CN114613995A - Carbon-coated nitrogen-doped Cu9S5And preparation method and application thereof - Google Patents

Carbon-coated nitrogen-doped Cu9S5And preparation method and application thereof Download PDF

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CN114613995A
CN114613995A CN202210163634.3A CN202210163634A CN114613995A CN 114613995 A CN114613995 A CN 114613995A CN 202210163634 A CN202210163634 A CN 202210163634A CN 114613995 A CN114613995 A CN 114613995A
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carbon
doped
nitrogen
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zns
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盛天都
刘勇奇
曹凯峰
彭海龙
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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Priority to PCT/CN2022/135945 priority patent/WO2023160102A1/en
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Abstract

The invention belongs to the technical field of battery materials, and discloses carbon-coated nitrogen-doped Cu9S5And preparation method and application thereof, the carbon-coated nitrogen-doped Cu9S5Has a chemical formula of Cu9S5@ NC, carbon-clad nitrogen-doped Cu9S5The structure of (1) is a bullet-like hollow nano structure. Cu prepared by the invention9S5@ NC has a high surface area and a unique bullet-like hollow nanostructure, showing good performance in high-performance sodium-ion batteries. The hollow nano structure can effectively adapt to the volume expansion change in the process of sodium intercalation and sodium deintercalation, and the structure bullet-like nano structure can be electrically connectedThe contact area between the electrode and the electrolyte is enlarged, and the electrochemical dynamic performance is improved.

Description

Carbon-coated nitrogen-doped Cu9S5And preparation method and application thereof
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to carbon-coated nitrogen-doped Cu9S5And a preparation method and application thereof.
Background
Sodium ion batteries are considered to be one of the most promising substitutes for lithium ion batteries due to the characteristics of abundant sodium resources, low cost, electrochemical reaction mechanism similar to that of lithium ion batteries, and the like. However with Li+In contrast, Na+The lithium ion battery has larger ionic radius, higher oxidation-reduction potential and slower reaction kinetics, so the requirements on the structural stability and kinetic performance of the material are more strict, and the lithium ion battery also becomes a bottleneck difficult to be commercially used in late. Therefore, the development of electrode materials with high reversible capacity and fast reaction kinetics remains a challenge. In the past few years, a number of promising sodium-ion battery electrode materials have been widely reported, including various negative electrode materials (e.g., alloy materials, metal chalcogenides, carbon-based materials). Among these materials, metal chalcogenides are of great interest due to compositional diversity and good electrochemical performance. But most of them have poor conductivity and large volume change during electrochemical reaction, thus showing poor rate capability and cycle performance.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a carbon-coated nitrogen-doped Cu9S5And preparation method and application thereof, the carbon-coated nitrogen-doped Cu9S5Available of Cu9S5@ NC indicates that it has a high surface area and a unique "bullet-like" hollow nanostructure, showing good performance in high performance sodium ion batteries.
In order to achieve the purpose, the invention adopts the following technical scheme:
carbon-coated nitrogen-doped Cu9S5Of the chemical formula Cu9S5@ NC, its structure is "bullet-like" hollow nano structure.
Preferably, the carbon-clad nitrogen-doped Cu9S5Has an impedance of 2-6 omega.
Preferably, the carbon-clad nitrogen-doped Cu9S5Reversible capacity of more than 300mAh g-1。
Preferably, the carbon-clad nitrogen-doped Cu9S5The capacity of (2) is more than 85% after 2000 cycles.
Preferably, the Cu9S5The carbon-nitrogen ratio in @ NC is 0.01-0.5.
