CN111682215B - Preparation method of nitrogen-doped yolk-shaped phenolic resin-based derivative carbon spheres - Google Patents
Preparation method of nitrogen-doped yolk-shaped phenolic resin-based derivative carbon spheres Download PDFInfo
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 24
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000004108 freeze drying Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000009656 pre-carbonization Methods 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 25
- 238000003763 carbonization Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000004005 microsphere Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 6
- 239000008098 formaldehyde solution Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 3
- 238000010000 carbonizing Methods 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000009210 therapy by ultrasound Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 35
- 239000011258 core-shell material Substances 0.000 description 6
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 5
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002717 carbon nanostructure Substances 0.000 description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a preparation method of nitrogen-doped yolk-shaped phenolic resin-based derivative carbon spheres. The preparation method comprises the following steps: the deionized water and the absolute ethyl alcohol are evenly treated by ultrasonic treatment, 1/3 solution is taken and poured into a 500ml three-mouth bottle, ammonia water is added, the rest solution is poured into a 250ml three-mouth bottle, and the two three-mouth bottles are all placed into a cold bath and stirred. Adding 1.0-3.0 g of resorcinol into a big three-necked bottle, and stirring for dissolving. The melamine and the formaldehyde are stirred and dissolved in water bath and then added into a small three-mouth bottle. After stirring for a period of time, the solutions in the three-necked flask were mixed and formaldehyde was added and stirred for 24 h. And (4) centrifugally washing the product, freeze-drying the product, and carrying out low-temperature pre-carbonization treatment. And then weighing 0.2g of product, activating and carbonizing the product with KOH, then acid-washing the carbonized product, removing residual KOH and salts generated in the high-temperature heat treatment process, and then centrifugally washing to neutrality to obtain the nitrogen-doped yolk-shaped phenolic resin-based derivative carbon spheres. The nitrogen-doped yolk-shaped phenolic resin-based derivative carbon spheres prepared by the method have unique appearance, uniform size and simple and easy experimental process, and the electrochemical performance is stably improved again after nitrogen atom doping.
Description
Technical Field
The invention belongs to the technical field of new energy electronic materials, and relates to a preparation method of nitrogen-doped yolk-shaped phenolic resin-based derivative carbon spheres.
Background
In the world of today, with the rapid development of social economy, the problem of environmental deterioration is increasingly highlighted. The lithium-sulfur battery is considered as one of the most application-promising energy storage systems of the next generation, uses sulfur simple substance with rich storage capacity, no toxicity, low cost and environmental friendliness as a positive active material, and has the theoretical specific capacity of 1675 mAh g-1And has 2600 Wh kg-1High energy density. However, sulfur and lithium sulfide are poor in conductivity, and during the electrochemical reaction, polysulfide (Li) is an intermediate product2SnN is more than or equal to 4 and less than or equal to 8) is easily dissolved in the electrolyte to generate shuttle effect, so thatThe multiplying power and the cycle stability are reduced. Therefore, the novel lithium-sulfur battery anode material is prepared through reasonable structural design, and is a research focus for improving the electrochemical performance of the batteries. The carbon spheres with hollow or core-shell structures have high specific surface area, large pore size, good structural stability and excellent electrical conductivity, so that the carbon spheres are not only beneficial to the storage and transfer of electrolyte ions in energy storage application, but also have good cycling stability, and are always the research hotspots of people for decades. It is also desirable to apply such a structure to the positive electrode of a lithium sulfur battery to avoid the shuttling effect and to improve the cycle stability of the lithium sulfur battery. The phenolic resin is a resin generated by condensation reaction of phenols and aldehydes under the catalysis of a catalyst. The resin is easy to synthesize, the structure is easy to regulate, and the thermal expansion coefficient is low in the carbonization process, so that the resin is a good precursor for preparing hollow or core-shell structure carbon spheres. For example, using formaldehyde and resorcinol as monomers, Tetraethoxysilane (TEOS) as a hard mask precursor, and cetyltrimethylammonium chloride (CTAC) as a soft mask, Qiao Z A, Guo B, Binder A J, et al, Controlled synthesis of mesoporous carbon spheres of meso-porous carbon nano-structure of "silicon-assisted" strategy [ J ] with controllable diameter between 180nm and 850nm was synthesized by Qiao et al]Nano Letters, 2013, 13 (1): 207-212.). Fang et al first synthesized SiO with TEOS of about 200 nm in size2The microspheres are prepared by polymerizing Resorcinol and Formaldehyde at low concentration by using Cetyl Trimethyl Ammonium Bromide (CTAB) as cationic surfactant, carbonizing, and etching to obtain phenolic Resin-based Carbon spheres (Fang X, Liu S, Zang J, et al. Precisely Controlled Resin in Coating for manufacturing Core-Shell, Hollow, and Yolk-Shell Carbon Nanostructures [ J ] with Core-Shell structure]Nanoscale, 2013, 5(15). However, in terms of current research, though the phenolic resin carbon spheres with yolk-shaped or core-shell-shaped structures have certain structural advantages in the aspect of energy storage, the preparation process is long and complicated, the problems that hard templates are difficult to completely remove and the like exist, and the preparation process is to be further improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a brand-new method for preparing nitrogen-doped yolk-shaped phenolic resin derived carbon spheres by a template-free method.
