CN112520730B - Polyatomic co-doped graphene, preparation method and application - Google Patents
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Abstract
The invention discloses polyatomic co-doped graphene, a preparation method and application thereof in a zinc-air battery air electrode catalyst. The preparation method comprises the following steps: adding precursors of a nitrogen source and a sulfur source into deionized water, and stirring until the precursors are completely dissolved to obtain a precursor solution; adding the precursor solution and graphene into a ball milling tank at the same time, and carrying out ball milling to obtain a ball milling mixture; freeze-drying the ball-milled mixture to obtain mixed powder of graphene and thiourea; carrying out in-situ phosphating treatment on the mixed powder of the graphene and the thiourea under the nitrogen condition to obtain the nitrogen, sulfur and phosphorus co-doped graphene. According to the method, the defect graphene is generated by mechanical acting force, the uniform mixing of the precursor is realized, in-situ phosphorization is carried out, the nitrogen, sulfur and phosphorus ternary co-doped graphene is obtained, and the polyatomic doped carbon-based catalyst shows good electrocatalytic oxygen reduction/oxygen evolution performance.
Description
Technical Field
The invention relates to polyatomic co-doped graphene, a preparation method and application, and belongs to the technical field of preparation and application of carbon-based non-metal electrocatalysts.
Background
In the world today, sustainable energy conversion and storage technologies are attracting much attention as resources are in short supply and the demand for new energy technologies is increasing dramatically. Among them, metal-air batteries are environmentally friendly and have a high theoretical energy density (1084 Wh. kg)-1) And the like, and becomes one of important energy technologies. For rechargeable zinc-air cells, the slow kinetics of oxygen reduction and evolution reactions are critical in determining cell performance. At present, the high-efficiency oxygen electrode catalyst mainly depends on noble metals such as Pt and Ir, and the development and wide application of the metal-air battery are limited by the high cost and low storage capacity of the noble metals. Over the past decades, researchers have been working on developing alternative catalysts that are low cost, efficient and stable, with low cost carbon-based non-metal catalysts becoming one of the catalyst systems that people strive for. However, the pure carbon material has low catalytic activity, and the structure of the pure carbon material needs to be reasonably regulated to improve the catalytic activity of the pure carbon material.
The doping of the heteroatom can effectively change the electronic structure and surface chemical characteristics of the carbon material, thereby inducing a synergistic catalytic effect among different active sites, and the change of the electron spin density caused by the electronegativity and the electron spin density difference between the heteroatom and the carbon is also beneficial to improving the catalytic activity of the carbon-based material (ACS Catalysis 2015,5, 7244-7253). Dynagen et al reported that high electronegativity N (3.04) causes adjacent low electronegativity C (2.55) to exhibit positive charge characteristics, favoring the adsorption of O2, thereby exhibiting high ORR catalytic activity (Science 2009,323, 760-764). The N-doped porous carbon obtained by pyrolysis and hydrothermal treatment shows good ORR and OER dual-functional catalytic activity under alkaline conditions, and is even better than Pt/C and RuO2And meanwhile, the assembled zinc-air battery has high power density and stability. Wherein the presence of N functional groups can improve the catalytic performance (ACS Catalysis 2015,5, 5207-. Low electronegativity P (2.19) doping in carbon can cause defects in the carbon structure and increase electron delocalization, thereby increasing ORR catalytically active sites (Journal of the American Chemical Society 2012,134, 16127-16130). The doping of the single atom can enhance the catalytic performance of the carbon material to a certain extent, but the total doping amount is low and the distribution is uneven, so that the further improvement of the catalytic performance is limited. The amount of heteroatom doping can be increased by binary heteroatom doping, for example, binary doping of N and S can greatly increase the ORR performance of the catalyst due to the high content of N and S heteroatom doping and the simultaneous generation of Carbon defects (Carbon 2020,156, 514-522). In addition, when the N and P binary doped porous carbon materials are used for the rechargeable zinc-air battery, the battery performance is high in specific capacitance and power density (Scientific reports 2018,8 and 4200).
