpm-1Ball milling for 1h, placing the mixed sample in a quartz boat, placing in a tube furnace, and heating at 3 deg.C for min-1Annealing at 400 deg.C, maintaining at 400 deg.C for 5 hr, and heating at 3 deg.C for min-1Heating to 950 ℃ at the heating rate, annealing, keeping the temperature at 950 ℃ for 5 hours, naturally cooling to room temperature, washing to be neutral by using deionized water, and drying at 100 ℃ for 12 hours to obtain the zinc-nitrogen modified double-carbon catalytic material.
The obtained zinc-nitrogen modified dual-carbon material catalyst is used as an air cathode to assemble a zinc-air battery, and the electrolyte is 6mol L- 1KOH, the maximum power density can reach 277.5mW cm-2。
Example 3
Respectively dissolving zinc nitrate hexahydrate (1.0g) and dimethylimidazole (0.9g) in 50mL of methanol, pouring the dissolved dimethylimidazole into the zinc nitrate hexahydrate, stirring for 5 minutes until white suspended matters appear, standing at 20 ℃ for 12 hours, centrifuging and washing to obtain ZIF-8. Placing prepared ZIF-8 in quartz boat, placing in tube furnace, introducing argon gas, and heating at 4 deg.C for min-1Heating to 800 ℃ at the heating rate, preserving heat for 3 hours at the temperature of 800 ℃, and finally naturally cooling to room temperature to obtain black solid powder; this powder (1g) was mixed with dimethylcyanamide. (1g) And glucose (0.08g), ball milling mixing rotation speed of 220r min-1Ball milling for 1h, placing the mixed sample in a quartz boat, placing in a tube furnace, and heating at 4 deg.C for min-1Annealing at 650 deg.C, maintaining at 650 deg.C for 3h, and then 4 deg.C for min-1Heating to 900 ℃ at the heating rate, annealing, keeping the temperature at 900 ℃ for 2h, naturally cooling to room temperature, washing to neutrality with deionized water, and drying at 100 ℃ for 12h to obtain the zinc-nitrogen modified double-carbon catalytic material. From the SEM of fig. 1, it can be seen that the zinc nitrogen modified dual-carbon catalytic material has a 3D interconnected porous network structure, and from the XPS of fig. 2, it can be shown that zinc and nitrogen are modified together, and through charging and discharging, it can be seen that the zinc nitrogen modified dual-carbon catalytic material has an excellent cycle life as an air electrode of a zinc-air battery.
The obtained zinc-nitrogen modified dual-carbon materialThe material catalyst is an air cathode to assemble a zinc-air battery, and the electrolyte is 6mol L- 1KOH, the maximum power density can reach 326.1mW cm-2The constant current discharge can last for 1500 min.
Comparative example 1
Respectively dissolving zinc nitrate hexahydrate (1.0g) and dimethylimidazole (0.9g) in 50mL of methanol, pouring the dissolved dimethylimidazole into the zinc nitrate hexahydrate, stirring for 5 minutes until white suspended matters appear, standing at 20 ℃ for 12 hours, centrifuging and washing to obtain ZIF-8. Placing prepared ZIF-8 in quartz boat, placing in tube furnace, introducing argon gas, and heating at 4 deg.C for min-1Heating to 800 ℃ at the heating rate, preserving heat for 3 hours at the temperature of 800 ℃, and finally naturally cooling to room temperature to obtain black solid powder; placing the powder (1g) directly into quartz boat, placing into tube furnace, and heating at 4 deg.C for min-1Annealing at 650 deg.C, maintaining at 650 deg.C for 3h, and then 4 deg.C for min-1Heating to 900 ℃ at the heating rate, annealing, keeping the temperature at 900 ℃ for 2h, naturally cooling to room temperature, washing to neutrality with deionized water, and drying at 100 ℃ for 12h to obtain the comparative zinc-modified carbon catalytic material.
In a control experiment, since the sugar compound and the nitrogen source compound are not added, the zinc modified carbon catalytic material is obtained, and the zinc modified carbon catalytic material is also used as an air cathode for assembling a zinc-air battery, wherein the electrolyte is 6mol L-1KOH, the maximum power density can reach 256.7mW cm-2The constant current discharge can last for 300 min.
Claims (8)
1. A preparation method of a zinc-nitrogen modified dual-carbon catalytic material is characterized by comprising the following steps: the method comprises the following steps:
1) synthesizing a metal framework ZIF-8 by using dimethyl imidazole and zinc salt as raw materials;
2) carrying out first heat treatment on the metal framework ZIF-8 under a protective atmosphere to obtain a zinc modified porous carbon material;
3) mixing the zinc modified porous carbon material with a carbohydrate compound and a nitrogen source compound by ball milling, and carrying out secondary heat treatment under a protective atmosphere to obtain a zinc nitrogen modified dual-carbon catalytic material; the mass ratio of the zinc modified porous carbon material to the carbohydrate compound and the nitrogen source compound is 1 (0.01-0.1) to 0.5-1; the nitrogen source compound is at least one of cyanamide, dimethyl cyanamide and dibenzyl cyanamide.
2. The preparation method of the zinc-nitrogen modified dual-carbon catalytic material as claimed in claim 1, wherein the preparation method comprises the following steps: dissolving dimethyl imidazole and zinc salt in an alcohol solvent, and reacting at the temperature of 20-40 ℃ for 8-16 hours to obtain the metal framework ZIF-8.
3. The preparation method of the zinc-nitrogen modified dual-carbon catalytic material according to claim 2, wherein the preparation method comprises the following steps: the molar ratio of the dimethyl imidazole to the zinc salt is (0.5-1): 1.
4. The preparation method of the zinc-nitrogen modified dual-carbon catalytic material according to claim 1, wherein the preparation method comprises the following steps: the conditions of the first heat treatment are as follows: and under the argon atmosphere, heating to 700-1000 ℃ at the heating rate of 3-5 ℃/min, and preserving heat for 1-4 h.
5. The preparation method of the zinc-nitrogen modified dual-carbon catalytic material according to claim 1, wherein the preparation method comprises the following steps: the saccharide compound is at least one of sucrose and fructose.
6. The preparation method of the zinc-nitrogen modified dual-carbon catalytic material according to claim 1, wherein the preparation method comprises the following steps: the conditions of the second heat treatment are as follows: in the argon atmosphere, firstly heating to 400-650 ℃ at a heating rate of 3-5 ℃/min, preserving heat for 2-6 h, then heating to 900-1000 ℃ at a heating rate of 3-5 ℃/min, and preserving heat for 2-6 h.
7. A zinc-nitrogen modified dual-carbon catalytic material is characterized in that: the method of any one of claims 1 to 6.
8. The application of the zinc-nitrogen modified dual-carbon catalytic material of claim 7, which is characterized in that: the catalyst is applied as a cathode catalytic material of a zinc-air battery.
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