Carbon-coated nitrogen-doped Cu9S5The preparation method comprises the following steps:
(1) mixing and dispersing bullet-like ZnO nano particles and a solvent, adding a sulfur-containing reactant, reacting, performing heat treatment, and performing solid-liquid separation to obtain bullet-like ZnS nano particles;
(2) dispersing the bullet-like ZnS nano particles and dopamine hydrochloride in a buffer solution, stirring, washing, carrying out solid-liquid separation, taking a solid phase, and calcining to obtain ZnS @ NC hollow nano particles;
(3) mixing the ZnS @ NC hollow nano particles with copper salt, adding a solvent, stirring, carrying out solid-liquid separation, and taking a solid phase to obtain the carbon-coated nitrogen-doped Cu9S5。
Preferably, in the step (1), the preparation steps of the bullet-like ZnO nanoparticles are as follows: reduction of Zn (Ac)2Mixing with hexamethylenetetramine, adding a solvent, stirring, performing reflux reaction, performing solid-liquid separation, and taking a solid phase to obtain bullet-shaped ZnO nanoparticles; said Zn (Ac)2And hexamethylenetetramine in a molar ratio of 1: (1-3).
Further preferably, the solvent is at least one of ethanol and water.
More preferably, the volume ratio of the ethanol to the water is 3 (5-7).
Further preferably, the temperature of the reflux reaction is 80-100 ℃, and the time of the reflux reaction is 1-5 h.
Preferably, in step (1), the solvent is one of ethanol, methanol and water.
Further preferably, the solvent is ethanol.
Preferably, in step (1), the sulfur-containing reactant is one of thiourea and thioacetamide.
Preferably, in step (1), after the dispersion, a dispersion liquid is obtained, and the liquid-solid ratio of the dispersion liquid to the sulfur-containing reactant is (40-60) ml: (120-140) mg.
Preferably, in the step (1), the temperature of the heat treatment is 180-.
Preferably, in the step (2), the mass ratio of the bullet-like ZnS to dopamine hydrochloride is (4-5): (2-3).
Preferably, in step (2), the buffer is tris.
Preferably, in step (2), the amount of the buffer added is 100-120 mL.
Preferably, in step (2), the concentration of the buffer is 8-10 mmol.
Preferably, in the step (2), the washing process is washing with water and ethanol.
Preferably, in the step (2), the solid phase is ZnS @ PDA.
Preferably, in the step (2), the calcination temperature is 500-600 ℃, and the calcination time is 2-5 h.
Preferably, in step (2), the atmosphere of the calcination is nitrogen or argon.
Preferably, in the step (3), the mass ratio of the ZnS @ NC hollow nanoparticles to the copper salt is 1: (2.1-5.4).
Preferably, in the step (3), the solvent is one of methanol, water or ethanol.
Further preferably, the solvent is one of methanol and ethanol.
Preferably, in the step (3), the temperature of the stirring reaction is 60-80 ℃, and the time of the stirring reaction is 20-35 h.
Preferably, in the step (3), the copper salt is Cu (NO)3)2·3H2O、CuCl2One kind of (1).
Further preferably, the copper salt is Cu (NO)3)2·3H2O。
The invention also provides the carbon-coated nitrogen-doped Cu9S5The application in the preparation of sodium ion battery materials.
Preferably, the sodium-ion battery material is a sodium-ion battery negative electrode material.
Compared with the prior art, the invention has the following beneficial effects:
(1) cu prepared by the invention9S5@ NC has a high surface area and a unique bullet-like hollow nanostructure, showing good performance in high-performance sodium-ion batteries. The hollow nano structure can effectively adapt to volume expansion change in the processes of sodium intercalation and sodium deintercalation, and the structure bullet-like nano structure can enlarge the contact area between an electrode and an electrolyte, thereby improving the electrochemical dynamic performance. The carbon-coated nitrogen-doped Cu prepared by the invention9S5The impedance of (2) to (6) omega; in 1Ag-1Reversible capacity under current density is more than 300mAh g-1(ii) a The capacity after 2000 cycles has a cycle retention rate of more than 85%.
(2) The method comprises the steps of preparing bullet-like ZnO nanoparticles, using the bullet-like ZnO nanoparticles as a template, preparing the bullet-like ZnS nanoparticles through ion exchange, obtaining ZnS @ NC hollow nanoparticles through nitrogen doping, and finally preparing Cu through ion exchange9S5@NC。
(3) The invention can easily prepare Cu by a template method9S5@ NC, easily available raw materials, and prepared nano particle Cu9S5The @ NC has uniform size and unique appearance, and can show the beauty of the micro nano structure.