Compared with the single-element and binary heteroatom doping, the ternary doping of the carbon material can further increase the doping amount of the heteroatoms, and meanwhile, the doping of different heteroatoms can induce more carbon structure defects, so that the improvement of the dual-function catalytic performance of the carbon-based non-metal catalyst ORR/OER is facilitated. Graphene has a high surface area and high Chemical stability, and is considered to be one of the most effective carbon-based catalysts (Chemical Reviews 2007,107, 718-747). So far, for heteroatom-doped graphene materials, the steps are complicated and the doping amount is relatively low by two methods, namely a top-down method and a bottom-up method. In addition, ternary doped graphene materials are rarely reported, so that effective doping of multiple heteroatoms on the surface of graphene by a simple method still faces a great challenge.
Disclosure of Invention
The invention aims to solve the problems that: the existing method for effectively doping the multi-element heteroatom on the surface of the graphene has the technical problem of complex process.
In order to solve the technical problem, the invention provides a preparation method of polyatomic co-doped Graphene (NSP-Graphene), which is characterized by comprising the following steps:
step 1): adding precursors of a nitrogen source and a sulfur source into deionized water, and stirring until the precursors are completely dissolved to obtain a precursor solution;
step 2): adding the precursor solution and graphene into a ball milling tank at the same time, and carrying out ball milling to obtain a ball milling mixture;
step 3): freeze-drying the ball-milled mixture to obtain mixed powder of graphene and thiourea;
step 4): carrying out in-situ phosphating treatment on the mixed powder of the graphene and the thiourea under the nitrogen condition to obtain the nitrogen, sulfur and phosphorus co-doped graphene. The prepared polyatomic co-doped Graphene (NSP-Graphene) can realize co-doping of nitrogen, sulfur and phosphorus in a Graphene structure, and the total doping amount of heteroatoms is more than 3.78 at%. The polyatomic doped graphene has oxygen reduction/oxygen evolution catalytic activity.
Preferably, the precursors of the nitrogen source and the sulfur source in step 1) are one common precursor or two separate precursors.
More preferably, when the precursor of the nitrogen source and the sulfur source is one common precursor, it is thiourea or L-cysteine; when the precursors of the nitrogen source and the sulfur source are two separate precursors, urea and thioacetamide respectively.
Preferably, the ball used for ball milling in the step 2) is zirconia, the diameter of the ball is 3mm, and the mass ratio of the ball to the mixture of the precursor solution and the graphene is 6: 1; the rotation speed of the ball mill is 250rpm, and the time is 30 min.
Preferably, the freeze-drying time in the step 4) is 12 h.
Preferably, the precursor used in the in-situ phosphating treatment in the step 4) is disodium hydrogen phosphate.
Preferably, the conditions of the in-situ phosphating treatment in the step 4) are as follows: under the condition of nitrogen, firstly heating to 300 ℃ at the heating rate of 2 ℃/min, preserving heat for 2h, then heating to 900 ℃ at the heating rate of 5 ℃/min, and preserving heat for 1 h.
The invention also provides the polyatomic co-doped graphene prepared by the preparation method of the polyatomic co-doped graphene.
The invention also provides application of the polyatomic co-doped graphene in a zinc-air battery air electrode catalyst.
According to the method, the defect graphene is generated by mechanical acting force, the uniform mixing of the precursor is realized, in-situ phosphorization is carried out, the nitrogen, sulfur and phosphorus ternary co-doped graphene is obtained, and the polyatomic doped carbon-based catalyst shows good electrocatalytic oxygen reduction/oxygen evolution (ORR/OER) performance.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the structural defects are generated on the surface of the graphene by virtue of the mechanical acting force generated by ball milling, so that the effective doping of the subsequent heteroatoms in the graphene is facilitated. Meanwhile, the ball milling can realize the uniform mixing of the graphene, the nitrogen source and the sulfur source, and is favorable for the uniform distribution of doped nitrogen and sulfur atoms on the surface of the graphene. The preparation process is clean, reliable, environment-friendly and high in repeatability, and can be used for large-scale preparation.
