CN116443851A - Method for preparing high-nitrogen-doped carbon material by molecular scale finite field pyrolysis and application - Google Patents
Method for preparing high-nitrogen-doped carbon material by molecular scale finite field pyrolysis and application Download PDFInfo
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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Abstract
The invention belongs to the technical field of carbon material preparation, and relates to a method for preparing a high-nitrogen-doped carbon material by molecular scale limited domain pyrolysis and application thereof, wherein the preparation method comprises the following steps: (1) Placing graphite-phase carbon nitride precursor, 2-mercaptobenzimidazole and zirconia ball-milling beads in a ball-milling tank for ball-milling until the mixture is uniform, and obtaining solid powder; (2) Transferring the solid powder obtained in the step 1 into a quartz boat, then placing the quartz boat into a quartz tube, then placing the quartz tube into a tube furnace, introducing protective gas, performing high-temperature carbonization treatment, and cooling to room temperature after the reaction is finished to obtain the high-nitrogen doped carbon material. The method realizes microscopic mixing and efficient utilization of the raw materials on the molecular scale, and has the advantages of simple process, low cost, high raw material utilization rate, high nitrogen atom doping amount, easiness in large-scale production and the like.
Description
Technical Field
The invention relates to a method for preparing a high-nitrogen-doped carbon material by molecular scale finite field pyrolysis and application thereof, and belongs to the technical field of carbon material preparation.
Background
The dye sensitized solar cell (dye sensitized cell) is used as one of the third generation solar cells, has the advantages of simple assembly process, low cost, high conversion rate and the like, and has wide application prospect. The dye-sensitized cell mainly comprises three parts, namely a photo-anode for adsorbing a sensitizer, electrolyte and a counter electrode. The counter electrode is a key component of the dye-sensitized cell and mainly plays a role in collecting external circuit electrons and catalyzing reduction of iodine three ions. Currently, the most commonly used counter electrode is the noble metal Pt. However, pt counter electrodes have disadvantages of high price, limited reserves, poor stability in electrochemical environment, etc., increasing the production cost of dye-sensitized cells, and limiting the large-scale application thereof. Research shows that the cheap nitrogen-doped carbon material can efficiently catalyze I 3 - Shows great potential for replacing Pt noble metals. Theoretical calculations prove that the high nitrogen doping amount can enhance the state density at the fermi level of the carbon material, thereby promoting the improvement of the catalytic performance of the carbon material. In addition, the high doping amount is favorable for the uniform distribution of nitrogen atoms in the carbon skeleton, so that the physical and chemical properties of the carbon material phase are consistent, the repeatability of the catalytic performance of the carbon material phase is ensured, and the carbon material phase has important practical significance for large-scale application. The preparation method of the nitrogen-doped carbon material mainly comprises an in-situ synthesis method and a post-treatment method. However, the existing developed method has the problems of higher cost, complex synthesis process, low raw material utilization rate, low nitrogen atom doping amount, environmental pollution and the like. Therefore, the development of an economically viable simple process for preparing high nitrogen doped carbon materials is of great importance.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a method for preparing a high-nitrogen-doped carbon material by molecular scale limited-area pyrolysis and application thereof, and a high-efficiency reaction path is designed by a substance micromixing method, so that the high-nitrogen-doped carbon material is simple in process, low in cost and easy to produce in large scaleThe preparation method of the doped carbon material realizes microscopic mixing and efficient utilization of raw material molecular scale, and the high nitrogen doping in the prepared material can induce more carbon atoms to become active sites of electrochemical reaction, and the active sites are used for dyeing counter electrode I of a battery 3 - The reduction aspect shows excellent performance.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing a high-nitrogen-doped carbon material by molecular-scale limited-range pyrolysis is characterized in that a nitrogen-rich graphite-phase carbon nitride precursor is used as a nitrogen source, 2-mercaptobenzimidazole is used as a carbon source, and a novel C-S-C bonding-induced limited-range pyrolysis strategy is established by utilizing the characteristic that C-N=C dissociation in a graphite-phase carbon nitride skeleton causes high-activity unpaired electrons on adjacent carbon atoms and triggering free radical reaction between the unpaired electrons and mercapto lone pairs on 2-mercaptobenzimidazole in the pyrolysis process. The molecular skeleton limited pyrolysis pool constructed in the process strengthens the reaction between the local graphite phase carbon nitride pyrolysis nitrogen-containing product and the carbon skeleton edge sites, effectively prolongs the residence time of reactants, improves the concentration of the local pyrolysis product in the limited pyrolysis pool, and further realizes high-efficiency nitrogen atom doping to obtain the high-nitrogen doped carbon material. The preparation method comprises the following steps:
step 1, placing 8-15 g of graphite-phase carbon nitride precursor, 0.5-2 g of 2-mercaptobenzimidazole and 50-80 g of zirconia ball-milling beads in a ball-milling tank, ball-milling for 2-3 h until the mixture is uniform, and obtaining solid powder, wherein the graphite-phase carbon nitride precursor is one of dicyandiamide, urea, thiourea or melamine;
step 2, transferring the solid powder obtained in the step 1 into a quartz boat, then placing the quartz boat into a quartz tube, and then placing the quartz tube into a tube furnace for high-temperature carbonization treatment, wherein the temperature of the quartz tube is 2-5 ℃ for min under the protection of gas -1 Heating to 800-1000 deg.c, carbonizing for 2-3 hr, cooling to room temperature to obtain high nitrogen doped carbon material, and the protecting gas is one of nitrogen, helium or argon.
