CN112086636B - Nitrogen-sulfur co-doped three-dimensional honeycomb carbon and preparation method and application thereof - Google Patents
Nitrogen-sulfur co-doped three-dimensional honeycomb carbon and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of new energy, and discloses nitrogen and sulfur co-doped three-dimensional honeycomb carbon and a preparation method and application thereof. The nitrogen and sulfur co-doped three-dimensional honeycomb carbon is prepared by immersing pretreated cicada wings in a coating solution, sucking off redundant solution by using filter paper, and reacting at 100-300 ℃; treating the obtained sample in concentrated sulfuric acid at 60-200 ℃, then cleaning the sample to be neutral by using deionized water, and carrying out carbonization treatment at 600-1600 ℃ under the protection of inert gas to obtain the product; the coating solution is prepared by adding water-soluble phenolic resin and thiourea into dimethyl sulfoxide. The nitrogen and sulfur co-doped three-dimensional honeycomb carbon has a regularly arranged honeycomb structure and graphitization of the surface layer, can accelerate the transportation of sodium ions/lithium ions, and improves the first coulombic efficiency of the battery, so that the high-capacity sodium ions/lithium ion battery cathode material is obtained.
Description
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to nitrogen and sulfur co-doped three-dimensional honeycomb carbon and a preparation method and application thereof.
Background
In nature, many organisms have a wide variety of excellent surface properties, since they achieve a nearly perfect micro/nano structured surface layer under conditions adapted for environmental survival. These ideal surfaces naturally also become an ideal source of innovation for new materials and structures. Such as the ability of nepenthes to continuously deliver water on surfaces, the anti-fog properties of mosquito eyes, the self-cleaning properties of lotus leaves and the water-fixing properties on rose petals. Research on how to replicate these structures into new functional surfaces has been the leading edge of research in micro-nano fabrication technology. Therefore, the artificial micro/nano structure has a very wide application prospect, such as an observation system, a new energy battery, an anti-fog film, liquid drop transmission and other promising applications.
Cicadas, one of the typical organisms in the field of bionics, have some distinct characteristics, such as hydrophobicity, light trapping and sterilization. The invention takes the functional surface of the conical micro/nano structure of the cicada wing as inspiration and constructs a three-dimensional carbon material with a layered structure through some artificial structural designs. The material is applied to a sodium ion battery to obtain the sodium ion battery cathode material with excellent performance.
Compared with the traditional electrode material, the biological material has inherent advantages in structure and performance. For example, the cicada wing has a conical micro/nano structure surface with super-hydrophobic property. Such natural ordered array structures are difficult to synthesize using chemical methods.
Disclosure of Invention
In order to solve the defects of the prior art, the nitrogen and sulfur co-doped three-dimensional honeycomb carbon is provided.
The invention also aims to provide a preparation method of the nitrogen-sulfur co-doped three-dimensional honeycomb carbon. According to the method, cicada wings are used as templates, water-soluble phenolic resin is used for coating, N, S heteroatom is used for doping, and then the cicada wings are directly carbonized at high temperature to prepare the nitrogen and sulfur co-doped three-dimensional honeycomb carbon.
The invention further aims to provide application of the nitrogen and sulfur co-doped three-dimensional honeycomb carbon.
The purpose of the invention is realized by the following technical scheme:
the nitrogen-sulfur co-doped three-dimensional honeycomb carbon is prepared by immersing pretreated cicada wings in a coating solution, sucking off redundant solution by using filter paper, and reacting at 100-300 ℃; treating the obtained sample in concentrated sulfuric acid at 60-200 ℃, cleaning the sample to be neutral by using deionized water, and carbonizing the sample at 600-1600 ℃ in a protective atmosphere to obtain the product; the coating solution is prepared by adding water-soluble phenolic resin and thiourea into dimethyl sulfoxide.
Preferably, the usage ratio of the water-soluble phenolic resin, the thiourea and the dimethyl sulfoxide is (1-3) g: (2-10) g: (5-50) mL.
Preferably, the reaction time at 100-300 ℃ is 1-48 h.
