CN108821249B - Carbon-nitrogen material, preparation method thereof, lithium-sulfur battery positive electrode material containing carbon-nitrogen material and lithium-sulfur battery - Google Patents

Carbon-nitrogen material, preparation method thereof, lithium-sulfur battery positive electrode material containing carbon-nitrogen material and lithium-sulfur battery Download PDF

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CN108821249B
CN108821249B CN201810604371.9A CN201810604371A CN108821249B CN 108821249 B CN108821249 B CN 108821249B CN 201810604371 A CN201810604371 A CN 201810604371A CN 108821249 B CN108821249 B CN 108821249B
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nitrogen
lithium
sulfur battery
sulfur
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CN108821249A (en
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柯菲
苗力孝
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Sander New Energy Technology Development Co ltd
Soundon New Energy Technology Co Ltd
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Abstract

The invention provides a carbon and nitrogen material, a preparation method thereof, a lithium-sulfur battery positive electrode material containing the carbon and nitrogen material and a lithium-sulfur battery, and relates to the technical field of new energy batteries, wherein the preparation method of the carbon and nitrogen material comprises the following steps: and sintering the mixture of the catalyst and the melamine in an inert atmosphere to obtain the carbon-nitrogen material. The carbon nitrogen nanotube prepared by the preparation method can solve the technical problem that the lithium sulfur battery in the prior art has poor cycle stability due to the fact that the intermediate product lithium polysulfide is easy to dissolve in the electrolyte, and achieves the technical effect of improving the cycle stability of the lithium sulfur battery.

Description

Carbon-nitrogen material, preparation method thereof, lithium-sulfur battery positive electrode material containing carbon-nitrogen material and lithium-sulfur battery
Technical Field
The invention relates to the technical field of new energy batteries, in particular to a carbon and nitrogen material, a preparation method thereof, a lithium-sulfur battery positive electrode material containing the carbon and nitrogen material and a lithium-sulfur battery.
Background
The lithium-sulfur battery has the advantages of light weight, large capacity, no memory effect and the like, wherein the theoretical specific capacity of the lithium-sulfur battery is up to 1675mAh/g, the theoretical energy density is up to 2600Wh/kg, and the theoretical capacity is obviously higher than that of a commercial lithium ion battery.
However, the conventional studies have revealed that lithium sulfur batteries generate lithium polysulfide as an intermediate product during charge and discharge, and lithium polysulfide is dissolved in an ether electrolyte, thereby deteriorating cycle performance of the lithium sulfur batteries.
Current research shows that doping carbon materials with nitrogen can inhibit lithium polysulfides from dissolving in the electrolyte. The carbon material is doped with nitrogen, generally, the carbon material is used as a skeleton, a few nitrogen atoms are doped with carbon atoms, and the schematic atomic structure arrangement diagram is shown in fig. 1. As can be seen from fig. 1, the nitrogen content is low, and the nitrogen atom content is generally not higher than 16% by mass, and the nitrogen has the ability to adsorb lithium polysulfide, so that when the nitrogen atom content is low, the ability of the nitrogen atom to inhibit the lithium polysulfide from dissolving in the electrolyte is greatly limited, and the cycling stability of the lithium sulfur battery is affected.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a carbon and nitrogen material and the carbon and nitrogen material obtained by the preparation method, so as to relieve the technical problem that the cycle stability of the lithium-sulfur battery is poor due to the fact that the intermediate product lithium polysulfide is easy to dissolve in an electrolyte in the prior art.
A second object of the present invention is to provide a positive electrode material for a lithium-sulfur battery and a lithium-sulfur battery comprising the same.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a preparation method of a carbon and nitrogen material comprises the following steps:
and sintering the mixture of the catalyst and the melamine in an inert atmosphere to obtain the carbon-nitrogen material.
Further, the catalyst is nickel chloride.
Further, the mass ratio of the nickel chloride to the melamine is 1-3: 7-9.
Furthermore, the sintering temperature is 450-700 ℃, and the sintering time is 3-5 h.
A carbon and nitrogen material obtained by the preparation method.
Further, the carbon and nitrogen material is carbon and nitrogen nano-tubes.
Furthermore, the pipe diameter of the carbon nitrogen nano-tube is 50-500 nm.
A positive electrode material of a lithium-sulfur battery comprises sulfur powder and the carbon and nitrogen material.
Further, the carbon and nitrogen material is carbon and nitrogen nano-tubes, and the sulfur powder is filled in the carbon and nitrogen nano-tubes.