(2) On one hand, the in-situ phosphorization realizes the uniform doping of heteroatom phosphorus in graphene; on the other hand, the nitrogen source and the sulfur source are thermally decomposed by high-temperature treatment, so that nitrogen and phosphorus co-doping is realized on the surface of the graphene in situ. The process avoids the problems of uneven distribution of heteroatoms in the graphene, poor catalytic performance and the like.
(3) The invention simultaneously realizes the uniform doping of three heteroatoms (nitrogen, sulfur and phosphorus) in the graphene, and has ORR and OER dual-functional catalytic activity. The nitrogen atom with high electronegativity makes carbon present positive charge property relative to carbon, which is beneficial to O2Adsorption of (3); the low electronegative phosphorus exhibits a positive charge characteristic and also facilitates O2 adsorption. In addition, co-doping of heteroatoms nitrogen, sulfur and phosphorus can increase graphene structural defects. The electrocatalytic performance of the graphene is enhanced by the factors, and the graphene is used as a zinc-air battery air electrode catalyst and shows good stability and cycle performance.
(4) The polyatomic co-doped graphene prepared by the invention can realize long-time charge-discharge cycle when being used for a rechargeable zinc-air battery.
Drawings
FIG. 1 is a schematic diagram of a polyatomic co-doped Graphene (NSP-Graphene) preparation process;
FIG. 2 is a TEM topography of different parts of polyatomic co-doped graphene; the Graphene material comprises a Graphene substrate, a Graphene layer, a Graphene oxide layer and a Graphene oxide layer, wherein a is polyatomic co-doped Graphene (NSP-Graphene), b is an NSP-Graphene edge structure, and c is an element distribution diagram of each atom of NSP-Graphene;
FIG. 3 is a graph of power density as a function of current density for NSP-Graphene, NS-Graphene and raw Graphene as air electrodes for zinc-air batteries;
FIG. 4 shows NSP-Graphene and NS-Graphene at 2mA cm-2Charge-discharge diagram under the conditions.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
And (3) performance determination: the microscopic morphology of the products of the examples of the invention was tested by TEM (JEOL JEM-2100F system), SEM (Hitachi S-4800) and elemental analysis was determined by XPS (RBDupgrad PHIE5000C ECSAsystem (Perkinelmer)). Half-cell performance testing was performed using a three-electrode system on the Chenghua CHI760D electrochemical workstation. Single cell testing was performed on a CT2001A blue cell testing system.
The manufacturers and specifications of the reagents used in examples 1 to 4 are shown in Table 1.
TABLE 1
| Name of reagent | Manufacturer of the product | Specification of |
| Thiourea | Shanghai Yixue chemical Co., Ltd | Analytical purity |
| Graphene | Shanghai Yixue chemical Co Ltd | 98％ |
| Disodium hydrogen phosphate | Shanghai Yixue chemical Co Ltd | Chemical purity |
Example 1
A preparation method of polyatomic co-doped Graphene (NSP-Graphene) with ORR/OER bifunctional catalytic activity (the flow is shown in figure 1) comprises the following steps:
step 1: weighing 4g of thiourea, adding the thiourea into 5mL of deionized water, and magnetically stirring until the thiourea is completely dissolved to obtain a thiourea solution;
step 2: putting 0.05g of graphene and the thiourea solution obtained in the step 1 into a ball milling tank, selecting zirconia balls with the diameter of 3mm, and the weight of the zirconia balls being 6 times of the total weight of the graphene and the thiourea, and installing the ball milling tank;
and step 3: setting ball milling speed (250rpm) and ball milling time (30min), and carrying out ball milling treatment on the graphene and thiourea;
and 4, step 4: carrying out freeze drying treatment on the ball-milled mixture obtained in the step 3 for 12h to finally obtain a dry powder sample of graphene and thiourea;
and 5: the step 4 dried powder sample and disodium hydrogen phosphate were placed in an atmosphere furnace with the disodium hydrogen phosphate placed in front of the air stream and the mass of the disodium hydrogen phosphate was 8 times that of the powder sample. Heating to 300 ℃ at a heating rate of 2 ℃/min under the condition of nitrogen and maintaining for 2 hours; subsequently, the temperature is increased to 900 ℃ at a heating rate of 5 ℃/min and maintained for 1 h. And naturally cooling to room temperature to obtain nitrogen, sulfur and phosphorus co-doped Graphene (NSP-Graphene).