Preferably, the treatment time at 60-200 ℃ is 1-12 h.
Preferably, the carbonization time is 2-12 h.
Preferably, the protective atmosphere is nitrogen or argon.
The preparation method of the nitrogen and sulfur co-doped three-dimensional honeycomb carbon comprises the following specific steps:
s1, ultrasonically cleaning cicada wing with deionized water and absolute ethyl alcohol, and drying at 40-150 ℃ to obtain pretreated cicada wing;
s2, adding water-soluble phenolic resin and thiourea into dimethyl sulfoxide, stirring to dissolve the water-soluble phenolic resin and the thiourea uniformly, and preparing a coating solution;
s3, immersing the pretreated cicada wing in a coating solution, sucking off redundant solution by using filter paper, and reacting at 100-300 ℃; and (3) treating the obtained sample in concentrated sulfuric acid at 60-200 ℃, cleaning the sample to be neutral by using deionized water, and carbonizing the sample at 600-1600 ℃ under a protective atmosphere to obtain the nitrogen-sulfur co-doped three-dimensional honeycomb carbon.
An electrode material is prepared by adding N-methyl pyrrolidone into nitrogen and sulfur co-doped three-dimensional honeycomb carbon, conductive carbon black and PVDF to prepare slurry and coating the slurry on copper foil.
Preferably, the nitrogen and sulfur co-doped three-dimensional honeycomb carbon has a mass ratio of conductive carbon black to PVDF (6-8): (1-3): 1.
the electrode material is applied to a sodium ion battery or a lithium battery.
The invention takes cicada's wings as a template, and water-soluble phenolic resin dissolved by dimethyl sulfoxide (DMSO) is coated on the cicada's wings. And heating to volatilize the DMSO, thus obtaining the cicada wing coated with the phenolic resin. And washing the cicada wing by using concentrated sulfuric acid, and carbonizing at high temperature to obtain the nitrogen-sulfur co-doped three-dimensional honeycomb carbon.
Compared with the prior art, the invention has the following beneficial effects:
1. the nitrogen-sulfur co-doped three-dimensional honeycomb carbon has a regularly arranged honeycomb structure and graphitization of the surface layer, and can accelerate the transportation of sodium/lithium ions, so that the first coulomb efficiency of a battery is improved.
2. The cicada wing surface layer ordered structure can be obtained by taking the cicada wing as a template as a basic framework; and the surface layer of the biological material can be graphitized after high-temperature treatment by the optimized design. The cicada wing special material is explored in the field of new energy, and meanwhile, reference is provided for designing a carbon electrode by taking a biomass material as a raw material.
Drawings
Fig. 1 is a scanning electron microscope image of nitrogen and sulfur co-doped three-dimensional honeycomb carbon in example 1.
Fig. 2 is a nitrogen adsorption/desorption graph of the nitrogen and sulfur co-doped three-dimensional honeycomb carbon in example 1.
Fig. 3 is a pore size distribution diagram of the nitrogen and sulfur co-doped three-dimensional honeycomb carbon in example 1.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
1. And ultrasonically cleaning the cut cicada wing by using deionized water and absolute ethyl alcohol for three times, drying in an oven at 60 ℃, then respectively cutting off dark black parts at the edges of all the cicada wings, and placing in a sealing bag for later use.
2. 1g of water-soluble phenolic resin and 3g of thiourea were put in a beaker, 10mL of DMSO was added, and the mixture was stirred to dissolve the mixture uniformly to prepare a mixed solution.
3. And (3) soaking the cicada wing treated in the step (1) in the mixed solution for coating, then placing the cicada wing on filter paper to absorb redundant solution, uniformly placing the coated cicada wing on the toothpick, and reacting in an oven at 200 ℃ for 24 hours.
4. And (3) treating the reacted sample with concentrated sulfuric acid at 80 ℃ for 3h, repeatedly performing suction filtration, washing with deionized water to be neutral, and finally carbonizing at a high temperature of 600 ℃ to obtain the nitrogen-sulfur co-doped three-dimensional honeycomb carbon.
