CN112429713A - Hollow nitrogen-doped porous carbon sphere and preparation method and application thereof - Google Patents
Hollow nitrogen-doped porous carbon sphere and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a hollow nitrogen-doped porous carbon sphere and a preparation method and application thereof, wherein zinc sulfide is used as a self-sacrificial template, a conductive polymer polydopamine is used as a carbon precursor, a polydopamine-zinc sulfide precursor (ZnS @ PDA) is prepared through hydrothermal reaction, and the hollow nitrogen-doped porous carbon sphere (NHPCS) is further prepared through calcination, the preparation method has fewer steps and is easy to operate, and when the prepared hollow nitrogen-doped porous carbon sphere is used as a lithium-sulfur battery anode material, the dissolution and diffusion of polysulfide can be avoided, the transportation and storage of charges and ions are promoted, the conductivity and polarity of a carbon material are improved, the polysulfide limiting capability of the synthesized electrode material is further improved, the prepared hollow nitrogen-doped porous carbon sphere is applied to a lithium-sulfur battery after sulfur loading, the battery capacity is high, and the excellent rate capability and cycle stability are shown, is far higher than the traditional carbon nano-tube based anode material.
Description
Technical Field
The invention relates to the technical field of lithium-sulfur battery materials, in particular to a hollow nitrogen-doped porous carbon sphere and a preparation method and application thereof.
Background
Lithium sulfur batteries are increasingly receiving attention. The lithium-sulfur battery is a lithium battery with sulfur as a battery anode material and metal lithium as a battery cathode material. The elemental sulfur has rich reserves in the earth, and has the characteristics of low price, environmental friendliness and the like. Although the theoretical specific capacity of the material and the theoretical specific energy of the battery are higher in the lithium-sulfur battery using sulfur as the cathode material, the commercial development of the lithium-sulfur battery still faces many challenges, and the main problems are: (1) active sulfur and a discharge product thereof, namely lithium sulfide, are electronic/ionic insulating materials and are not beneficial to the electrochemical reaction; (2) during the charging and discharging process, lithium polysulfide generated in the battery is easily dissolved in electrolyte, and a shuttle effect and various side reactions occur, so that a large amount of active materials are lost, and the performance of the lithium-sulfur battery can be improved to a certain extent by reasonably designing a sulfur anode material.
For example, chinese patent CN106927498A (published japanese 2019.8.16) discloses a zinc sulfide nanobelt, a preparation method thereof, and an application thereof in the preparation of a positive electrode material for a lithium-sulfur battery, wherein a zinc source, a sulfur source, and a surfactant are first utilized to prepare a banded zinc sulfide through a hydrothermal reaction, then the banded zinc sulfide reacts with a carbon source at a ph of 8.5 for 6 hours, and the banded zinc sulfide is heated at 600 ℃ to obtain a product, and then the product is continuously treated in a ferric chloride solution to prepare a positive electrode material having a nano-banded core-shell structure in which sulfur is used as a core and carbon or nitrogen-doped carbon is used as a shell; but the adsorption and fixation effects on polysulfide are weaker, and the lithium sulfur battery is used for preparing the lithium sulfur battery, and the lithium sulfur battery has low specific capacity and poor rate capability.
Disclosure of Invention
The invention aims to solve the technical problems of low specific capacity and poor rate capability of the lithium-sulfur battery when the conventional lithium-sulfur battery cathode material is used for preparing the lithium-sulfur battery, and provides a preparation method of a hollow nitrogen-doped porous carbon sphere.
It is still another object of the present invention to provide a hollow nitrogen-doped porous carbon sphere.
The invention also aims to provide application of the hollow nitrogen-doped porous carbon spheres.