The lithium-sulfur battery comprises a lithium cathode, electrolyte and a cathode, wherein the cathode is prepared by using the cathode material of the lithium-sulfur battery.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the carbon and nitrogen material provided by the invention takes melamine as a reaction raw material, and rapidly synthesizes the carbon and nitrogen material (such as carbon and nitrogen nano-tubes) through high-temperature sintering under the action of a catalyst (such as nickel chloride). In the preparation method, melamine is used as a raw material, and the schematic atomic arrangement structure of the carbon and nitrogen material obtained after sintering is shown in fig. 2, and it can be seen that the nitrogen content is obviously improved by comparing the schematic structural diagram of fig. 2 with that of fig. 1.
In general, the chemical formula of the carbon-nitrogen material can be represented as CnN（1-n）Wherein the value range of n is 0.3<n<0.6, therefore, the mass percent content of nitrogen atoms in the carbon-nitrogen material can reach more than 40 percent. The carbon-nitrogen material of the invention also has general carbon-nitrogen material universality, the mass percentage of nitrogen atoms can also reach more than 40%, because the nitrogen atoms have the capability of adsorbing lithium polysulfide, when the mass percentage reaches more than 40%, the carbon-nitrogen material increases the quantity of adsorbing lithium polysulfide, thereby reducing the dissolution quantity of lithium polysulfide in electrolyte and further improving the cycle stability of the lithium-sulfur battery.
In addition, in the preparation method of the invention, the carbon nitrogen material can form the carbon nitrogen nano tube by controlling the reaction conditions, particularly the reaction temperature, and when the carbon nitrogen material is the carbon nitrogen nano tube, the tubular structure of the carbon nitrogen nano tube plays a certain role in blocking lithium polysulfide generated in the tubular structure, so that the chance of the lithium polysulfide dissolving in the electrolyte is reduced, the dissolving amount of the lithium polysulfide in the electrolyte is further reduced, and the cycle stability of the lithium sulfur battery is further improved.
The positive electrode material of the lithium-sulfur battery provided by the invention comprises sulfur powder and the carbon and nitrogen material. The positive electrode material of the lithium-sulfur battery takes a carbon-nitrogen material as a carrier, and sulfur powder is loaded on the carbon-nitrogen material. On one hand, the carbon and nitrogen material can improve the conductivity of the sulfur powder; on the other hand, as the mass percentage of nitrogen in the carbon-nitrogen material is more than 40%, the adsorption amount of lithium polysulfide can be improved, and the amount of lithium polysulfide dissolved in the electrolyte is reduced, so that the cycle stability of the lithium-sulfur battery is improved. When the carbon and nitrogen material is the carbon and nitrogen nanotube, on one hand, the carbon and nitrogen nanotube has a certain barrier effect on lithium polysulfide generated in the tubular structure due to the tubular structure of the carbon and nitrogen nanotube, and the opportunity that the lithium polysulfide is dissolved in the electrolyte is reduced, so that the dissolving amount of the lithium polysulfide in the electrolyte is further reduced, and the cycle stability of the lithium-sulfur battery is improved; on the other hand, since the elemental sulfur is loaded (filled) in the carbon nitrogen nanotube, the volume change rate of the cathode material during charge and discharge can be reduced, and the cycle stability of the lithium-sulfur battery can be improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic diagram of an atomic arrangement of a conventional nitrogen-doped carbon nanotube;
FIG. 2 is a schematic view of the atomic arrangement of carbon-nitrogen nanotubes according to the present invention;
FIG. 3 is an SEM photograph of carbon-nitrogen nanotubes in example 1 of the present invention;
FIG. 4 is an SEM photograph of carbon-nitrogen nanotubes in example 3 of the present invention;
fig. 5 is a cycle stability test graph at 1C for a lithium sulfur battery fabricated using the lithium sulfur battery cathode material of example 2;
fig. 6 is a cycle stability test graph at 1C for a lithium sulfur battery fabricated using the positive electrode material for a lithium sulfur battery of comparative example 2.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In one aspect, the invention provides a preparation method of a carbon and nitrogen material, which comprises the following steps:
and sintering the mixture of the catalyst and the melamine in an inert atmosphere to obtain the carbon-nitrogen material.