And co-doping the obtained nitrogen and sulfur with three-dimensional honeycomb carbon, wherein the conductive carbon black and PVDF are mixed according to a mass ratio of 8: 1: 1, uniformly mixing and grinding, dropwise adding a proper amount of N-methyl pyrrolidone to prepare slurry, uniformly mixing, coating on a copper foil, drying in vacuum at 60 ℃ for 12 hours, and rolling to obtain the nitrogen-sulfur co-doped three-dimensional honeycomb carbon electrode plate. Punching the prepared nitrogen and sulfur co-doped three-dimensional honeycomb carbon electrode plate
Of wafers of
Metal sodium sheet as counter electrode, glass fiber as diaphragm, 1mol/L NaPF6The electrolyte solution is DMC + EMC + EC (volume ratio is 1: 1: 1), and the button cell is assembled in a glove box filled with argon. A battery testing system (CT2001A) is adopted to test the battery, and the charging and discharging voltage range is 0.01-3V. 200mA g-1The first charging specific capacity of charging and discharging is 243mAh g-1Specific discharge capacity of 468mAh g-1The charge-discharge efficiency is 52%; 1000mA g-1Specific capacity of first discharge under the condition of 318mAh g-1。
FIG. 1 is a scanning electron micrograph of nitrogen and sulfur co-doped three-dimensional honeycomb carbon in example 1, wherein a and b are 10% -N, S-800 ℃ scanning electron micrographs, c and d are 10% -N, S-1000 ℃ scanning electron micrographs, e and f are 10% -N, S-1300 ℃ scanning electron micrographs, and g and h are scanning electron micrographs of cicada wings. As can be seen from fig. 1, the honeycomb structure of the cicada wing is obtained by successful preparation; fig. 2 is a nitrogen adsorption/desorption graph of the nitrogen and sulfur co-doped three-dimensional honeycomb carbon in example 1. As can be seen from FIG. 2, at 600-1000 ℃, the specific surface area of the nitrogen-sulfur co-doped three-dimensional honeycomb carbon is reduced along with the temperature rise; the material has resilience at 1300 ℃, which shows that the carbon shrinks along with the rise of the temperature at the temperature of over 1000 ℃, thereby causing the specific surface area of the material to increase and generating resilience; this can also be seen in fig. 1, e. Fig. 3 is a pore size distribution diagram of the nitrogen and sulfur co-doped three-dimensional honeycomb carbon in example 1. As can be seen from fig. 3, as the temperature rises, the medium and large pore structures in the nitrogen and sulfur co-doped three-dimensional honeycomb carbon gradually increase.
Example 2
Table 1 shows the values at 200mA g-1Influence of the carbonization temperature on the electrochemical performance of the electrode material under the constant current charging and discharging conditions. The difference from example 1 is that the carbonization temperature was different. As can be seen from table 1, as the carbonization temperature increases, it is helpful to improve the first charge and discharge specific capacity and efficiency value of the battery.
TABLE 1 influence of carbonization temperature on electrochemical properties of electrode materials
Example 3
Table 2 shows the values at 200mA g-1Under the condition of constant current charge and discharge, N and S atom doping influences the electrochemical performance of the material. Unlike example 2, no thiourea doping was used. It can be seen from table 2 that the first charge/discharge specific capacity of the battery is reduced without doping nitrogen and sulfur elements.
TABLE 2 influence of N, S atom doping on the electrochemical behavior of electrode materials
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The nitrogen-sulfur co-doped three-dimensional honeycomb carbon is characterized in that the nitrogen-sulfur co-doped three-dimensional honeycomb carbon is prepared by taking cicada wings, ultrasonically cleaning the cicada wings with deionized water and absolute ethyl alcohol, drying the cicada wings at 40-150 ℃ to obtain pretreated cicada wings, soaking the pretreated cicada wings in a coating solution, sucking off the redundant solution with filter paper, and reacting at 100-300 ℃; treating the obtained sample in concentrated sulfuric acid at 60-200 ℃, cleaning the sample to be neutral by using deionized water, and carbonizing the sample at 600-1600 ℃ in a protective atmosphere to obtain the product; the coating solution is prepared by adding water-soluble phenolic resin and thiourea into dimethyl sulfoxide.