Drawings
FIG. 1 shows bullet-like Cu obtained in example 1 of the present invention9S5XRD pattern of @ NC;
FIG. 2 shows bullet-like Cu obtained in example 1 of the present invention9S5EDX graph of @ NC;
FIG. 3 shows bullet-like Cu obtained in example 1 of the present invention9S5SEM picture of @ NC;
FIG. 4 shows bullet-like Cu obtained in example 1 of the present invention9S5TEM image of @ NC;
FIG. 5 shows bullet-like Cu obtained in example 1 of the present invention9S5The magnification graph of the @ NC material under different current densities;
FIG. 6 shows bullet-like Cu obtained in example 1 of the present invention9S5@ NC material at 2Ag-1Cycling stability plot at current density.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
Carbon-coated nitrogen-doped Cu of the present example9S5The preparation method comprises the following steps:
(1) 1mmol of Zn (Ac)2Adding 1mmol of hexamethylenetetramine into 100mL of mixed solution (the volume ratio of ethanol to water is 3:7), stirring, heating to 90 ℃, refluxing for 1h, washing with water and ethanol for multiple times, centrifuging and collecting to obtain bullet-shaped ZnO nanoparticles;
(2) dispersing bullet-shaped ZnO nano particles in 80ml of ethanol, performing ultrasonic treatment for 10min to obtain a dispersion liquid, then adding 120mg of thiourea into 40ml of the dispersion liquid, reacting, transferring the solution after reaction into a stainless steel high-pressure autoclave lined with polytetrafluoroethylene, heating in an oven at 180 ℃ for 8 hours, performing solid-liquid separation, washing precipitates with ethanol, and performing centrifugal collection to obtain the bullet-shaped ZnS nano particles;
(3) dispersing 80mg of bullet-shaped ZnS nanoparticles and 40mg of dopamine hydrochloride in Tris buffer (10mM, 100mL), magnetically stirring for 4h, washing with water and ethanol and centrifuging, performing solid-liquid separation, collecting ZnS @ PDA product, and separating the product in N2Annealing for 2h at 600 ℃ in atmosphere to obtain ZnS @ NC hollow nanoparticles;
(4) mixing 15mgZnS @ NC hollow nanoparticles and 200mg Cu (NO)3)2·3H2Mixing O, dispersing in 15mL ethanol, magnetizing and stirring at 60 ℃ for 30h, washing with water and ethanol, centrifuging, and taking the solid phase to obtain carbon-coated nitrogen-doped Cu9S5(Cu9S5@NC)。
FIG. 1 shows bullet-shaped Cu obtained in example 1 of the present invention9S5XRD pattern of @ NC; FIG. 2 shows bullet-shaped Cu obtained in example 1 of the present invention9S5EDX graph of @ NC; FIG. 3 shows bullet-shaped Cu obtained in example 1 of the present invention9S5SEM picture of @ NC; FIG. 4 shows bullet-shaped Cu obtained in example 1 of the present invention9S5TEM image of @ NC; XRD analysis shown in figure 1 shows that the diffraction peak of the obtained product is hexagonal Cu9S5(JCPDS card number 47-1748). EDX analysis (FIG. 2) further confirmed the composition of Cu, S, C, N in the structure, indicating that ZnS is completely converted to Cu by an ion exchange process9S5. Figure 3 shows that the bullet-like structure remains good after the ion exchange process. It is clear from fig. 4 that the hollow interior structure still retains the bullet-like morphology.
FIG. 5 shows bullet-shaped Cu obtained in example 1 of the present invention9S5The magnification graph of the @ NC material under different current densities; cu9S5@ NC electrode at 0.1-5Ag-1Discharge and charge rate capabilities at different current densities. At 0.1, 0.2, 0.3, 0.5, 1, 2 and 3Ag-1The average reversible capacity of the electrode is 360, 312, 306, 290, 283272 and 260mAh g-1. Even at 5Ag-1At high current density of 242mAh g can still be maintained-1The reversible capacity of (a). When the current density is reduced to 0.2Ag-1Then 292mAh g can be recovered-1Reversible stable capacity of (B), illustrating Cu9S5The @ NC electrode has good reversibility. Cu9S5The discharge voltage distribution of the @ NC electrode under different current densities also verifies the excellent rate performance of the @ NC electrode.
