CN113387342A - Co/CoO-loaded nitrogen-doped carbon composite material and preparation method and application thereof - Google Patents

Co/CoO-loaded nitrogen-doped carbon composite material and preparation method and application thereof Download PDF

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CN113387342A
CN113387342A CN202110652345.5A CN202110652345A CN113387342A CN 113387342 A CN113387342 A CN 113387342A CN 202110652345 A CN202110652345 A CN 202110652345A CN 113387342 A CN113387342 A CN 113387342A
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coo
nitrogen
doped carbon
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CN113387342B (en
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李保军
武现丽
刘艳艳
崔星宇
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Zhengzhou University
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Abstract

The invention discloses a preparation method of a Co/CoO-loaded nitrogen-doped carbon composite material, wherein a biomass material is subjected to nitrogen doping treatment to obtain a nitrogen-doped carbon material, so that a carrier with a large specific surface area is provided for a Co/CoO heterojunction, the contact with an electrolyte is increased, and the polarization phenomenon in the electrochemical reaction process is reduced; and then loading a metal compound on the nitrogen-doped carbon material pipeline by a constant-current electrodeposition method, wherein the method can effectively control the loading amount of metal, and simultaneously, the metal compound forms a uniform lamellar structure, so that the effective area of the reaction is effectively increased. The invention also discloses a nitrogen-doped carbon composite material loaded with Co/CoO, and the composite material has a Co/CoO heterostructure and shows a good catalytic activity. The carbon material is doped with nitrogen element to form C-N bond, which increases the active sites of catalytic reaction. The invention also discloses application of the composite material in a zinc-air battery, and the composite material is used as a cathode material and shows good activity and ultrahigh stability.

Description

Co/CoO-loaded nitrogen-doped carbon composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of biomass-based electro-catalysis energy storage, and relates to a Co/CoO-loaded nitrogen-doped carbon composite material, and a preparation method and application thereof.
Background
At present, environmental crisis and energy shortage have attracted common attention of scientists, and a great deal of research has been devoted to the development of efficient conversion devices of renewable energy. Rechargeable zinc-air battery with higher theoretical energy density 1086Wh kg-1The advantages of environmental protection, stable and safe electrolyte and the like attract wide attention. The zinc-air battery is mainly composed of a metal zinc anode, an air cathode, electrolyte, a diaphragm and the like. Wherein the air cathode comprises a hydrophobic Gas Diffusion Layer (GDL) and a hydrophilic catalytic layer, and the electrode reaction comprises an Oxygen Reduction Reaction (ORR) during discharging and an Oxygen Evolution Reaction (OER) during charging. The slow kinetics of ORR and OER lead to poor performance of zinc-air batteries. The ORR reaction in the battery mainly occurs on a gas-liquid-solid three-phase interface, and the abundant three-phase interfaces are constructed, so that catalytic active sites participate in the reaction, the reaction rate of cathode reaction is improved, and further various indexes of the zinc-air battery are improved. The construction of the high-efficiency air electrode is an important way for improving the performance of the zinc-air battery. The interfacial engineering and the intrinsic catalytic activity of the catalyst play equally important roles in the electrode construction.
The transition metal group ORR/OER bifunctional catalyst mainly comprises nitride, sulfide, phosphide and the like. The inherent electrocatalytic activity and the dynamics speed of the transition metal can be further improved through defect creation, shape regulation and electronic structure optimization. The catalytic metal nanoparticles are compounded with high-conductivity porous carbon materials (such as carbon nanotubes, carbon fibers, graphene nanosheets and the like) so as to be an effective way for improving the catalytic activity and stability of the catalyst. The heteroatom doping can adjust the electronic configuration of the carbon substrate, increase the interaction between the carrier and the transition metal nanoparticles and effectively prevent the aggregation of the metal nanoparticles. The ORR reaction on the air electrode of the zinc-air battery mainly occurs in the gas-liquid-solid three-phase interface region. Only the catalyst located in the interface region can sufficiently exert the catalytic action. A three-phase interface is constructed on an electrode to the maximum extent so that more catalytic active sites participate in the reaction, and the method is an effective strategy for improving the performance of the zinc-air battery.