Example 2
A preparation method of polyatomic co-doped Graphene (NSP-Graphene) with ORR/OER bifunctional catalytic activity (the flow is shown in figure 1) comprises the following steps:
step 1: putting 0.05g of graphene and a small amount of deionized water into a ball milling tank, selecting zirconia balls with the diameter of 3mm, which are 6 times of the total weight of the graphene, and installing the ball milling tank;
step 2: setting ball milling speed (250rpm) and ball milling time (30min), and carrying out ball milling treatment on the graphene;
and step 3: carrying out freeze drying treatment on the ball-milled mixture obtained in the step 2 for 12h to finally obtain a dry powder sample of graphene;
and 4, step 4: the step 3 dried powder sample and disodium hydrogen phosphate were placed in an atmosphere furnace with the disodium hydrogen phosphate placed in front of the air stream and the mass of the disodium hydrogen phosphate was 8 times that of the powder sample. Heating to 300 ℃ at a heating rate of 2 ℃/min under the condition of nitrogen and maintaining for 2 hours; subsequently, the temperature is increased to 900 ℃ at a heating rate of 5 ℃/min and maintained for 1 h. And naturally cooling to room temperature to obtain the phosphorus-doped Graphene (P-Graphene).
Example 3
A preparation method of polyatomic co-doped Graphene (NSP-Graphene) with ORR/OER bifunctional catalytic activity (the flow is shown in figure 1) comprises the following steps:
step 1: weighing 4g of thiourea, adding the thiourea into 5mL of deionized water, and magnetically stirring until the thiourea is completely dissolved to obtain a thiourea solution;
step 2: putting 0.05g of graphene and the thiourea solution obtained in the step 1 into a ball milling tank, selecting zirconia balls with the diameter of 3mm, and the weight of the zirconia balls is 6 times that of the graphene and the thiourea, and installing the ball milling tank;
and step 3: setting ball milling speed (250rpm) and ball milling time (30min), and carrying out ball milling treatment on the graphene and thiourea;
and 4, step 4: carrying out freeze drying treatment on the ball-milled mixture obtained in the step 3 for 12h to finally obtain a dry powder sample of graphene and thiourea;
and 5: the step 4 dried powder sample was placed in an atmosphere furnace. Heating to 300 ℃ at a heating rate of 2 ℃/min under the condition of nitrogen and maintaining for 2 hours; subsequently, the temperature is increased to 900 ℃ at a heating rate of 5 ℃/min and maintained for 1 h. And naturally cooling to room temperature to obtain the nitrogen and sulfur co-doped Graphene (NS-Graphene).
Example 4
A preparation method of polyatomic co-doped Graphene (NSP-Graphene) with ORR/OER bifunctional catalytic activity (the flow is shown in figure 1) comprises the following steps:
step 1: weighing 4g of thiourea, adding the thiourea into 5mL of deionized water, and magnetically stirring until the thiourea is completely dissolved to obtain a thiourea solution;
and 2, step: uniformly stirring 0.05g of graphene and the thiourea solution obtained in the step 1;
and step 3: carrying out freeze drying treatment on the ball-milled mixture obtained in the step 2 for 12h to finally obtain a dry powder sample of graphene and thiourea;
and 4, step 4: the step 3 dry powder sample was placed in an atmosphere furnace. Heating to 300 ℃ at a heating rate of 2 ℃/min under the condition of nitrogen and maintaining for 2 hours; subsequently, the temperature is increased to 900 ℃ at a heating rate of 5 ℃/min and maintained for 1 h. And naturally cooling to room temperature to obtain nitrogen, sulfur and phosphorus co-doped Graphene (NSP-Graphene).