FIG. 6 shows bullet-shaped Cu obtained in example 1 of the present invention9S5@ NC material in 2Ag-1Cycling stability plot at current density. In contrast, Cu9S5The specific capacity of the electrode decays rapidly with increasing current density. Cu9S5The @ NC electrode has good cycling stability. At higher 2Ag-1At the current density, even after 2000 cycles, the capacity retention rate can still reach 85%, and the corresponding average capacity loss is only 0.0025%. Cu prepared in inventive example 19S5The @ NC electrode also exhibited excellent cycling performance at other current densities, showing an ultra-stable cycle life. During the cycling, the coulombic efficiency of the electrode at all current densities was kept around 100%.
Example 2
Carbon-coated nitrogen-doped Cu of the present example9S5The preparation method comprises the following steps:
(1) 1mmol of Zn (Ac)2Adding 1mmol of hexamethylenetetramine into 100mL of mixed solution (the volume ratio of ethanol to water is 3:7), stirring, heating to 80 ℃, refluxing for 1h, washing with water and ethanol for multiple times, centrifuging and collecting to obtain bullet-shaped ZnO nanoparticles;
(2) dispersing bullet-shaped ZnO nano particles in 80ml of ethanol, carrying out ultrasonic treatment for 10min to obtain a dispersion liquid, then adding 120mg of thiourea into 40ml of the dispersion liquid, reacting, transferring the solution after the reaction into a stainless steel high-pressure autoclave lined with polytetrafluoroethylene, heating in an oven at 180 ℃ for 8 hours, carrying out solid-liquid separation, washing the precipitate with ethanol, centrifuging and collecting to obtain the bullet-shaped ZnS nano particles;
(3) will 80Dispersing the mg of bullet ZnS nanoparticles and 40mg of dopamine hydrochloride in Tris buffer (10mM, 100mL), magnetically stirring for 4h, washing with water and ethanol, centrifuging, performing solid-liquid separation, collecting ZnS @ PDA product, and purifying with N2Annealing for 2h at 550 ℃ in atmosphere to obtain ZnS @ NC hollow nanoparticles;
(4) mixing 15mgZnS @ NC hollow nanoparticles and 200mg Cu (NO)3)2·3H2Mixing O, dispersing in 15mL ethanol, magnetizing and stirring at 60 ℃ for 30h, washing with water and ethanol, centrifuging, and taking the solid phase to obtain carbon-coated nitrogen-doped Cu9S5(Cu9S5@NC)。
Example 3
Carbon-coated nitrogen-doped Cu of the present example9S5The preparation method comprises the following steps:
(1) 1mmol of Zn (Ac)2Adding 1mmol of hexamethylenetetramine into 100mL of mixed solution (the volume ratio of ethanol to water is 3:7), stirring, heating to 100 ℃, refluxing for 1h, washing with water and ethanol for multiple times, centrifuging and collecting to obtain the bullet-shaped ZnO nanoparticles;
(2) dispersing bullet-shaped ZnO nano particles in 80ml of ethanol, carrying out ultrasonic treatment for 15min to obtain a dispersion liquid, then adding 120mg of thiourea into 40ml of the dispersion liquid, reacting, transferring the solution after reaction into a stainless steel high-pressure autoclave lined with polytetrafluoroethylene, heating in an oven at 190 ℃ for 10 hours, carrying out solid-liquid separation, washing precipitates with ethanol, centrifuging and collecting to obtain the bullet-shaped ZnS nano particles;
(3) dispersing 80mg of bullet-shaped ZnS nanoparticles and 40mg of dopamine hydrochloride in Tris buffer (10mM, 100mL), magnetically stirring for 4h, washing with water and ethanol, centrifuging, performing solid-liquid separation, collecting ZnS @ PDA product, and separating with N2Annealing for 2h at 600 ℃ in atmosphere to obtain ZnS @ NC hollow nanoparticles;