The above purpose of the invention is realized by the following technical scheme:
a preparation method of hollow nitrogen-doped porous carbon spheres comprises the following steps:
s1, dissolving zinc salt and a sulfur source in a solvent to obtain a first mixed solution, reacting at 90-150 ℃ for 1-3 h, separating, and drying the solid to obtain a zinc sulfide ball template; wherein the molar ratio of the zinc salt to the sulfur source is 1: 1-3;
s2, dissolving the zinc sulfide ball template prepared in the step S1 and dopamine hydrochloride in a solvent to obtain a second mixed solution, carrying out hydrothermal reaction for 2-5 h at 90-150 ℃, separating, and drying the solid to obtain a polydopamine-zinc sulfide precursor; wherein the molar ratio of the zinc sulfide sphere template to the dopamine hydrochloride is 1-5: 1;
s3, calcining the polydopamine-zinc sulfide precursor prepared in the step S3 for 1-3 h at 700-1000 ℃ in an inert atmosphere to prepare the hollow nitrogen-doped porous carbon spheres.
The invention takes zinc sulfide as a self-sacrifice template, conductive polymer polydopamine as a carbon precursor, polydopamine-zinc sulfide precursor (ZnS @ PDA) is prepared through hydrothermal reaction, hollow nitrogen-doped porous carbon spheres (NHPCS) are prepared after calcination, the hollow nitrogen-doped porous carbon spheres of the invention contain abundant nitrogen elements and carbon elements and can provide abundant carbon sources and nitrogen sources, when the prepared hollow nitrogen-doped porous carbon spheres are used as a positive electrode material of a lithium sulfur battery, because the zinc sulfide is easy to decompose as the self-sacrifice template and can decompose at the temperature of more than 900 ℃ under the condition of nitrogen, a large number of micropores and mesopores can be formed, the positive electrode material has a hollow porous structure, is favorable for loading a large amount of sulfur, has strong adsorption and fixation effects on polysulfide, avoids the dissolution and diffusion of the polysulfide, promotes the transportation and storage of charges and ions, and in addition, the invention also introduces polydopamine as a nitrogen source, and heteroatom is introduced on the basis of the carbon precursor, so that the conductivity and polarity of the carbon material are improved, the electrochemical reaction is facilitated, and the limit polysulfide capacity of the synthesized electrode material is further improved.
Preferably, the first mixed solution in step S1 is reacted at 100-140 ℃ for 1.5-2.5 h.
Preferably, the concentration of the zinc salt in the first mixed solution in the step S1 is 0.01-0.05 mol/L.
Preferably, the concentration of the sulfur source in the first mixed solution in the step S1 is 0.02-0.08 mol/L.
Preferably, the temperature of the hydrothermal reaction in the step S2 is 110-140 ℃, and the reaction time is 3-4 h.
Preferably, the concentration of the zinc sulfide spherical template in the second mixed solution in the step S2 is 0.01-0.05 mol/L.
Preferably, the concentration of the dopamine hydrochloride in the second mixed solution in the step S2 is 0.005-0.02 mol/L.
Preferably, the solvent in the step S2 is a mixed solution of ethanol and water, wherein the volume ratio of ethanol to water is 5-1: 1.
Preferably, the calcining temperature in the step S3 is 750-950 ℃, and the reaction time is 1.5-2.5 h.
Preferably, the zinc salt in step S1 is one or more of zinc nitrate hexahydrate, zinc sulfate heptahydrate, zinc chloride hexahydrate and zinc acetate dihydrate.
Preferably, the sulfur source in step S1 is one or more of thioacetamide, thiourea, glutathione, and cysteine.
Preferably, the temperature rise rate of the calcination in the step S3 is 2-10 ℃/min.
Preferably, the inert atmosphere of step S3 is nitrogen and/or argon.
Preferably, the inert atmosphere gas flow of step S3 is 60 mL/min.
The invention protects the hollow nitrogen-doped porous carbon spheres prepared by the preparation method.
The invention also protects the application of the hollow nitrogen-doped porous carbon spheres in preparing the cathode material of the lithium-sulfur battery.