The preparation method of the carbon and nitrogen material provided by the invention takes melamine as a reaction raw material, and rapidly synthesizes the carbon and nitrogen material (such as carbon and nitrogen nano-tubes) through high-temperature sintering under the action of a catalyst (such as nickel chloride). In the preparation method, melamine is used as a raw material, and the schematic atomic arrangement structure of the carbon and nitrogen material obtained after sintering is shown in fig. 2, and it can be seen that the nitrogen content is obviously improved by comparing the schematic structural diagram of fig. 2 with that of fig. 1.
In addition, in the preparation method of the carbon nitrogen nano tube, the reaction raw material is only melamine, so the production of the carbon nitrogen material can be realized by controlling the reaction temperature, the carbon nitrogen nano tube can be generated by controlling the reaction temperature, the tube diameter of the obtained carbon nitrogen nano tube can be controlled by adjusting the reaction temperature, and the method is simple and quick to operate and is suitable for industrial production.
In the present invention, the catalyst is, for example, nickel chloride, and the inert gas in the production method may be, for example, argon, helium, neon, or the like.
In some embodiments of the invention, the mass ratio of the nickel chloride to the melamine is 1-3: 7-9. The reaction can be fully carried out by controlling the weight ratio of the catalyst nickel chloride to the reaction raw material melamine. Wherein, the mass ratio of the nickel chloride to the melamine can be 1: 9. 1: 8. 1: 7. 2: 9. 2: 8. 2: 7. 3: 9. 3: 8 or 3: 7.
in some embodiments of the present invention, the sintering temperature is 450-720 ℃, the sintering time is 3-5h, carbon nitrogen nanotubes can be obtained by using the sintering process (especially the sintering temperature), and the diameter of the carbon nitrogen nanotubes is in the range of 50-500 nm. By controlling the sintering temperature and the sintering time, carbon nitrogen nanotubes with different tube diameters can be obtained, for example, when other conditions are unchanged, the carbon nitrogen nanotubes with relatively large tube diameters can be obtained within the temperature range of the invention and at lower temperature.
The sintering temperature may be, for example, but not limited to: 450 ℃, 480 ℃, 500 ℃, 530 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃, 660 ℃, 670 ℃, 680 ℃, 690 ℃ or 700 ℃; the sintering time may be, for example, without limitation, 3h, 4h, or 5 h.
In another aspect, the invention provides a carbon and nitrogen material prepared by the method.
In general, the chemical formula of the carbon-nitrogen material can be represented as CnN（1-n）Wherein the value range of n is 0.3<n<0.6, therefore, the mass percent content of nitrogen atoms in the carbon-nitrogen material can reach more than 40 percent. The carbon-nitrogen material of the invention also has general carbon-nitrogen material universality, the mass percentage of nitrogen atoms can also reach more than 40%, because the nitrogen atoms have the capability of adsorbing lithium polysulfide, when the mass percentage reaches more than 40%, the carbon-nitrogen material increases the quantity of adsorbing lithium polysulfide, thereby reducing the dissolution quantity of lithium polysulfide in electrolyte and further improving the cycle stability of the lithium-sulfur battery.
In some embodiments of the invention, the carbon nitrogen material is carbon nitrogen nanotubes. Wherein the tube diameter of the carbon-nitrogen nano tube is 50-500 nm.
When the carbon and nitrogen material is carbon and nitrogen nano-tubes, the carbon and nitrogen nano-tubes have a tubular structure, so that lithium polysulfide generated in the tubular structure is blocked to a certain extent, the chance of dissolving the lithium polysulfide in the electrolyte is reduced, the dissolving amount of the lithium polysulfide in the electrolyte is further reduced, and the cycle stability of the lithium-sulfur battery is further improved.
In a third aspect, the invention provides a lithium-sulfur battery positive electrode material, which comprises sulfur powder and the carbon-nitrogen material.
The positive electrode material of the lithium-sulfur battery provided by the invention comprises sulfur powder and the carbon and nitrogen material. The positive electrode material of the lithium-sulfur battery takes a carbon-nitrogen material as a carrier, and sulfur powder is loaded on the carbon-nitrogen material. On one hand, the carbon and nitrogen material can improve the conductivity of the sulfur powder; on the other hand, as the mass percentage of nitrogen in the carbon-nitrogen material is more than 40%, the adsorption amount of lithium polysulfide can be improved, and the amount of lithium polysulfide dissolved in the electrolyte is reduced, so that the cycle stability of the lithium-sulfur battery is improved.
In some embodiments of the present invention, the carbon and nitrogen material is carbon and nitrogen nanotubes, and the sulfur powder is filled in the carbon and nitrogen nanotubes. Wherein, the weight ratio of the sulfur powder to the carbon nitrogen nano tube can be (70-80): (20-30).