The high-nitrogen doped carbon material prepared by the method is used as a counter electrode in the dye-sensitized solar cell.
The beneficial effects of the invention are as follows: a method for preparing a high-nitrogen-doped carbon material by molecular-scale finite-domain pyrolysis comprises the following steps: (1) Placing graphite-phase carbon nitride precursor, 2-mercaptobenzimidazole and zirconia ball-milling beads in a ball-milling tank for ball-milling until the graphite-phase carbon nitride precursor, the 2-mercaptobenzimidazole and the zirconia ball-milling beads are uniformly mixed to obtain solid powder; (2) Transferring the solid powder obtained in the step 1 into a quartz boat, then placing the quartz boat into a quartz tube, placing the quartz tube into a tube furnace, introducing protective gas for high-temperature carbonization treatment, and cooling to room temperature after the reaction is finished to obtain a high-nitrogen-doped carbon material; the prepared high-nitrogen doped carbon material contains the following elements: and C, N and O, wherein the atomic percentage of the nitrogen atoms is 10-15 at%. The invention provides a method for preparing a high-nitrogen-doped carbon material based on a C-S-C bonding induction finite field pyrolysis strategy, which can realize in-situ nitrogen doping of a graphite phase carbon nitride finite field in a carbon skeleton formed by polymerizing 2-mercaptobenzimidazole.
Drawings
FIG. 1 is an X-ray diffraction analysis chart of the high nitrogen-doped carbon material prepared in example 1.
Fig. 2 is a graph of photocurrent density versus voltage for the high nitrogen doped carbon material prepared in example 2 and a commercially available Pt electrode as counter electrode material for a dye-sensitized cell, respectively.
FIG. 3 is a scanning electron microscope image of the high nitrogen doped carbon material prepared in example 3.
Fig. 4 is an X-ray photoelectron spectrum of the high nitrogen doped carbon material prepared in example 4.
Fig. 5 is an X-ray photoelectron spectrum of the high nitrogen doped carbon material prepared in example 5.
Fig. 6 is a graph of photocurrent density versus voltage for the high nitrogen-doped carbon material, the three-dimensional reduced graphene oxide, and the multiwall carbon nanotubes prepared in example 6, respectively, as counter electrode materials for dye-sensitized cells.
FIG. 7 is a high-order S2 p spectrum of the reaction intermediate product prepared at different carbonization temperatures in example 7.
Detailed Description
The invention is further illustrated below with reference to examples.
Example 1
Weighing 12g dicyandiamide, 0.8g 2-mercaptobenzimidazole and 64g zirconia ball-milling beads, and placing the ball-milling beads in a ball-milling tank for ball-milling treatment for 3 hours until the mixture is uniform, thus obtaining solid powder; transferring the obtained solid powder into quartz boat, placing the quartz boat into quartz tube, placing the quartz tube into tube furnace, carbonizing at high temperature under nitrogen protection at 5deg.C for min -1 And (3) raising the temperature to 900 ℃, controlling the carbonization time to 2h, and cooling to room temperature after the reaction is finished to obtain the high-nitrogen doped carbon material. As shown in the X-ray diffraction analysis chart of FIG. 1, the prepared high-nitrogen-doped carbon material has a wide diffraction peak at about 26 degrees, and belongs to a graphite (002) crystal face, so that the high-nitrogen-doped carbon material has an amorphous structure.