Specifically, the method comprises the following steps:
uniformly mixing hollow nitrogen-doped porous carbon spheres with elemental sulfur, and reacting at 120-180 ℃ for 10-20 h to obtain a hollow nitrogen-doped porous carbon sphere composite sulfur positive electrode material; wherein the mass ratio of the hollow nitrogen-doped porous carbon spheres to the elemental sulfur is 1: 3-5.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses zinc sulfide as a self-sacrifice template, conductive polymer polydopamine as a carbon precursor, and prepares a polydopamine-zinc sulfide precursor (ZnS @ PDA) through hydrothermal reaction, and further prepares hollow nitrogen-doped porous carbon spheres (NHPCS) after calcination, the preparation method of the invention has fewer steps and easy operation, and when the prepared hollow nitrogen-doped porous carbon spheres are used as a positive electrode material of a lithium sulfur battery, the preparation method can avoid the dissolution and diffusion of polysulfide, promote the transportation and storage of charges and ions, introduce heteroatoms on the basis of the carbon precursor, improve the conductivity and polarity of the carbon material, be beneficial to the proceeding of electrochemical reaction, and further improve the capability of limiting polysulfide of the synthesized electrode material, after the hollow nitrogen-doped porous carbon spheres are loaded with sulfur, the hollow nitrogen-doped porous carbon spheres are applied to the lithium sulfur battery as the positive electrode material, have high battery capacity, and show excellent rate performance and cycling stability, is far higher than the traditional carbon nano-tube based anode material.
Drawings
Fig. 1 is a scanning electron microscope image of a hollow nitrogen-doped porous carbon sphere prepared in example 1 of the present invention.
Fig. 2 is a graph of rate performance of lithium sulfur batteries of examples 2 and 3 of the present invention.
Fig. 3 is a graph of cycle performance of the lithium sulfur batteries of examples 2 and 3 of the present invention at a current density of 1C.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Example 1
A preparation method of hollow nitrogen-doped porous carbon spheres comprises the following steps:
s1, respectively dissolving 0.73g of zinc nitrate hexahydrate and 0.3g of thioacetamide in 50mL of water, mixing, carrying out reflux reaction at 120 ℃ for 2 hours, centrifuging, washing, separating, and freeze-drying to obtain a zinc sulfide sphere template (ZnS); wherein the molar ratio of zinc nitrate hexahydrate to thioacetamide is 1: 2;
s2.0.5g of ZnS and 0.45g of dopamine hydrochloride are dissolved in a mixed solution of 37.5mL of ethanol and 25mL of water, hydrothermal reaction is carried out for 2h at the temperature of 140 ℃, and then zinc sulfide (ZnS @ PDA) coated with polydopamine is obtained through centrifugal washing separation and vacuum drying; wherein the molar ratio of the zinc sulfide sphere template to the dopamine hydrochloride is 2: 1;
and S3, calcining ZnS @ PDA at 900 ℃ for 3 hours in an inert gas atmosphere to obtain hollow nitrogen-doped porous carbon spheres (NHPCS).
Example 2
The preparation method of the hollow nitrogen-doped porous carbon sphere of this example is the same as that of example 1, except that the molar ratio of zinc nitrate to thioacetamide is replaced with 1: 1; the molar ratio of the zinc sulfide sphere template to the dopamine hydrochloride is replaced by 5: 1.
Example 3
The preparation method of the hollow nitrogen-doped porous carbon sphere of this example is the same as that of example 1 except that the reaction temperature of step S1 is replaced with 90 ℃.
Example 4
The preparation method of the hollow nitrogen-doped porous carbon sphere of this example is the same as that of example 1 except that the reaction temperature of step S1 is replaced with 150 ℃.
Example 5
The preparation method of the hollow nitrogen-doped porous carbon sphere of this example is the same as that of example 1 except that the reaction temperature of step S2 is replaced with 90 ℃.
Example 6
The preparation method of the hollow nitrogen-doped porous carbon sphere of this example is the same as that of example 1 except that the reaction temperature of step S3 is replaced with 700 ℃.
Example 7
The hollow nitrogen-doped porous carbon sphere of this example was prepared in the same manner as in example 1, except that zinc nitrate hexahydrate was replaced with zinc acetate dihydrate.