As can be seen from a in fig. 2, a TEM morphology of nitrogen, sulfur and phosphorus polyatomic-co-doped Graphene (NSP-Graphene) obtained after in-situ phosphating of ball-milled mixed powder of Graphene and thiourea (example 1) can be seen, and the obtained polyatomic-co-doped Graphene maintains the original morphology of Graphene; as can be seen from b in fig. 2, the edge profile of graphene shows that the number of layers of graphene is about 4; as can be seen from c in fig. 2, the distribution diagram of each element in the polyatomic co-doped graphene indicates that nitrogen, sulfur and phosphorus can be uniformly dispersed on the surface of the graphene. On one hand, a large number of structural defects are generated on the surface of graphene through ball milling, so that effective doping of three heteroatoms, namely nitrogen, sulfur and phosphorus is facilitated; on the other hand, in the co-ball milling process of thiourea and graphene, a sulfur source and a nitrogen source are uniformly mixed with the graphene, and then uniform doping of ternary heteroatoms is realized in the in-situ phosphating process of the later stage. The specific surface area of the graphene enables a large number of oxygen reduction active sites to be exposed, and meanwhile, three heteroatoms, namely nitrogen, sulfur and phosphorus, are codoped in the graphene, so that the carbon electronic structure can be effectively regulated and controlled to show high ORR and OER catalytic activity.
FIGS. 3 and 4 show the power density of the zinc-air battery with the current density and the power density of the battery at 2mA · cm when the nitrogen, sulfur and phosphorus ternary doped Graphene (NSP-Graphene), the nitrogen and sulfur doped Graphene (NS-Graphene) and the original Graphene are respectively used as the air electrode of the zinc-air battery-2And (3) a charge-discharge schematic diagram under the condition, and therefore, the polyatomic co-doped graphene shows higher power density and good charge-discharge stability as the zinc-air battery air electrode catalyst.
Claims (9)
1. The preparation method of the polyatomic co-doped graphene is characterized by comprising the following steps:
step 1): adding precursors of a nitrogen source and a sulfur source into deionized water, and stirring until the precursors are completely dissolved to obtain a precursor solution;
step 2): simultaneously adding the precursor solution and graphene into a ball milling tank for ball milling to obtain a ball milling mixture; the ball body adopted by the ball milling in the step 2) is zirconia, and the mass ratio of the ball body to the mixture of the precursor solution and the graphene is 6: 1; the rotation speed of the ball mill is 250rpm, and the time is 30 min;
step 3): freeze-drying the ball-milled mixture to obtain mixed powder of graphene and thiourea;
step 4): carrying out in-situ phosphating treatment on the mixed powder of the graphene and the thiourea under the nitrogen condition to obtain the nitrogen, sulfur and phosphorus co-doped graphene.
2. The method according to claim 1, wherein the precursors of the nitrogen source and the sulfur source in step 1) are a common precursor or two separate precursors.
3. The method according to claim 2, wherein when the precursor of the nitrogen source and the sulfur source is a common precursor, the common precursor is thiourea or L-cysteine; when the precursors of the nitrogen source and the sulfur source are two separate precursors, urea and thioacetamide respectively.
4. The method for preparing the polyatomic co-doped graphene according to claim 1, wherein the ball used for ball milling in the step 2) has a diameter of 3 mm.
5. The method for preparing the polyatomic co-doped graphene according to claim 1, wherein the freeze-drying time in the step 4) is 12 hours.
6. The method for preparing the polyatomic co-doped graphene according to claim 1, wherein a precursor used in the in-situ phosphating treatment in the step 4) is disodium hydrogen phosphate.
7. The method for preparing the polyatomic co-doped graphene according to claim 1 or 6, wherein the conditions of the in-situ phosphating treatment in the step 4) are as follows: under the condition of nitrogen, firstly heating to 300 ℃ at the heating rate of 2 ℃/min, preserving heat for 2h, then heating to 900 ℃ at the heating rate of 5 ℃/min, and preserving heat for 1 h.
8. The polyatomic co-doped graphene prepared by the preparation method of the polyatomic co-doped graphene according to any one of claims 1 to 7.
9. The use of the polyatomic co-doped graphene according to claim 8 in a zinc-air battery air electrode catalyst.
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