Paulownia is widely distributed in China and has great potential application value. At present, paulownia wood is commonly used as furniture and the like in China, and belongs to primary processing application. The ordered layered structure of paulownia wood provides an ideal template for the design of functional materials, and the vertical pipeline structure is an excellent mass transfer channel. The layered structure is very beneficial to the construction of a 3D integral catalytic material and is applied to the catalytic reaction of a three-phase interface.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of a Co/CoO-loaded nitrogen-doped carbon composite material, which has the characteristics of mild conditions and simple steps.
The invention also aims to provide a nitrogen-doped carbon composite material loaded with Co/CoO, which has the characteristics of uniform appearance, large specific surface area, good catalytic activity and the like.
The invention also aims to provide application of the nitrogen-doped carbon composite material loaded with Co/CoO in a zinc-air battery.
One of the purposes of the invention is realized by adopting the following technical scheme:
a preparation method of a Co/CoO-loaded nitrogen-doped carbon composite material comprises the following steps:
(1) soaking wood raw material in a solution containing NH4 +After soaking, drying and calcining in an inert atmosphere to obtain a nitrogen-doped carbon material, which is marked as NWC;
(2) immersing the NWC prepared in the step (1) in a solution containing Co2+And Na+In the mixed solution, the supported Co (OH) is prepared by the electrodeposition process2Of nitrogen-doped carbon material, noted as Co (OH)2@NWC；
(3) The Co (OH) prepared in the step (2)2And calcining the @ NWC in an inert atmosphere to obtain the final product Co/CoO-loaded nitrogen-doped carbon composite material, which is marked as Co/CoO @ NWC.
Further, the mixed solutionThe liquid is Co (NO)3)2·6H2O and NaNO3Mixed solution, Co (NO)3)2·6H2O and NaNO3The molar 3 concentration ratio of (a) is 10: 1.
Further, the nitrogen-doped carbon material is mixed with Co (NO)3)2·6H2The mass ratio of O is 1: 15.
Further, the nitrogen-doped carbon material is nitrogen-doped carbonized paulownia wood.
Further, the water solution in the step (1) is 4mol/L NH4Soaking in Cl aqueous solution for 12-24 h; the calcination was carried out at 500 ℃ for 1h and then at 900 ℃ for 2 h.
Further, the current density of the electrodeposition process of the step (2) is 0.1mAcm-2And the deposition time is 2 h.
Further, the inert atmosphere in the step (3) is argon, the calcining temperature is 500 ℃, and the time is 1 h.
The second purpose of the invention is realized by adopting the following technical scheme:
the nitrogen-doped carbon composite material loaded with Co/CoO prepared by the method.
The third purpose of the invention is realized by adopting the following technical scheme:
the nitrogen-doped carbon composite material loaded with Co/CoO is applied to a zinc-air battery.
Further, the nitrogen-doped carbon composite material loaded with the Co/CoO is applied as a cathode catalyst of a zinc-air battery.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a preparation method of a Co/CoO-loaded nitrogen-doped carbon composite material, which comprises the steps of pretreating a biomass material to obtain a nitrogen-doped carbon material ━ nitrogen-doped carbonized wood chip, reserving the original vertical pipeline structure of the biomass material, contributing to enlarging the specific surface area of a catalyst, increasing the contact with electrolyte and reducing the polarization phenomenon in the electrochemical reaction process.
The Co/CoO heterostructure loaded nitrogen-doped carbon composite material (Co/CoO @ NWC) is constructed by a constant-current electrodeposition method, and has the advantages of mild reaction conditions and simplicity in operation. The method can effectively control the loading amount of metal, and simultaneously, the metal compound forms a uniform lamellar structure which is uniformly loaded on the tube wall of the nitrogen-doped carbon material, thereby effectively increasing the effective area of the reaction.