2. The nitrogen-sulfur co-doped three-dimensional honeycomb carbon according to claim 1, wherein the water-soluble phenolic resin, thiourea and dimethyl sulfoxide are used in an amount of (1-3) g: (2-10) g: (5-50) mL.
3. The nitrogen and sulfur co-doped three-dimensional honeycomb carbon according to claim 1, wherein the reaction time at 100-300 ℃ is 1-48 h.
4. The nitrogen-sulfur co-doped three-dimensional honeycomb carbon according to claim 1, wherein the treatment time at 60-200 ℃ is 1-12 h.
5. The nitrogen-sulfur co-doped three-dimensional honeycomb carbon according to claim 1, wherein the carbonization time is 2-12 h.
6. The nitrogen and sulfur co-doped three-dimensional honeycomb carbon according to claim 1, wherein the protective atmosphere is nitrogen or argon.
7. The preparation method of nitrogen and sulfur co-doped three-dimensional honeycomb carbon according to any one of claims 1 to 6, comprising the following specific steps:
s1, ultrasonically cleaning cicada wing with deionized water and absolute ethyl alcohol, and drying at 40-150 ℃ to obtain pretreated cicada wing;
s2, adding water-soluble phenolic resin and thiourea into dimethyl sulfoxide, stirring to dissolve the water-soluble phenolic resin and the thiourea uniformly, and preparing a coating solution;
s3, immersing the pretreated cicada wing in a coating solution, sucking off redundant solution by using filter paper, and reacting at 100-300 ℃; and (3) treating the obtained sample in concentrated sulfuric acid at 60-200 ℃, cleaning the sample to be neutral by using deionized water, and carbonizing the sample at 600-1600 ℃ under a protective atmosphere to obtain the nitrogen-sulfur co-doped three-dimensional honeycomb carbon.
8. An electrode material, which is prepared by adding N-methyl pyrrolidone into nitrogen and sulfur co-doped three-dimensional honeycomb carbon of any one of claims 1 to 6, conductive carbon black and PVDF to prepare slurry and coating the slurry on a copper foil.
9. The electrode material according to claim 8, wherein the nitrogen and sulfur co-doped three-dimensional honeycomb carbon is prepared by mixing (6-8) conductive carbon black and PVDF in a mass ratio of: (1-3): 1.
10. use of the electrode material of claim 8 or 9 in a sodium ion battery or a lithium battery.
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| CN106505213A (en) * | 2016-10-31 | 2017-03-15 | 天津理工大学 | A kind of method that graphene-based elctro-catalyst is prepared with insect wing |
| CN106505217A (en) * | 2016-10-31 | 2017-03-15 | 天津理工大学 | A kind of method that carbon-based elctro-catalyst is prepared with insect wing |
| CN107706403A (en) * | 2017-11-20 | 2018-02-16 | 中国科学院过程工程研究所 | A kind of complex carbon material and the modified electrode material and lithium ion battery using its preparation |
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| US7794880B2 (en) * | 2005-11-16 | 2010-09-14 | California Institute Of Technology | Fluorination of multi-layered carbon nanomaterials |
| CN106848332A (en) * | 2017-02-17 | 2017-06-13 | 天津理工大学 | A kind of method for preparing efficient oxygen reduction catalyst as substrate with insect wing |
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| CN106505213A (en) * | 2016-10-31 | 2017-03-15 | 天津理工大学 | A kind of method that graphene-based elctro-catalyst is prepared with insect wing |
| CN106505217A (en) * | 2016-10-31 | 2017-03-15 | 天津理工大学 | A kind of method that carbon-based elctro-catalyst is prepared with insect wing |
| CN107706403A (en) * | 2017-11-20 | 2018-02-16 | 中国科学院过程工程研究所 | A kind of complex carbon material and the modified electrode material and lithium ion battery using its preparation |
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| Few-layer MoS2 embedded in N-doped carbon fibers with interconnected macropores for ultrafast sodium storage;Ao Cheng，et al.;《Carbon》;20200706;第691-700页 * |
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