Comparative example 1
The preparation method of the hollow nitrogen-doped porous carbon sphere of this comparative example is the same as that of example 1 except that sodium lauryl sulfate, a surfactant, is added to the first mixed solution of step S1.
Comparative example 2
The preparation method of the hollow nitrogen-doped porous carbon sphere of this comparative example is the same as example 1 except that step S2 is adjusted to pH 8.5.
Comparative example 3
The preparation method of the hollow nitrogen-doped porous carbon sphere of this comparative example was the same as example 1 except that the pH was adjusted to 8.5 in step S2, and the hydrothermal reaction was not performed, but directly freeze-dried.
Comparative example 4
The preparation method of the hollow nitrogen-doped porous carbon sphere of this comparative example was the same as example 1 except that the calcination of step S3 was adjusted to 600 ℃.
Comparative example 5
The comparative example is a hollow carbon nanotube, wherein the diameter is 5 to 10nm and the length is 10 to 20 μm.
Applications of
1. Application of hollow nitrogen-doped porous carbon spheres in lithium-sulfur battery
0.05g of the hollow nitrogen-doped porous carbon spheres prepared in the embodiments 1-6 and 0.15mg of elemental sulfur are mixed according to the mass ratio of 1:3, and the mixture is placed in a stainless steel reaction kettle to react for 12 hours at 155 ℃ to obtain the hollow nitrogen-doped porous carbon sphere composite sulfur electrode material (S @ NHPCS).
Mixing S @ NHPCS, adhesives polytetrafluoroethylene and carbon nano tubes according to the mass ratio of 8:1:1, uniformly coating the mixture on a current collector (aluminum foil, the thickness of the aluminum foil is 0.03mm), and performing vacuum drying to obtain an electrode plate; then, the electrode plate is used as a positive electrode, and the lithium plate is used as a negative electrode to assemble the lithium-sulfur battery.
2. Application of carbon nano tube in lithium-sulfur battery
0.05g of the hollow carbon nanotube of the comparative example 5 and 0.15mg of elemental sulfur were mixed in a mass ratio of 1:3, and placed in a stainless steel reaction kettle for reaction at 155 ℃ for 12 hours to obtain a carbon nanotube composite sulfur electrode material (S @ CNT).
Mixing S @ CNT with polytetrafluoroethylene and carbon nanotubes according to the mass ratio of 8:1:1, uniformly coating the mixture on a current collector, performing vacuum drying to obtain an electrode plate, namely a carbon nanotube-based positive electrode material, and then assembling the lithium sulfur battery by taking the electrode plate as a positive electrode and a lithium plate as a negative electrode.
Performance testing
1. Test method
(1) The prepared hollow nitrogen-doped porous carbon spheres are subjected to microscopic morphology test under 9 ten thousand magnification by using an SU 8010-Hitachi novel high-resolution field emission scanning electron microscope.
(2) The lithium-sulfur batteries prepared by the application 1 and the application 2 are subjected to rate performance test and cycle performance test in a Xinwei test cabinet respectively. The rate performance test was performed by charging and discharging at rates of 0.2C, 0.5C, 1C, 2C, and 0.2C (1C: 1675mAh/g) in this order. The cycle performance test is carried out by constant current charging and discharging under the multiplying power of 1C.
2. Test results
As can be seen from the scanning electron microscope image in fig. 1, the particle size of the hollow nitrogen-doped porous carbon sphere prepared in example 1 is about 250nm, the hollow nitrogen-doped porous carbon sphere has a uniform size and a flat surface, and has an obvious hollow porous structure, and the hollow nitrogen-doped porous carbon spheres prepared in examples 2 to 7 have the same structure as that in example 1, and are all of the hollow porous structure. Such a structure is advantageous in accommodating more sulfur, limiting the diffusion of polysulfides, and inhibiting the shuttling effect of polysulfides. The lauryl sodium sulfate surfactant added in the comparative example 1 limits the nucleation of the zinc sulfide microspheres, and microspheres with regular shapes and uniform sizes cannot be obtained. Comparative example 2, which carries out hydrothermal reaction after adjusting pH to 8.5, and comparative example 3, which does not carry out hydrothermal reaction after adjusting pH to 8.5, are not favorable for polymerization of dopamine molecules and cannot form hollow nitrogen-doped porous carbon spheres in subsequent calcination. The calcination temperature of comparative example 4 was lowered, zinc sulfide was not completely decomposed, and the resulting carbon spheres had no hollow porous structure, could not accommodate more sulfur and effectively limit the diffusion of polysulfide.