2. The invention also provides a Co/CoO loaded nitrogen-doped carbon composite material prepared by the method, and the composite material can be used as a catalyst for a zinc-air battery cathode material and shows good catalytic activity and stability. The composite material has a Co/CoO heterostructure and shows good catalytic activity. The carbon material is doped with nitrogen element to form C-N bond, which increases the active sites of catalytic reaction.
3. The invention also provides application of the Co/CoO loaded nitrogen-doped carbon composite material in a zinc-air battery, wherein the Co/CoO @ nitrogen-doped carbon composite material is used as a cathode material of the zinc-air battery, and the maximum discharge power density of the Co/CoO @ nitrogen-doped carbon composite material is up to 152.8mW/cm2Far better than commercial 20% Pt/C and RuO2The properties of the mixture. And simultaneously, the catalyst shows ultrahigh stability, and the Co/CoO loaded nitrogen-doped carbon can maintain 270h and hardly decay with 10min charging and 10min discharging as a period.
Drawings
FIG. 1 is an XRD pattern of the products prepared in example 1 of the present invention and comparative examples 1 to 3;
FIG. 2 is a schematic representation of the morphology of the product prepared in example 1 of the present invention, wherein FIG. 2a is an SEM image, FIG. 2b is a TEM image, and FIGS. 2c and 2d are HRTEM images;
FIG. 3 is an XPS spectrum of a product prepared in example 1 of the present invention, wherein 3a is an XPS survey, 3b is a high resolution XPS spectrum of C1s and Co2p, 3C is a high resolution XPS spectrum of N1s, and 3d is a high resolution XPS spectrum of O1 s;
FIG. 4 is a BET test chart of the products prepared in example 1 and comparative examples 1 to 3 of the present invention, wherein 4a is a nitrogen adsorption and desorption isotherm diagram, and FIG. 4b is a pore size distribution diagram;
FIG. 5 is a graph showing electrocatalytic properties of products prepared in examples 1 and comparative examples 1 to 4 of the present invention, wherein FIG. 5a is an ORR property graph and FIG. 5b is an OER property graph;
fig. 6 is a graph of the performance of a zinc-air battery of the product prepared in example 1 of the present invention, in which fig. 6a is an open circuit voltage stability graph, fig. 6b is a discharge power density graph, and fig. 6c is a cycle stability graph.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and the detailed description, and it should be noted that any combination of the embodiments or technical features described below can be used to form a new embodiment without conflict.
Example 1
The preparation method of the Co/CoO loaded nitrogen-doped carbon composite material comprises the following steps:
(1) cutting a fresh paulownia wood into 1.5 x 0.5cm slices, then putting the slices into a 0.1M dilute hydrochloric acid solution for full washing, then washing the slices to be neutral by using distilled water, and then putting the slices into a vacuum oven at 60 ℃ for drying for 12 hours; the treated wood chips are soaked in 4mol/L ammonium chloride aqueous solution, vacuum impregnation is carried out for 1 hour, and then standing is carried out for 24 hours. Taking out the impregnated wood chips, placing the wood chips in a vacuum oven at 60 ℃ for drying for 12 hours, then heating to 500 ℃ at the heating rate of 5 ℃/min in the argon atmosphere, and keeping the temperature for 1 hour; then the temperature is raised to 900 ℃ again at the temperature rising rate of 5 ℃/min and kept for 2 h. And cooling to room temperature to obtain the nitrogen-doped carbon material ━ nitrogen-doped carbonized wood chips, which are recorded as NWC.
