CN109037678B - Preparation method of nitrogen and sulfur co-doped three-dimensional graphene foam electrode active material - Google Patents
Preparation method of nitrogen and sulfur co-doped three-dimensional graphene foam electrode active material Download PDFInfo
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a preparation method of a nitrogen and sulfur co-doped three-dimensional graphene foam electrode material, which comprises the following steps: soaking foamed nickel in dispersion liquid containing graphene oxide, melamine, trithiocyanuric acid and sufficient solvent, and carrying out solvothermal reaction; carrying out heat treatment on the solvothermal reaction product at 500-1200 ℃ under inert atmosphere; and etching the foamed nickel in the heat treatment product through strong acid to obtain the nitrogen-sulfur co-doped three-dimensional graphene foam. The nitrogen and sulfur co-doped three-dimensional graphene foam electrode material prepared based on the method has three-dimensional doped graphene foam and doped nitrogen and sulfur elements; the content of doped nitrogen element is 3-7%, the content of sulfur element is 1-3%, the content of oxygen is 4-12%, and the doping amount is controllable. The experimental method is safe and nontoxic, low in cost and simple and convenient to operate. The prepared doped three-dimensional doped graphene foam electrode can be applied to the fields of lithium ion batteries, supercapacitors, electrocatalysis and the like, and has wide application prospects.
Description
Technical Field
The invention relates to the technical field of graphene electrode materials, in particular to a preparation method of a nitrogen and sulfur co-doped three-dimensional graphene foam electrode material.
Background
Graphene is known as a two-dimensional crystal with a perfect structure, a thickness of a single atomic layer consisting of carbon atoms. However, the practical application of graphene in various fields is limited by the problems that graphene lacks an inherent band gap and is easily stacked again in experiments. Research shows that hetero-atom doping can effectively open the band gap of graphene, so that the physical, chemical and electrical properties are obviously improved. In addition, the problem of easy stacking of the graphene structure can be solved by three-dimensionally regulating the graphene structure. Common methods for doping graphene are CVD, ball milling, plasma, arc discharge, wet chemical, and heat treatment. In contrast, the wet chemistry method is widely used because it occupies the advantages of simple experimental conditions and it can realize a three-dimensional gel carbon network.
In the energy source direction of lithium ion batteries, sodium ion batteries and the like, doped graphene has excellent electrochemical properties and has been widely researched as an electrode material, for example, a high-density nitrogen-doped graphene and a preparation method thereof are disclosed in the patent with the application publication number of CN 105565306A. The method reports that nitrogen-doped graphene is prepared from graphene oxide and a nitrogen source by a hydrothermal method and applied to a lithium battery, and the specific capacity of the material is improved compared with that of the graphene. Although the specific capacity of the material can be obviously improved by using the two-dimensional doped graphene as the electrode material, a great promotion space still exists in the aspect of dynamics. Many researches show that the three-dimensional structure has a through cross-linked structure, so that the diffusion path of lithium ions or sodium ions can be effectively shortened, and the kinetics of electrochemical reaction is improved.
Disclosure of Invention
The invention aims to provide a preparation method of a nitrogen and sulfur co-doped three-dimensional graphene foam electrode material, which is simple to operate, safe and nontoxic. The product has large specific surface area and has the advantages of simultaneously realizing doping and constructing a three-dimensional structure. The carbon-supported lithium-sulfur or lithium-selenium battery anode can be applied to energy sources such as lithium ion batteries and sodium ion batteries, and can be used as a carbon carrier to load sulfur or selenium for the lithium-sulfur or lithium-selenium battery anode. The electrode prepared by the method can be applied to the fields of lithium ion batteries and sodium ion batteries, and can be used as a carbon carrier to load sulfur or selenium for the positive electrode of a lithium sulfur or lithium selenium battery.
The specific technical scheme is as follows: a preparation method of a nitrogen and sulfur co-doped three-dimensional graphene foam electrode material comprises the following steps:
(1) and dispersing graphene oxide in a mixed solvent of deionized water and ethanol to obtain a graphene oxide dispersion solution, then sequentially adding melamine and trithiocyanuric acid, and uniformly stirring.
(2) And (3) directly cutting the foamed nickel into 30 x 60mm, immersing the foamed nickel into the liquid in the step (1), and then putting the foamed nickel into a 100ml polytetrafluoroethylene reaction kettle for hydrothermal reaction.