(4) mixing 15mgZnS @ NC hollow nanoparticles and 200mg Cu (NO)3)2·3H2Mixing O, dispersing in 15mL ethanol, magnetizing and stirring at 60 ℃ for 30h, washing with water and ethanol, centrifuging, and taking the solid phase to obtain carbon-coated nitrogen-doped Cu9S5(Cu9S5@NC)。
Comparative example 1
The preparation method of the carbon-coated nitrogen-doped CuS comprises the following steps:
(1) 1mmol of Zn (Ac)2Adding 1mmol of hexamethylenetetramine into 100mL of mixed solution (the volume ratio of ethanol to water is 3:7), stirring, heating to 100 ℃, refluxing for 2 hours, washing with water and ethanol for multiple times, centrifuging and collecting to obtain bullet-like ZnO nanoparticles;
(2) dispersing bullet-like ZnO nanoparticles in 80ml of ethanol, performing ultrasonic treatment for 10min to obtain a dispersion solution, then adding 120mg of thiourea into 40ml of the dispersion solution, reacting, transferring the solution after reaction into a stainless steel high-pressure autoclave lined with polytetrafluoroethylene, heating for 8 hours in an oven at 200 ℃, performing solid-liquid separation, washing precipitates with ethanol, and performing centrifugal collection to obtain the bullet-like ZnS nanoparticles;
(3) dispersing 80mg of bullet-like ZnS nanoparticles and 40mg of dopamine hydrochloride in Tris buffer (10mM, 100mL), magnetically stirring for 4h, washing with water and ethanol and centrifuging, performing solid-liquid separation, collecting ZnS @ PDA product, and separating the product in N2Annealing for 3h at 1000 ℃ in atmosphere to obtain ZnS @ NC hollow nanoparticles;
(4) mixing 15mgZnS @ NC hollow nanoparticles and 200mg Cu (NO)3)2·3H2And O, mixing, dispersing in 15mL ethanol, magnetizing and stirring at 100 ℃ for 30h, washing with water and ethanol, centrifuging, and taking a solid phase to obtain carbon-coated nitrogen-doped CuS (CuS @ NC).
Comparative example 2
Cu of this comparative example9S5The preparation method comprises the following steps:
(1) 1mmol of Zn (Ac)2Adding 1mmol of hexamethylenetetramine into 100mL of mixed solution (the volume ratio of ethanol to water is 3:7), stirring, heating to 90 ℃, refluxing for 1h, washing with water and ethanol for multiple times, centrifuging and collecting to obtain bullet-shaped ZnO nanoparticles;
(2) dispersing bullet-shaped ZnO nano particles in 80ml of ethanol, carrying out ultrasonic treatment for 10min to obtain a dispersion liquid, then adding 120mg of thiourea into 40ml of the dispersion liquid, reacting, transferring the solution after the reaction into a stainless steel high-pressure autoclave lined with polytetrafluoroethylene, heating in an oven at 180 ℃ for 8 hours, carrying out solid-liquid separation, washing the precipitate with ethanol, centrifuging and collecting to obtain the bullet-shaped ZnS nano particles;
(3) mixing 15mg ZnS hollow nanoparticles and 200mg Cu (NO)3)2·3H2Mixing with O, dispersing in 15mL ethanol, magnetizing and stirring at 60 deg.C for 30h, washing with water and ethanol, centrifuging, and collecting solid phase to obtain Cu9S5。
And (3) analysis:
TABLE 1 Cu at different reaction temperatures and reaction solventsxEnd phase of S material
Reactants (molar ratio) Solvent(s) Temperature of Product of
Cu(NO3)2+ZnS(5.4:1) Water (I) 90 CuS
Cu(NO3)2+ZnS(5.4:1) Ethylene glycol 90 Cu8S5
Cu(NO3)2+ZnS(5.4:1) Water (W) 26 Cu9S5
Cu(NO3)2+ZnS(5.4:1) Methanol 60 Cu9S5
Cu(NO3)2+ZnS(2.1:1) Ethanol 80 Cu9S5
From Table 1, the reaction conditions are shown for the obtained CuxThe phase of the S material has great influence, and the obtained phases have certain difference under different reaction temperatures and reaction solvents. It can be found through experiments that the reducing power, complexing power and reactant concentration of the solvent determine CuxFinal phase of S material.