(2) Polishing the NWC obtained in the step (1) to 1mm, and then placing the NWC into 60mL of aqueous solution containing cobalt nitrate and sodium nitrate, wherein the molar concentration ratio of the cobalt nitrate to the sodium nitrate is 10: 1. The nitrogen-doped carbon material and Co (NO)3)2·6H2The mass ratio of O is 1:15, and the ultrasonic dipping method is adopted for dipping for 12 h. After the impregnation is finished, NWC is used as a working electrode, a platinum electrode is used as a counter electrode, a calomel electrode is used as a reference electrode, and 0.1mA/cm is used2The galvanostatic deposition process was carried out at a current density of CHI660 on an electrochemical workstation with a deposition time of 2 h. After deposition, fully washing the wood chips with distilled water to remove residues on the surface, and finally drying the wood chips in a vacuum oven at 60 ℃ for 12h to obtain Co (OH)2@NWC。
(3) The Co (OH) obtained in the step (2)2@ NWC is placed in a tube furnace, the temperature is raised to 500 ℃ at the heating rate of 5 ℃/min in the argon atmosphere and is kept for 1h, and the nitrogen-doped carbon composite material loaded with Co/CoO can be obtained after cooling to the room temperature, and the composite material is marked as Co/CoO @ NWC.
Comparative example 1
Comparative example 1 differs from example 1 in that: the procedure in example 1 was repeated except that the step (3) was omitted to obtain Co (OH) as a final product2@NWC。
Comparative example 2
Comparative example 2 differs from example 1 in that: the steps (2) and (3) were omitted, and the nitrogen-doped carbon material ━, which is a final product of nitrogen-doped carbonized wood chips NWC, was prepared in the same manner as in example 1.
Comparative example 3
Comparative example 3 differs from example 1 in that: and (2) the paulownia wood in the step (1) is not doped with nitrogen, and a final product of carbonized wood chips ━ WC is obtained after calcination.
Comparative example 4
Comparative example 4 differs from example 1 in that: the paulownia wood obtained in the step (1) is not doped with nitrogen, and is directly used as the carrier material in the steps (2) and (3) after being calcined, and the rest corresponds to the embodiment 1, so that the final product Co/CoO @ WC is obtained.
Experimental example 1
The morphology, components, chemical bonds and microstructure of the products obtained in example 1 and comparative examples 1 to 4 are systematically studied by modern nanometer test analysis technologies such as XRD, SEM, TEM, HRTEM, XPS, BET and the like, and the results are as follows:
the XRD characterization of the products obtained in example 1 and comparative examples 1-3 was performed, and the results are shown in FIG. 1. The XRD patterns of the products correspond to a standard card, so that the product obtained in example 1 contains characteristic peaks of Co and CoO, and the fact that the final product simultaneously comprises Co and CoO is proved, and a Co/CoO heterojunction is obtained. COMPARATIVE EXAMPLE 1 Co (OH) prepared2@ NWC Co (OH) free2Corresponding characteristic peaks, indicating Co (OH)2In an amorphous state.
The product obtained in example 1 was further characterized by morphology, fig. 2a is an SEM image of the Co/CoO @ NWC composite material, from which it can be seen that the Co/CoO @ NWC composite material maintained a good wall structure of paulownia wood, and fig. 2b and 2c are TEM images of the Co/CoO @ NWC composite material, showing that the Co/CoO heterostructure is in a lamellar micron-scale structure, and is uniformly supported on the wall of the charcoal without blocking the original charcoal channels. HRTEM is carried out on the Co/CoO @ NWC composite material to further analyze the microstructure, the crystal nucleus stripe orientation of the lamellar microstructure is obviously different in figure 2d, the lattice spacing of 0.21nm corresponds to the XRD Co (111) crystal plane and CoO (200) crystal plane in figure 1, the lattice spacing of 0.25nm corresponds to the CoO (111) crystal plane, and the lattice spacing of 0.17nm corresponds to the Co (200) crystal plane. The lamellar microstructure in the product of example 1 is shown to be a composite of Co and CoO, consistent with XRD results.