(3) After the hydrothermal reaction is finished, the product is freeze-dried and finally is subjected to heat treatment in a tube furnace under the protection of argon.
(4) After the heat treatment was completed, the product was placed in 5% dilute hydrochloric acid, and the nickel foam was etched away. And drying the sample after multiple times of centrifugal washing to obtain the nitrogen and sulfur co-doped three-dimensional graphene foam.
The specific mass ratio of the graphene oxide to the melamine trithiocyanuric acid is 1: 0.2-2: 0.2-2.5. The volume ratio of the mixed solvent deionized water to the ethanol is 1-7: 1.
The thickness of the foamed nickel is 0.5-2 mm.
In the hydrothermal reaction, the hydrothermal reaction time is 4-36 h, and the hydrothermal temperature is 100-200 ℃.
In the heat treatment, the heating rate is 2-20 ℃/min, the heat treatment temperature is 500-1200 ℃, and the time is 1-5 h.
The invention prepared by the process method has the following beneficial effects:
the invention adopts melamine and trithiocyanuric acid dopant to realize nitrogen, sulfur and oxygen multi-element doping in the hydrothermal reaction and heat treatment process. Meanwhile, the foam nickel is used as a matrix, melamine and trithiocyanuric acid are polymerized and grown on the foam nickel in a hydrothermal reaction, and the catalytic graphitization of the hard carbon material is simultaneously realized by the graphene oxide in the high-temperature treatment process, so that the three-dimensional doped graphene foam with high graphitization degree is generated. The invention has the advantages that the doping, the three-dimensional structure construction and the catalytic graphitization are simultaneously realized by adopting a hydrothermal method. The nitrogen content of the product is 3-7%, the sulfur content is 1-3%, the oxygen content is 4-12%, and the doping amount is controllable; and the experimental method is safe and nontoxic, low in cost and simple and convenient to operate. The prepared doped three-dimensional doped graphene foam electrode can be applied to the fields of lithium ion batteries, supercapacitors, electrocatalysis and the like. Therefore, the method provided by the invention has wide application prospect.
Drawings
FIG. 1 is a scanning electron micrograph of unetched nickel foam of example 3;
FIG. 2 is a SEM photograph of example 3 after the foam nickel is etched away;
fig. 3 is an X-ray diffraction pattern of the nitrogen and sulfur co-doped three-dimensional graphene foam of example 3.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1:
(1) firstly, 50mg of graphene oxide is dispersed in a mixed solvent of 70ml of deionized water and 10ml of ethanol to obtain a graphene oxide dispersion liquid, 0.03g of melamine and 0.04g of trithiocyanuric acid are sequentially added after the graphene oxide is ultrasonically stripped, and the mixture is stirred at 80 ℃ until the mixture is completely dissolved.
(2) 30 x 60 x 0.5mm of nickel foam was immersed in the liquid of (1) and then charged into a 100ml polytetrafluoroethylene reaction vessel for hydrothermal reaction. The hydrothermal reaction time is 4h, and the hydrothermal temperature is 100 ℃.
(3) And (3) after the hydrothermal product is freeze-dried, placing the product in a tube furnace, and heating to 500 ℃ at a heating rate of 2 ℃/min under the atmosphere of argon protection and preserving the temperature for 5 h.
(4) The product is soaked in 5 percent dilute hydrochloric acid, and is magnetically stirred for 12 hours at the temperature of 80 ℃, and the foam nickel is etched. Then centrifugally washing for 6 times, and drying to obtain a sample.
Example 2:
(1) firstly, 100mg of graphene oxide is dispersed in a mixed solvent of 25ml of deionized water and 25ml of ethanol to obtain a graphene oxide dispersion liquid, then 0.03g of melamine and 0.04g of trithiocyanuric acid are sequentially added, and the mixture is stirred at 80 ℃ until the mixture is completely dissolved.
(2) 30 x 60 x 1mm of nickel foam was immersed in the liquid of (1) and then charged into a 100ml teflon reaction vessel for hydrothermal reaction. The hydrothermal reaction time is 24h, and the hydrothermal temperature is 150 ℃.