When the carbon and nitrogen material is the carbon and nitrogen nanotube, on one hand, the carbon and nitrogen nanotube has a certain barrier effect on lithium polysulfide generated in the tubular structure due to the tubular structure of the carbon and nitrogen nanotube, and the opportunity that the lithium polysulfide is dissolved in the electrolyte is reduced, so that the dissolving amount of the lithium polysulfide in the electrolyte is further reduced, and the cycle stability of the lithium-sulfur battery is improved; on the other hand, since the elemental sulfur is loaded (filled) in the carbon nitrogen nanotube, the volume change rate of the cathode material during charge and discharge can be reduced, and the cycle stability of the lithium-sulfur battery can be improved.
In the present invention, the weight ratio of the sulfur powder to the carbon nitrogen nanotube may be, for example, without limitation, 70: 30. 70: 25. 70: 20. 75: 30. 75: 25. 75: 20. 80: 30. 80: 25 or 80: 20.
the preparation method of the lithium-sulfur battery positive electrode material comprises the step of filling the sulfur powder into the carbon nitrogen nano tube to obtain the lithium-sulfur battery positive electrode material. For example, the sulfur powder and the carbon nitrogen nano tube are mixed and then are subjected to heat preservation for 10-13h at the temperature of 130-170 ℃ to obtain the lithium-sulfur battery cathode material.
The lithium-sulfur battery with the carbon-nitrogen nano-tube as the carrier is prepared by adopting a high-temperature sulfurizing method, so that sulfur can permeate into the internal structure of the carbon-nitrogen nano-tube, the mixing uniformity of the sulfur and the carbon-nitrogen nano-tube is improved, and the anisotropic performance of the positive electrode material of the lithium-sulfur battery is more consistent.
In the above embodiment, the sulfurization temperature after mixing the sulfur powder with the carbon nitrogen nanotubes may be 130 ℃, 140 ℃, 150 ℃, 160 ℃ or 170 ℃, and the incubation time may be 10 hours, 11 hours, 12 hours or 13 hours, for example.
The mixing of the sulfur powder and the carbon nitrogen nano tube can be carried out by adopting a high-energy ball milling process, and the ball milling time is 2-4 h. The sulfur powder and the carbon nitrogen nano-tube can be mixed more uniformly by adopting a high-energy ball milling process for mixing.
In another aspect, the invention provides a lithium-sulfur battery, which comprises a lithium cathode, an electrolyte and a cathode, wherein the cathode is a cathode prepared by using the cathode material of the lithium-sulfur battery.
According to the lithium-sulfur battery provided by the invention, the positive electrode adopts the positive electrode material of the lithium-sulfur battery, which can reduce the dissolution amount of lithium polysulfide in the electrolyte, and the lithium-sulfur battery has higher cycle stability.
The lithium-sulfur battery provided by the invention can be used in various electric equipment, such as automobiles, movable dining cars, communication base station power supply equipment and the like, so that the electric equipment can be used for obtaining more durable power supply.
The present invention will be described in further detail with reference to examples and comparative examples.
Example 1
The embodiment is a carbon nitrogen nanotube, and the preparation method of the carbon nitrogen nanotube comprises the following steps: and (2) mixing the following components in percentage by mass: the nickel chloride 8 and the melamine are uniformly mixed by high-energy ball milling, then are heated to 600 ℃ under the argon atmosphere condition, and are kept warm for 4 hours, so that the direct carbon nitrogen nano tube with the diameter of about 100nm is obtained, and the structure of the carbon nitrogen nano tube is shown in figure 3.
Example 2
The embodiment is a lithium-sulfur battery cathode material, which comprises sulfur powder and carbon-nitrogen nanotubes in embodiment 1, wherein the mass ratio of the sulfur powder to the carbon-nitrogen nanotubes is 70: 30.
the preparation method of the lithium-sulfur battery positive electrode material comprises the following steps: mixing the following components in percentage by mass of 70: and (3) performing high-energy ball milling on 30 sulfur powder and the carbon nitrogen nano tube for 2 hours, then putting the prepared powder into a 200ml reaction kettle, heating to 155 ℃, and preserving heat for 12 hours to obtain the lithium-sulfur battery cathode material.