In order to determine the chemical bonding state of each element in the product, the product obtained in example 1 is subjected to XPS full spectrum analysis, and the result is shown in fig. 3, where fig. 3a is an XPS energy spectrum full spectrum, which indicates that C, N, O, Co four elements exist in the product obtained in example 1, and the N element is successfully doped into paulownia wood; 3b, 3c and 3d are high-resolution XPS energy spectra of each element, which prove that the valence states of cobalt in the product obtained in example 1 are 0 valence and +2 valence, and further prove that the product contains a Co/CoO heterostructure.
FIG. 4 is a BET analysis of the products obtained in example 1 and comparative examples 1 to 3, and the results of nitrogen adsorption and desorption tests performed on the materials show that the specific surface area of the materials is reduced and the micropores are reduced after loading the Co/CoO heterostructure, which shows that the Co/CoO heterostructure is successfully loaded on the NWC. But still has higher specific surface area, is beneficial to fully contacting with the electrolyte and increases the activity of the catalytic process.
Experimental example 2
And (3) testing the catalytic performance:
the performance tests of the oxygen reduction reaction ORR and the oxygen evolution reaction OER adopt a three-electrode system test, and final products prepared in the embodiment 1 and the comparative examples 1 to 4 are respectively used as catalysts to be loaded on a glassy carbon electrode to be used as working electrodes. The catalyst slurry was prepared by mixing 4mg of catalyst, 50. mu.L of LNafion and 500. mu.L of ethanol. The invention takes 5 mul catalyst slurry to drop on the glassy carbon electrode, and dries for substitution. The catalytic performance test was compared to commercial Pt/C.
The ORR performance of the different products obtained in inventive example 1 and comparative examples 1-4 as catalysts is shown in FIG. 5a, and it can be seen from the figure that the half-wave potential (vs. RHE) of Co/CoO @ NWC is 0.85V, respectively, the half-wave potential of Co/CoO @ NWC obtained in inventive example 1 is equivalent to that of Pt/C electrode, and good catalytic activity is shown.
The ORR performance of the different products obtained in inventive example 1 and comparative examples 1-4 as catalysts is shown in FIG. 5b, from which it can be seen that Co/CoO @ NWC is at a current density of 10mA/cm2The potential (vs. RHE) was 1.62V. The overpotential of the Co/CoO @ NWC catalyst electrode obtained in the embodiment 1 of the invention is lower, and the performance is better.
Experimental example 3
Zinc-air cell testing:
the zinc-air battery testing device takes a zinc sheet as an anode, and carbon paper loaded with a catalyst is attached to an air electrode group as a cathode. Wherein the catalyst slurry was prepared in the same manner as in Experimental example 2, and the catalyst loading was 1mg/cm2. 20% Pt/C and RuO2The mixture of (a) was used as a control group and tested under the same conditions.
The performance of the product of example 1 of the present invention as a cathode catalyst for a zinc-air cell is shown in FIG. 6, FIG. 6a is a graph comparing the open circuit voltage curves of a zinc-air cell, and the Co/CoO @ NWC of example 1 of the present invention exhibits 20% Pt/C and RuO within 24h2The mixture had a considerable level of stability, the open circuit voltage being kept at 1.42V. FIG. 6b is a graph of the discharge power density of a zinc-air cell, with the Co/CoO @ NWC of example 1 of the invention exhibiting a maximum discharge power density as high as 152.8mW/cm2Far better than commercial 20% Pt/C and RuO2The properties of the mixture. FIG. 6c is a graph of the cycling stability of a zinc-air cell at a constant current density of 10mA/cm2In one cycle of 10min charging and 10min discharging, the Co/CoO @ NWC of example 1 of the present invention maintained 270h with almost no decay. While commercial 20% Pt/C and RuO2The mixture can only be maintained for 60 hours, and has large voltage fluctuation and poor stability. As a result, it was found that example 1 of the present invention gaveThe Co/CoO @ NWC has stronger stability and activity in a zinc-air battery.