(3) And (3) after the hydrothermal product is freeze-dried, placing the product in a tube furnace, and heating to 600 ℃ at the heating rate of 5 ℃/min for heat preservation for 2h under the atmosphere of argon protection.
(4) The product is soaked in 5 percent dilute hydrochloric acid, and is magnetically stirred for 12 hours at the temperature of 80 ℃, and the foam nickel is etched. Then centrifugally washing for 6 times, and drying to obtain a sample.
Example 3:
(1) firstly, 100mg of graphene oxide is dispersed in a mixed solvent of 50ml of deionized water and 10ml of ethanol to obtain a graphene oxide dispersion solution, then 0.12g of melamine and 0.17g of trithiocyanuric acid are sequentially added, and the mixture is stirred at 80 ℃ until the mixture is completely dissolved.
(2) 30 x 60 x 2mm of nickel foam was immersed in the liquid of (1) and then charged into a 100ml teflon reaction vessel for hydrothermal reaction. The hydrothermal reaction time is 36h, and the hydrothermal temperature is 200 ℃.
(3) And (3) after the hydrothermal product is freeze-dried, placing the product in a tube furnace, and heating to 800 ℃ at a heating rate of 10 ℃/min under the atmosphere of argon protection and preserving the temperature for 1 h.
(4) The product is soaked in 5 percent dilute hydrochloric acid, and is magnetically stirred for 12 hours at the temperature of 80 ℃, and the foam nickel is etched. Then centrifugally washing for 6 times, and drying to obtain a sample.
Referring to attached drawings 1-3, fig. 1 is a scanning electron microscope photomicrograph of nitrogen and sulfur co-doped three-dimensional graphene foam unetched nickel foam prepared in the embodiment. FIG. 2 is a high-power scanning electron micrograph of the foam nickel etched away, and a three-dimensional structure composed of graphene nanoplatelets can be seen by observing the morphology of the foam nickel by using a Scanning Electron Microscope (SEM) of model S-4800 of Japan Electron corporation. Fig. 3 is an X-ray diffraction pattern of nitrogen and sulfur co-doped three-dimensional graphene foam, which indicates that the nickel foam has been completely etched, leaving only the carbon material, and the steamed bun peak at 2-Theta =23 ° is a characteristic peak of the carbon material.
Example 4:
(1) firstly, 100mg of graphene oxide is dispersed in a mixed solvent of 50ml of deionized water and 20ml of ethanol to obtain a graphene oxide dispersion solution, then 0.18g of melamine and 0.25g of trithiocyanuric acid are sequentially added, and the mixture is stirred at 80 ℃ until the mixture is completely dissolved.
(2) 30 x 60 x 0.5mm of nickel foam was immersed in the liquid of (1) and then charged into a 100ml polytetrafluoroethylene reaction vessel for hydrothermal reaction. The hydrothermal reaction time is 12h, and the hydrothermal temperature is 180 ℃.
(3) And (3) after the hydrothermal product is freeze-dried, placing the product in a tube furnace, and heating to 1000 ℃ at a heating rate of 15 ℃/min under the atmosphere of argon protection and preserving the temperature for 1 h.
(4) The product is soaked in 5 percent dilute hydrochloric acid, and is magnetically stirred for 12 hours at the temperature of 80 ℃, and the foam nickel is etched. Then centrifugally washing for 6 times, and drying to obtain a sample.
Example 5:
(1) firstly, 100mg of graphene oxide is dispersed in a mixed solvent of 40ml of deionized water and 40ml of ethanol to obtain a graphene oxide dispersion solution, then 0.12g of melamine and 0.08g of trithiocyanuric acid are sequentially added, and the mixture is stirred at 80 ℃ until the mixture is completely dissolved.
(2) 30 x 60 x 1mm of nickel foam was immersed in the liquid of (1) and then charged into a 100ml teflon reaction vessel for hydrothermal reaction. The hydrothermal reaction time is 24h, and the hydrothermal temperature is 120 ℃.
(3) And (3) after the hydrothermal product is freeze-dried, placing the hydrothermal product in a tube furnace, and heating to 900 ℃ at the heating rate of 20 ℃/min for heat preservation for 2h under the atmosphere of argon protection.
(4) The product is soaked in 5 percent dilute hydrochloric acid, and is magnetically stirred for 12 hours at the temperature of 80 ℃, and the foam nickel is etched. Then centrifugally washing for 6 times, and drying to obtain a sample.