Example 2
Weighing 10g of urea, 0.5g of 2-mercaptobenzimidazole and 52.5g of zirconia ball-milling beads, and placing the ball-milling beads in a ball-milling tank for ball-milling treatment for 2 hours until the mixture is uniformly mixed to obtain solid powder; transferring the obtained solid powder into quartz boat, placing the quartz boat into quartz tube, placing the quartz tube into tube furnace, carbonizing at high temperature under helium protection at 3deg.C for min -1 And (3) raising the temperature to 800 ℃, controlling the carbonization time to 3 hours, and cooling to room temperature after the reaction is finished to obtain the high-nitrogen doped carbon material. The high nitrogen doped carbon material prepared in the embodiment is used for a counter electrode of a dye-sensitized cell, 5mg of the high nitrogen doped carbon material is weighed, mixed and ground with 1mL of a binder (ethyl cellulose, ethanol and terpineol are prepared according to the mass ratio of 1:9:8), uniform slurry is obtained, the uniform slurry is smeared on FTO conductive glass by a doctor blade method, the counter electrode is obtained by drying at the high temperature of 500 ℃, and the counter electrode and a photo anode are assembled into the complete dye-sensitized cell. Pt counter electrode is commercially purchased, and 94032A type AAA-level solar simulator manufactured by Newport corporation in U.S. is adopted to test photocurrent density-voltage curve, wherein the test condition is that AM 1.5 simulates sunlight, and the illumination intensity is 100mW cm -2 The test voltage range is 0-0.8V. The photocurrent density-voltage curve chart is shown in fig. 2, the corresponding detailed photoelectric parameters are shown in table 1, and the photoelectric conversion efficiency of the high-nitrogen doped carbon material prepared by the embodiment is as high as 8.57% by adopting the high-nitrogen doped carbon material as a counter electrode, which is superior to that of a commercially available Pt counter electrode (7.78%).
TABLE 1
| Counter electrode | J sc (mA cm -2 ) | V oc (V) | FF(％) | PCE(％) |
| High nitrogen doped carbon material | 16.62 | 0.74 | 69.68 | 8.57 |
| Pt | 15.10 | 0.74 | 69.63 | 7.78 |
Example 3
Weighing 10g of melamine, 2g of 2-mercaptobenzimidazole and 60g of zirconia ball-milling beads, putting the mixture into a ball-milling tank, and ball-milling for 3 hours until the mixture is uniformly mixedObtaining solid powder; transferring the obtained solid powder into a quartz boat, placing the quartz boat into a quartz tube, placing the quartz tube into a tube furnace for high-temperature carbonization treatment, and under the protection of argon gas at 2deg.C for min -1 And (3) raising the temperature to 1000 ℃, controlling the carbonization time to 2h, and cooling to room temperature after the reaction is finished to obtain the high-nitrogen doped carbon material. As shown in a scanning electron microscope image in FIG. 3, the prepared high-nitrogen-doped carbon material has an irregular shape and presents a block stacking structure.
Example 4
Weighing 15g of dicyandiamide, 1g of 2-mercaptobenzimidazole and 80g of zirconia ball-milling beads, and placing the ball-milling beads in a ball-milling tank for ball-milling treatment for 2 hours until the mixture is uniformly mixed to obtain solid powder; transferring the obtained solid powder into a quartz boat, placing the quartz boat into a quartz tube, placing the quartz tube into a tube furnace for high-temperature carbonization treatment, and under the protection of argon gas at 5 ℃ for min -1 And (3) raising the temperature to 1000 ℃, controlling the carbonization time to 2h, and cooling to room temperature after the reaction is completed to obtain the high-nitrogen doped carbon material. As shown in FIG. 4, the high nitrogen doped carbon material has a nitrogen doping amount of up to 12.4at%.
Example 5
Weighing 14g of thiourea, 1g of 2-mercaptobenzimidazole and 75g of zirconia ball-milling beads, and placing the ball-milling beads in a ball-milling tank for ball-milling treatment for 2 hours until the mixture is uniform, so as to obtain solid powder; transferring the obtained solid powder into quartz boat, placing the quartz boat into quartz tube, placing the quartz tube into tube furnace, carbonizing at high temperature under nitrogen protection at 4deg.C for min -1 And (3) raising the temperature to 900 ℃, controlling the carbonization time to 3 hours, and cooling to room temperature after the reaction is completed to obtain the high-nitrogen doped carbon material. As shown in FIG. 5, the high nitrogen doped carbon material has a nitrogen doping amount of up to 11.3at%.