The technical scheme of the invention is as follows:
according to the invention, the preparation method of the nitrogen-doped yolk-shaped phenolic resin-based derivative carbon spheres comprises the following steps:
(1) 160ml of deionized water and a certain amount of absolute ethyl alcohol are subjected to ultrasonic homogenization, 1/3 is poured into a 500ml three-necked bottle, 0.5-1.0 ml of ammonia water is added, and the rest solution is poured into a 250ml three-necked bottle. Placing the three-mouth bottles at-10 to 0oC, under the condition of cold bath;
(2) adding 1.0-3.0 g of resorcinol into the 500ml volumetric flask in the step (1), and stirring for about 30min until the resorcinol is dissolved. Simultaneously, 2.0g of melamine and a certain amount of formaldehyde were weighed into a beaker, 60oC, stirring in a water bath for 10-30 min;
(3) pouring the liquid in the beaker in the step (2) into a 250ml three-necked bottle, and stirring for 10 min;
(4) pouring the 250ml of solution in the three-necked bottle in the step (3) into a 500ml three-necked bottle, stirring for several minutes, adding 0-5.0 ml of formaldehyde solution into the three-necked bottle, and stirring for 24 hours;
(5) alternately washing the product obtained in the step (4) with deionized water and absolute ethyl alcohol for 4 times respectively, and freeze-drying the product to obtain a phenolic resin-based hollow sphere;
(6) and (6) placing the product obtained in the step (5) in a crucible to carry out pre-carbonization in a tube furnace. The conditions are as follows: argon atmosphere 300-500oC, the heating rate is 1-3oC min-1Keeping the temperature for 1-3 h to obtain a carbonized product which is dark orange powder;
(7) weighing 0.2g of the pre-carbonized product obtained in the step (6), uniformly dispersing the pre-carbonized product in 100ml of deionized water, weighing 0.2-0.6 g of KOH, dissolving the KOH in 50ml of deionized water, and mechanically blending the two solutions for 1 hour;
(8) freeze-drying the mixed solution obtained in the step (7), and then putting the dried product into the containerAnd (5) placing the mixture in a tubular furnace for high-temperature carbonization treatment. The conditions are as follows: argon atmosphere 600-800oC, the heating rate is 2-5oC min-1Keeping the temperature for 1-3 h to obtain black carbonized powder;
(9) the carbonized product in the step (8) is added in 0.1mol L-1And (4) pickling in a hydrochloric acid solution for 6 hours, centrifuging and washing the product for several times to be neutral, and completely drying in an air-blast drying oven.
According to the invention, preferably, the absolute ethyl alcohol in the step (1) is 60ml, and the ammonia water is 0.8 ml.
According to the present invention, it is preferable that the cooling bath temperature in the step (1) is 0oC。
According to the present invention, it is preferred that the amount of formaldehyde used in step (2) is 4.5238 g.
According to the present invention, it is preferred that the stirring time in step (2) is 25 min.
According to the present invention, it is preferred that the stirring time in step (4) is 10 min.
According to the invention, it is preferred that the amount of formaldehyde used in step (4) is 2.5 ml.
According to the present invention, it is preferable that the carbonization temperature in the step (6) is 300oC, rate of temperature rise 1oC min-1。
According to the present invention, it is preferred that the incubation time in step (6) is 1 hour.
According to the invention, it is preferred that KOH in step (7) is used in an amount of 0.6 g.
According to the present invention, it is preferable that the carbonization temperature in step (8) is 750oC。
According to the invention, the incubation time in step (8) is preferably 1 h.
The technical advantages of the invention are as follows:
(1) the preparation method is simple and convenient in preparation process and controllable, soft and hard templates are not used in the preparation process, and the phenolic resin-based derivative carbon spheres with the core-shell structure can be obtained without a subsequent treatment process.