In conclusion, the Co/CoO @ NWC composite material obtained by the invention has the advantages that the simple substance cobalt and the cobalt oxide both have stronger catalytic activity, and the nitrogen-doped carbon material forms a C-N bond, so that the catalytic activity sites of ORR and OER are increased. According to the method, firstly, a biomass material, namely paulownia wood, is pretreated to obtain the nitrogen-doped carbonized wood chips, the original vertical pipeline structure of the biomass material is reserved, the specific surface area of the catalyst is increased, the contact with an electrolyte is increased, and the polarization phenomenon in the electrochemical reaction process is reduced. And then constructing a Co/CoO heterostructure loaded nitrogen-doped carbon material composite material (Co/CoO @ NWC) by a constant-current electrodeposition method, wherein the reaction condition is mild, and the operation is simple. The method can effectively control the loading amount of metal, and simultaneously, the metal compound forms a uniform lamellar structure which is uniformly loaded on the tube wall of the nitrogen-doped carbon material, thereby effectively increasing the effective area of the reaction. The maximum discharge power density of the Co/CoO @ NWC composite material obtained by the invention in a zinc-air battery is as high as 152.8mW/cm2Far better than commercial 20% Pt/C and RuO2The properties of the mixture. And simultaneously, the Co/CoO @ NWC of the embodiment 1 of the invention can maintain 270h and hardly attenuate with 10min charging and 10min discharging as a period.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.

Claims (10)

1. A preparation method of a Co/CoO-loaded nitrogen-doped carbon composite material is characterized by comprising the following steps:
(1) soaking wood raw material in a solution containing NH4 +After soaking, drying and calcining in an inert atmosphere to obtain a nitrogen-doped carbon material, which is marked as NWC;
(2) immersing the NWC prepared in the step (1) in a solution containing Co2+And Na+In the mixed solution of (A) and (B), by an electrodeposition processObtaining Co (OH) Supported2Of nitrogen-doped carbon material, noted as Co (OH)2@NWC；
(3) The Co (OH) prepared in the step (2)2And calcining the @ NWC in an inert atmosphere to obtain the final product Co/CoO-loaded nitrogen-doped carbon composite material, which is marked as Co/CoO @ NWC.
2. The method of claim 1, wherein the mixed solution is Co (NO)3)2·6H2O and NaNO3Mixed solution, Co (NO)3)2·6H2O and NaNO3The molar concentration ratio of (a) to (b) is 10: 1.
3. The method of claim 1, wherein the nitrogen-doped carbon material is doped with Co (NO)3)2·6H2The mass ratio of O is 1: 15.
4. The method of making a Co/CoO loaded nitrogen doped carbon composite of claim 1, wherein the nitrogen doped carbon material is nitrogen doped carbonized paulownia wood.
5. The method of claim 1, wherein the aqueous solution in the step (1) is 4mol/L NH4Soaking in Cl aqueous solution for 12-24 h; the calcination was carried out at 500 ℃ for 1h and then at 900 ℃ for 2 h.
6. The method of claim 1, wherein the step (2) electrodeposition process has a current density of 0.1mA cm-2And the deposition time is 2 h.
7. The method of preparing a Co/CoO loaded nitrogen doped carbon composite material according to claim 1, wherein the inert atmosphere in step (3) is argon, the calcination temperature is 500 ℃, and the calcination time is 1 hour.
8. A Co/CoO loaded nitrogen doped carbon composite, prepared by the method of any one of claims 1 to 7.
9. Use of the Co/CoO loaded nitrogen doped carbon composite of claim 8 in a zinc-air battery.
10. Use of the Co/CoO-loaded nitrogen-doped carbon composite as a cathode catalyst for a zinc-air battery according to claim 9.
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