Example 6:
(1) firstly, 100mg of graphene oxide is dispersed in a mixed solvent of 70ml of deionized water and 10ml of ethanol to obtain graphene oxide dispersion liquid, then 0.02g of melamine and 0.02g of trithiocyanuric acid are sequentially added, and the mixture is stirred at 80 ℃ until the mixture is completely dissolved.
(2) 30 x 60 x 0.5mm of nickel foam was immersed in the liquid of (1) and then charged into a 100ml polytetrafluoroethylene reaction vessel for hydrothermal reaction. The hydrothermal reaction time is 36h, and the hydrothermal temperature is 100 ℃.
(3) And (3) after the hydrothermal product is freeze-dried, placing the product in a tube furnace, and heating to 500 ℃ at a heating rate of 20 ℃/min under the atmosphere of argon protection and preserving the temperature for 5 h.
(4) The product is soaked in 5 percent dilute hydrochloric acid, and is magnetically stirred for 12 hours at the temperature of 80 ℃, and the foam nickel is etched. Then centrifugally washing for 6 times, and drying to obtain a sample.
Example 7:
(1) firstly, 100mg of graphene oxide is dispersed in a mixed solvent of 40ml of deionized water and 40ml of ethanol to obtain a graphene oxide dispersion liquid, then 0.2g of melamine and 0.25g of trithiocyanuric acid are sequentially added, and the mixture is stirred at 80 ℃ until the mixture is completely dissolved.
(2) 30 x 60 x 2mm of nickel foam was immersed in the liquid of (1) and then charged into a 100ml teflon reaction vessel for hydrothermal reaction. The hydrothermal reaction time is 4h, and the hydrothermal temperature is 200 ℃.
(3) And (3) after the hydrothermal product is freeze-dried, placing the product in a tube furnace, and heating to 1200 ℃ at a heating rate of 20 ℃/min under the atmosphere of argon protection and preserving the temperature for 1 h.
(4) The product is soaked in 5 percent dilute hydrochloric acid, and is magnetically stirred for 12 hours at the temperature of 80 ℃, and the foam nickel is etched. Then centrifugally washing for 6 times, and drying to obtain a sample.
Claims (1)
1. The preparation method of the nitrogen and sulfur co-doped three-dimensional graphene foam electrode material is characterized by comprising the following specific steps of:
1) dispersing 100mg of graphene oxide in a mixed solvent of 50ml of deionized water and 10ml of ethanol to obtain a graphene oxide dispersion liquid, then sequentially adding 0.12g of melamine and 0.17g of trithiocyanuric acid, and uniformly stirring at 80 ℃ to obtain a mixed dispersion liquid;
2) directly cutting foamed nickel into 30 x 60mm, immersing into the mixed dispersion liquid obtained in the step 1), and then putting into a 100ml polytetrafluoroethylene reaction kettle for hydrothermal reaction at 100-200 ℃ for 4-36 h;
3) after the hydrothermal process is finished, freeze-drying the product, and finally, carrying out heat treatment for 1-5 h in a tube furnace at the temperature of 500-1200 ℃ under the protection of argon;
4) after the heat treatment is finished, placing the product in 5% dilute hydrochloric acid, and etching off the foamed nickel; drying the sample after multiple times of centrifugal washing to obtain nitrogen and sulfur co-doped three-dimensional graphene foam;
the thickness of the foamed nickel is 0.5-2 mm;
the heating rate of the heat treatment is 2-20 ℃/min.
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| CN109911889A (en) * | 2019-04-19 | 2019-06-21 | 陕西科技大学 | A kind of nitrogen sulphur codope porous graphene and its preparation method and application |
| CN112174119B (en) * | 2020-08-28 | 2022-05-06 | 中南大学 | Method for preparing graphene foam from antibiotic fungi residues |
| CN114045512A (en) * | 2021-06-24 | 2022-02-15 | 有研工程技术研究院有限公司 | Porous high-specific-surface-area integrated electrode material for hydrogen production by water electrolysis and preparation method thereof |
| CN115050943A (en) * | 2022-07-12 | 2022-09-13 | 北京北化工程技术有限公司 | Selenium-doped thiotrithiocyanuric acid material with high compaction density, preparation method thereof and battery positive plate |
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