(2) The nitrogen-doped yolk-shaped phenolic resin-based derivative carbon spheres are used as a conductive carrier of the active substance sulfur, so that a high specific capacity value can be obtained, and the cycle stability and the rate capability are improved to a great extent.
(3) The phenolic resin-based derivative carbon spheres prepared by the invention are doped with nitrogen atoms, and experimental exploration shows that the electrochemical performance of the electrode material of the lithium-sulfur battery is improved to a greater extent after the nitrogen atoms are doped.
Drawings
FIG. 1 is a transmission electron microscope image of yolk-shaped nitrogen-doped phenolic resin microspheres prepared in example 1 of the present invention after freeze drying.
FIG. 2 is a scanning electron microscope image of the yolk-shaped nitrogen-doped phenolic resin microspheres prepared in example 2 of the present invention after freeze-drying.
Detailed Description
The invention is further described below, but not limited thereto, with reference to the following specific examples and the accompanying drawings.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
Ultrasonic treating 160ml deionized water and 60ml anhydrous alcohol to obtain uniform mixed solution, pouring 1/3 solution into 500ml three-necked bottle, adding 0.8ml ammonia water, pouring the rest solution into 250ml three-necked bottle, placing 0 into both three-necked bottlesoC, stirring in a cold bath. To a 500ml three-necked flask, 1.8g of resorcinol was added and dissolved with stirring. Another 50ml beaker was taken, 2g melamine and 4.5238g formaldehyde were added to it, 60 g was put inoC, stirring in a water bath until the solution is clear, and adding the solution into a three-necked bottle to continue stirring. After 10min, the solution in the 250ml three-necked flask was slowly poured into the 500ml three-necked flask, 2.5ml of formaldehyde solution was added dropwise, and stirred for 24 h. The product was washed with deionized water and absolute ethanol alternately 4 times, after which the product was freeze-dried. After the drying is finished, putting the obtained product into a tubular furnace for pre-carbonization, wherein the carbonization temperature is 300 DEGoC, keeping the temperature for 1 h. 0.2g of the product was weighed out and uniformly dispersed in 100ml of deionized water,at the same time, 0.2g KOH was weighed again and dissolved in 50ml deionized water, mechanically stirred for 1 hour and then freeze-dried. Putting the dried product into a tubular furnace for high-temperature carbonization treatment at the carbonization temperature of 750 DEG CoC, keeping the temperature for 1 h. After heat treatment, the product was washed with 0.1mol L-1And (4) pickling for 6 hours in a hydrochloric acid solution, centrifugally washing the product for several times until the product is neutral, and completely drying the product in an air-blast drying oven.
Example 2
Ultrasonic treating 160ml deionized water and 60ml anhydrous alcohol to obtain uniform mixed solution, pouring 1/3 solution into 500ml three-necked bottle, adding 0.8ml ammonia water, pouring the rest solution into 250ml three-necked bottle, placing 0 into both three-necked bottlesoC, stirring in a cold bath. To a 500ml three-necked flask, 1.8g of resorcinol was added and dissolved with stirring. Another 50ml beaker was taken, 2g of melamine and 4.5238g of formaldehyde were added thereto, and 60 g of formaldehyde was placed in the beakeroC, stirring in a water bath until the solution is clear, and adding the solution into a three-necked bottle to continue stirring. After 10min, the solution in the 250ml three-necked flask was slowly poured into the 500ml three-necked flask, 2.5ml of formaldehyde solution was added dropwise, and stirred for 24 h. The product was washed with deionized water and absolute ethanol alternately 4 times, after which the product was freeze-dried. After the drying is finished, putting the obtained product into a tubular furnace for pre-carbonization, wherein the carbonization temperature is 300 DEGoC, keeping the temperature for 1 h. 0.2g of the product was weighed out and homogeneously dispersed in 100ml of deionized water, while 0.4g of KOH was weighed out and dissolved in 50ml of deionized water, mechanically stirred for 1h and then freeze-dried. Putting the dried product into a tube furnace for high-temperature carbonization treatment at the carbonization temperature of 750 DEG CoC, keeping the temperature for 1 h. After heat treatment, the product was kept at 0.1mol L-1And (4) pickling for 6 hours in a hydrochloric acid solution, centrifugally washing the product for several times until the product is neutral, and completely drying the product in an air-blast drying oven.