The data in fig. 2 show that when the lithium-sulfur battery assembled in application 1 is charged and discharged at 0.2C, 0.5C, 1C, and 2C and then at 0.2C, the specific discharge capacity can reach 1253mAh/g, 1054mAh/g, 858mAh/g, 704mAh/g, and 1129mAh/g, it can be seen that the lithium-sulfur battery has a high capacity, and the battery capacity at 0.2C is the same as the initial 0.2C, which shows excellent rate capability, and the capacity and rate capability are both significantly better than the lithium-sulfur battery based on the conventional hollow carbon nanotube positive electrode material of comparative example 5 in application 2. The hollow nitrogen-doped porous carbon spheres prepared in the embodiments 2 to 7 are applied to the positive electrode of the lithium-sulfur battery, and the test results of the capacity and rate performance are equivalent to those of the experiment results in the embodiment 1. The size and morphology of the carbon spheres in comparative example 1 are not uniform, and the carbon spheres with a hollow porous structure cannot be obtained in comparative examples 2, 3 and 4, and these results lead to a large amount of dissolution and shuttling of polysulfide, so that the capacity of the assembled lithium-sulfur battery is rapidly attenuated, and the rate performance is poor.
From the data in fig. 3, it can be found that the lithium-sulfur battery assembled in application 1 can reach 521mAh/g after being charged and discharged at a rate of 1C and being cycled for 500 cycles at a high rate of 1C, and the single-cycle decay rate is only 0.07%, which proves that the assembled battery has good cycling stability, and the cycling stability is obviously superior to that of the lithium-sulfur battery assembled in application 2. The cycle stability test result of the graphene/functionalized metal-organic framework material composite intercalation prepared in the embodiments 2-7 is equivalent to the experiment result of the embodiment 1.
The results show that the preparation method takes zinc sulfide as a self-sacrificial template, conductive polymer polydopamine as a carbon precursor, prepares a polydopamine-zinc sulfide precursor (ZnS @ PDA) through hydrothermal reaction, further prepares hollow nitrogen-doped porous carbon spheres (NHPCS) after calcination, can avoid the dissolution and diffusion of polysulfide, promotes the transportation and storage of charges and ions when the prepared hollow nitrogen-doped porous carbon spheres are used as a lithium-sulfur battery anode material, introduces heteroatoms on the basis of the carbon precursor, improves the conductivity and polarity of a carbon material, and further improves the capability of the synthesized electrode material for limiting the polysulfide.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of hollow nitrogen-doped porous carbon spheres is characterized by comprising the following steps:
s1, dissolving zinc salt and a sulfur source in a solvent to obtain a first mixed solution, reacting at 90-150 ℃ for 1-3 h, separating, and drying the solid to obtain a zinc sulfide ball template; wherein the molar ratio of the zinc salt to the sulfur source is 1: 1-3;
s2, dissolving the zinc sulfide ball template prepared in the step S1 and dopamine hydrochloride in a solvent to obtain a second mixed solution, carrying out hydrothermal reaction for 2-5 h at 90-150 ℃, separating, and drying the solid to obtain a polydopamine-zinc sulfide precursor; wherein the molar ratio of the zinc sulfide sphere template to the dopamine hydrochloride is 1-5: 1;
s3, calcining the polydopamine-zinc sulfide precursor prepared in the step S3 for 1-3 h at 700-1000 ℃ in an inert atmosphere to prepare the hollow nitrogen-doped porous carbon spheres.
2. The method according to claim 1, wherein the mixture in step S1 is reacted at 100-140 ℃ for 1.5-2.5 h.
3. The method according to claim 1 or 2, wherein the hydrothermal reaction in step S2 is carried out at a temperature of 110-140 ℃ for a reaction time of 3-4 hours.