TABLE 2 electrochemical Performance test data for materials prepared in the examples and comparative examples
Figure BDA0003515045890000071
As can be seen from Table 1, the carbon-clad nitrogen-doped Cu of examples 1 to 3 of the present invention9S5In 1Ag-1Reversible capacity under current density is more than 320mAh g-1Carbon-coated nitrogen-doped Cu of examples 1 to 3 of the present invention9S5The capacity of (2) is more than 85% after 2000 cycles.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.

Claims (10)

1. Carbon-coated nitrogen-doped Cu9S5Characterized in that the carbon is coated with nitrogen-doped Cu9S5Has a chemical formula of Cu9S5@ NC, said carbon-clad nitrogen-doped Cu9S5The structure of (1) is a bullet-like hollow nano structure.
2. The carbon-clad nitrogen-doped Cu according to claim 19S5Characterized in that the carbon is coated with nitrogen-doped Cu9S5The impedance of (2) to (6) omega; the carbon-coated nitrogen-doped Cu9S5Reversible capacity of more than 300mAh g-1(ii) a The carbon-coated nitrogen-doped Cu9S5The capacity of (2) is more than 85% after 2000 cycles.
3. The carbon-clad nitrogen-doped Cu according to claim 19S5Characterized in that the Cu9S5The carbon-nitrogen ratio in @ NC is 0.01-0.5.
4. The carbon-clad nitrogen-doped Cu as claimed in any one of claims 1 to 39S5The preparation method is characterized by comprising the following steps:
(1) mixing and dispersing bullet-like ZnO nanoparticles and a solvent, adding a sulfur-containing reactant, reacting, performing heat treatment, and performing solid-liquid separation to obtain bullet-like ZnS nanoparticles;
(2) dispersing the bullet-like ZnS nano particles and dopamine hydrochloride in a buffer solution, stirring, washing, carrying out solid-liquid separation, taking a solid phase, and calcining to obtain ZnS @ NC hollow nano particles;
(3) mixing the ZnS @ NC hollow nano particles with copper salt, adding a solvent, stirring for reaction, carrying out solid-liquid separation, and taking a solid phase to obtain the carbon-coated nitrogen-doped Cu9S5。
5. The preparation method according to claim 4, wherein in the step (1), the preparation steps of the bullet-like ZnO nanoparticles are as follows: reduction of Zn (Ac)2Mixing with hexamethylenetetramine, adding a solvent, stirring, performing reflux reaction, performing solid-liquid separation, and taking a solid phase to obtain bullet-shaped ZnO nanoparticles; the Zn (Ac)2And hexamethylenetetramine in a molar ratio of 1: (1-3).
6. The preparation method according to claim 4, wherein in the step (1), the sulfur-containing reactant is one of thiourea and thioacetamide.
7. The preparation method according to claim 4, wherein in the step (3), the mass ratio of the ZnS @ NC hollow nanoparticles to the copper salt is 1: (2.1-5.4); the temperature of the stirring reaction is 60-80 ℃, and the time of the stirring reaction is 20-35 h.
8. The method according to claim 4, wherein in the step (3), the solvent is one of methanol, water, and ethanol.
9. The method according to claim 4, wherein in the step (3), the copper salt is Cu (NO)3)2`3H2O、CuCl2One kind of (1).
10. The carbon-coated nitrogen-doped Cu of any one of claims 1 to 39S5The application in the preparation of sodium ion battery materials.
CN202210163634.3A 2022-02-22 2022-02-22 Carbon-coated nitrogen-doped Cu9S5And preparation method and application thereof Pending CN114613995A (en)

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