Example 3
Ultrasonically treating 160ml deionized water and 60ml absolute ethyl alcohol to obtain uniform mixed solution, pouring 1/3 solution into 500ml three-neck flask, adding 0.8ml ammonia water, pouring the rest solution into 250ml three-neck flask, putting two three-neck flasks into 0oC, stirring in a cold bath. To a 500ml three-necked flask, 1.8g of resorcinol was added and dissolved with stirring. Another 50ml beaker was taken and 2g of melamine and 4.5238g of melamine were added to itFormaldehyde, adding 60oC, stirring in a water bath until the solution is clear, and adding the solution into a three-necked bottle to continue stirring. After 10min, the solution in the 250ml three-necked flask was slowly poured into the 500ml three-necked flask, 2.5ml of formaldehyde solution was added dropwise, and stirred for 24 h. The product was washed with deionized water and absolute ethanol alternately 4 times, after which the product was freeze-dried. After the drying is finished, putting the obtained product into a tubular furnace for pre-carbonization, wherein the carbonization temperature is 300 DEGoC, keeping the temperature for 1 h. 0.2g of the product was weighed out and homogeneously dispersed in 100ml of deionized water, while 0.6g of KOH was weighed out and dissolved in 50ml of deionized water, mechanically stirred for 1h and then freeze-dried. Putting the dried product into a tubular furnace for high-temperature carbonization treatment at the carbonization temperature of 750 DEG CoC, keeping the temperature for 1 h. After heat treatment, the product was washed with 0.1mol L-1And (4) pickling for 6 hours in a hydrochloric acid solution, centrifugally washing the product for several times to be neutral, and completely drying the product in an air-blast drying oven.
The transmission electron microscope image of the yolk-shaped nitrogen-doped phenolic resin microspheres prepared in the embodiment after freeze drying is shown in fig. 1, and the formation of the nitrogen-doped yolk-shaped phenolic resin microspheres can be seen from fig. 1, and the yolk-shaped nitrogen-doped phenolic resin microspheres have obvious core-shell structures.
Fig. 2 shows a scanning electron micrograph of the yolk-shaped nitrogen-doped phenolic resin microspheres prepared in this example after freeze drying, and it can be seen from fig. 2 that the nitrogen-doped yolk-shaped phenolic resin microspheres have uniform size and surface micropores and mesopores coexist.
Claims (1)
1. A preparation method of nitrogen-doped yolk-shaped phenolic resin-based derivative carbon spheres is characterized in that,
(1) ultrasonically mixing 160ml of deionized water and 60ml of absolute ethyl alcohol uniformly, pouring 1/3 into a 500ml three-necked bottle, adding 0.8ml of ammonia water, pouring the rest solution into a 250ml three-necked bottle, and placing the three-necked bottle under the condition of 0 ℃ cold bath;
(2) adding 1.8g of resorcinol into the 500ml volumetric flask in the step (1), stirring for about 30min until the resorcinol is dissolved, simultaneously weighing 2.0g of melamine and 4.5238g of formaldehyde into a beaker, and stirring for 25min in a water bath at 60 ℃;
(3) pouring the liquid in the beaker in the step (2) into a 250ml three-necked bottle, and stirring for 10 min;
(4) pouring the solution in the 250ml three-necked bottle in the step (3) into a 500ml three-necked bottle, stirring for 10min, adding 2.5ml of formaldehyde solution, and stirring for 24 h;
(5) alternately washing the product obtained in the step (4) with deionized water and absolute ethyl alcohol for 4 times respectively, and freeze-drying the product to obtain the yolk-shaped phenolic resin-based microspheres;
(6) placing the product obtained in the step (5) in a crucible to carry out pre-carbonization in a tube furnace, wherein the conditions are as follows: argon atmosphere 300 ℃, heating rate 1 ℃ for min-1Keeping the temperature for 1h to obtain a carbonized product which is dark orange powder;
(7) weighing 0.2g of the powder obtained in the step (6), uniformly dispersing the powder in 100ml of deionized water, meanwhile weighing 0.6g of KOH, dissolving the KOH in 50ml of deionized water, and mechanically stirring for 1 hour;
(8) and (5) freeze-drying the mixed solution obtained in the step (7), and placing the dried product in a tubular furnace for high-temperature carbonization treatment under the conditions that: argon atmosphere is 750 ℃, and the heating rate is 2-5 ℃ for min-1Keeping the temperature for 1h to obtain black carbonized powder;
(9) the carbonized product obtained in the step (8) is added in 0.1mol L-1And (4) pickling for 6 hours in a hydrochloric acid solution, centrifugally washing the product for several times to be neutral, and completely drying the product in an air-blast drying oven.
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