4. The method according to claim 1, wherein the calcining temperature in step S3 is 750-950 ℃, and the reaction time is 1.5-2.5 h.
5. The preparation method of claim 1, wherein the zinc salt in step S1 is one or more of zinc nitrate hexahydrate, zinc sulfate heptahydrate, zinc chloride hexahydrate, and zinc acetate dihydrate.
6. The method according to claim 1, wherein the sulfur source in step S1 is one or more of thioacetamide, thiourea, glutathione, and cysteine.
7. The method according to claim 1, wherein the temperature increase rate of the calcination in step S3 is 2-10 ℃/min.
8. The hollow nitrogen-doped porous carbon spheres prepared by the preparation method of any one of claims 1 to 7.
9. Use of the hollow nitrogen-doped porous carbon spheres of claim 8 in the preparation of a positive electrode material for a lithium-sulfur battery.
10. Use according to claim 9, characterized in that it comprises the following steps:
uniformly mixing hollow nitrogen-doped porous carbon spheres with elemental sulfur, and reacting at 120-180 ℃ for 10-20 h to obtain a hollow nitrogen-doped porous carbon sphere composite sulfur positive electrode material; wherein the mass ratio of the hollow nitrogen-doped porous carbon spheres to the elemental sulfur is 1: 3-5.
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| CN115513468A (en) * | 2022-11-22 | 2022-12-23 | 河北北方学院 | Preparation method of CNTs/OMC ordered microporous carbon nanospheres and application method of CNTs/OMC ordered microporous carbon nanospheres in lithium-sulfur battery |
| CN116042286A (en) * | 2022-11-22 | 2023-05-02 | 中国林业科学研究院林产化学工业研究所 | Preparation method and application of glucosyl/amino acid composite carbon sphere |
| CN116199206A (en) * | 2023-02-13 | 2023-06-02 | 华南理工大学 | High-mesoporosity nitrogen-sulfur double-doped lignin-based carbon material and preparation and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113410579A (en) * | 2021-05-18 | 2021-09-17 | 北京化工大学 | Monoatomic metal/nitrogen co-doped hollow carbon sphere photo/electro-catalytic material and preparation method and application thereof |
| CN113381015A (en) * | 2021-06-18 | 2021-09-10 | 郑州大学 | Nitrogen-doped hollow amorphous carbon shell material, preparation method and application |
| CN115050938A (en) * | 2022-06-18 | 2022-09-13 | 福州大学 | Preparation method of heteroatom-doped hollow carbon material and application of heteroatom-doped hollow carbon material in lithium-sulfur battery |
| CN115050938B (en) * | 2022-06-18 | 2024-03-08 | 福州大学 | Preparation method of heteroatom doped hollow carbon material and application of heteroatom doped hollow carbon material in lithium sulfur battery |
| CN115513468A (en) * | 2022-11-22 | 2022-12-23 | 河北北方学院 | Preparation method of CNTs/OMC ordered microporous carbon nanospheres and application method of CNTs/OMC ordered microporous carbon nanospheres in lithium-sulfur battery |
| CN115513468B (en) * | 2022-11-22 | 2023-02-28 | 河北北方学院 | Preparation method of CNTs/OMC ordered microporous carbon nanospheres and application method of CNTs/OMC ordered microporous carbon nanospheres in lithium-sulfur battery |
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| CN116042286B (en) * | 2022-11-22 | 2023-08-11 | 中国林业科学研究院林产化学工业研究所 | Preparation method and application of glucosyl/amino acid composite carbon sphere |
| CN116199206A (en) * | 2023-02-13 | 2023-06-02 | 华南理工大学 | High-mesoporosity nitrogen-sulfur double-doped lignin-based carbon material and preparation and application thereof |
| CN116199206B (en) * | 2023-02-13 | 2024-05-24 | 华南理工大学 | High-mesoporosity nitrogen-sulfur double-doped lignin-based carbon material and preparation and application thereof |
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