Example 6
Weighing 8g of urea, 2g of 2-mercaptobenzimidazole and 50g of zirconia ball-milling beads, and placing the ball-milling beads in a ball-milling tank for ball-milling treatment for 3 hours until the mixture is uniform, so as to obtain solid powder; transferring the obtained solid powder into quartz boat, placing the quartz boat into quartz tube, and placing the quartz tube into tubeHigh-temperature carbonization treatment is carried out in a furnace under the protection of nitrogen at 3 ℃ for min -1 And (3) raising the temperature to 900 ℃, controlling the carbonization time to 2h, and cooling to room temperature after the reaction is completed to obtain the high-nitrogen doped carbon material. The high nitrogen doped carbon material prepared in the embodiment, the three-dimensional reduced graphene oxide and the multi-wall carbon nanotube are respectively used for dyeing the counter electrode of the battery. Weighing 5mg of high-nitrogen-doped carbon material, mixing and grinding with 1mL of binder (prepared from ethyl cellulose, ethanol and terpineol according to the mass ratio of 1:9:8), obtaining uniform slurry, coating the uniform slurry on FTO conductive glass by a knife coating method, drying at a high temperature of 500 ℃ to obtain a counter electrode, and assembling the counter electrode and a photo anode into a complete dye-sensitive battery. A94032A-level AAA-level solar simulator manufactured by Newport corporation in America is adopted to test a photocurrent density-voltage curve, wherein the test condition is that AM 1.5 simulates sunlight, and the illumination intensity is 100mW cm -2 The test voltage range is 0-0.8V. The photocurrent density-voltage curve chart is shown in fig. 6, the detailed photoelectric parameters corresponding to the curve chart are shown in table 2, and the photoelectric conversion efficiency (8.38%) of the high-nitrogen doped carbon material prepared by the embodiment is higher than that of the novel all-carbon counter electrode material (three-dimensional reduced graphene oxide and multi-wall carbon nanotubes).
TABLE 2
| Counter electrode | J sc (mA cm -2 ) | V oc (V) | FF(％) | PCE(％) |
| High nitrogen doped carbon material | 15.72 | 0.75 | 71.08 | 8.38 |
| Three-dimensional reduced graphene oxide | 14.71 | 0.75 | 65.72 | 7.25 |
| Multiwall carbon nanotubes | 12.57 | 0.75 | 69.48 | 6.55 |
Example 7
In order to prove that a C-S-C induced molecular skeleton finite field pyrolysis pool is generated in the high-temperature carbonization treatment process, the reaction intermediate products at different carbonization temperatures are subjected to X-ray photoelectron spectroscopy analysis. Weighing 14g of melamine, 2g of 2-mercaptobenzimidazole and 80g of zirconia ball-milling beads, and placing the ball-milling beads in a ball-milling tank for ball-milling treatment for 2 hours until the mixture is uniform, so as to obtain solid powder; transferring the obtained solid powder into a quartz boat, placing the quartz boat into a quartz tube, placing the quartz tube into a tube furnace for high-temperature carbonization treatment, and under the protection of argon gas at 2deg.C for min -1 Heating to 550 deg.c for 2 hr, cooling to room temperature to obtain intermediate S-g-C 3 N 4 -550. Reaction intermediates at different carbonization temperatures (600 ℃,650 ℃ and 700 ℃) were prepared under the same process conditions. The high-power S2 p spectrum of the reaction intermediate product prepared at different carbonization temperatures is shown in FIG. 7, and the C-S-C bond is formed in the pyrolysis process. Moreover, with increasing temperature, the stoneMore and more C-N=C dissociation in the carbon nitride skeleton of the ink phase causes the characteristic of high-activity unpaired electrons on adjacent carbon atoms, promotes the free radical reaction between the unpaired electrons and the sulfydryl lone pair electrons on the 2-sulfydryl benzimidazole, and continuously increases the content of C-S-C bonds.
Claims (2)
1. The method for preparing the high-nitrogen-doped carbon material by molecular-scale limited-domain pyrolysis is characterized by comprising the following steps of:
step 1, placing 8-15 g of graphite-phase carbon nitride precursor, 0.5-2 g of 2-mercaptobenzimidazole and 50-80 g of zirconia ball-milling beads in a ball-milling tank, ball-milling for 2-3 h until the mixture is uniform, and obtaining solid powder, wherein the graphite-phase carbon nitride precursor is one of dicyandiamide, urea, thiourea or melamine;
step 2, transferring the solid powder obtained in the step 1 into a quartz boat, then placing the quartz boat into a quartz tube, and then placing the quartz tube into a tube furnace for high-temperature carbonization treatment, wherein the temperature of the quartz tube is 2-5 ℃ for min under the protection of gas -1 Heating to 800-1000 deg.c, carbonizing for 2-3 hr, cooling to room temperature to obtain high nitrogen doped carbon material, and the protecting gas is one of nitrogen, helium or argon.
2. The use of the high nitrogen doped carbon material prepared according to the method of claim 1 as a counter electrode in dye sensitized solar cells.
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