Example 3
The embodiment is a carbon nitrogen nanotube, and the preparation method of the carbon nitrogen nanotube comprises the following steps: mixing the components in a mass ratio of 1: the nickel chloride and the melamine of 9 are evenly mixed by high-energy ball milling, then are heated to 550 ℃ under the argon atmosphere condition, and are kept warm for 4 hours, so that the direct carbon nitrogen nano tube with the diameter of about 200nm is obtained, and the structure of the carbon nitrogen nano tube is shown in figure 4.
Example 4
The embodiment is a lithium-sulfur battery cathode material, which comprises sulfur powder and carbon-nitrogen nanotubes in embodiment 3, wherein the mass ratio of the sulfur powder to the carbon-nitrogen nanotubes is 70: 30.
the preparation method of the lithium-sulfur battery positive electrode material comprises the following steps: mixing the following components in percentage by mass of 70: and (3) performing high-energy ball milling on 30 sulfur powder and the carbon nitrogen nano tube for 2 hours, then putting the prepared powder into a 200ml reaction kettle, heating to 155 ℃, and preserving heat for 12 hours to obtain the lithium-sulfur battery cathode material.
Example 5
The embodiment is a carbon nitrogen nanotube, and the preparation method of the carbon nitrogen nanotube comprises the following steps: and (3) mixing the following components in percentage by mass: and 7, uniformly mixing the nickel chloride and the melamine through high-energy ball milling, then heating to 600 ℃ under the argon atmosphere condition, and preserving heat for 4 hours to obtain the direct carbon nitrogen nano tube with the diameter of about 100 nm.
Example 6
The embodiment is a lithium-sulfur battery cathode material, which comprises sulfur powder and carbon-nitrogen nanotubes in embodiment 5, wherein the mass ratio of the sulfur powder to the carbon-nitrogen nanotubes is 80: 20.
the preparation method of the lithium-sulfur battery positive electrode material comprises the following steps: and (2) mixing the following components in percentage by mass: and (3) performing high-energy ball milling on 20 sulfur powder and the carbon nitrogen nano tube for 2 hours, then putting the prepared powder into a 200ml reaction kettle, heating to 155 ℃, and preserving heat for 12 hours to obtain the lithium-sulfur battery cathode material.
Example 7
The embodiment is a carbon nitrogen nanotube, and the preparation method of the carbon nitrogen nanotube comprises the following steps: and (2) mixing the following components in percentage by mass: and (3) uniformly mixing the nickel chloride 8 and the melamine through high-energy ball milling, then heating to 500 ℃ under the argon atmosphere condition, and preserving heat for 4 hours to obtain the direct carbon nitrogen nano tube with the diameter of about 200 nm.
Example 8
The embodiment is a lithium-sulfur battery cathode material, which comprises sulfur powder and carbon-nitrogen nanotubes in embodiment 7, wherein the mass ratio of the sulfur powder to the carbon-nitrogen nanotubes is 80: 20.
the preparation method of the lithium-sulfur battery positive electrode material comprises the following steps: and (2) mixing the following components in percentage by mass: and (3) performing high-energy ball milling on 20 sulfur powder and the carbon nitrogen nano tube for 2 hours, then putting the prepared powder into a 200ml reaction kettle, heating to 155 ℃, and preserving heat for 12 hours to obtain the lithium-sulfur battery cathode material.
Example 9
The embodiment is a carbon nitrogen nanotube, and the preparation method of the carbon nitrogen nanotube comprises the following steps: and (2) mixing the following components in percentage by mass: and (3) uniformly mixing the nickel chloride 8 and the melamine through high-energy ball milling, then heating to 600 ℃ under the argon atmosphere condition, and preserving heat for 2 hours to obtain the direct carbon nitrogen nano tube with the diameter of about 100 nm.
Example 10
The embodiment is a lithium-sulfur battery cathode material, which comprises sulfur powder and carbon-nitrogen nanotubes in embodiment 9, wherein the mass ratio of the sulfur powder to the carbon-nitrogen nanotubes is 80: 20.
the preparation method of the lithium-sulfur battery positive electrode material comprises the following steps: and (2) mixing the following components in percentage by mass: and (3) performing high-energy ball milling on 20 sulfur powder and the carbon nitrogen nano tube for 2 hours, then putting the prepared powder into a 200ml reaction kettle, heating to 155 ℃, and preserving heat for 12 hours to obtain the lithium-sulfur battery cathode material.
Example 11
The embodiment is a lithium-sulfur battery cathode material, which comprises sulfur powder and carbon-nitrogen nanotubes in embodiment 9, wherein the mass ratio of the sulfur powder to the carbon-nitrogen nanotubes is 70: 30.
the preparation method of the lithium-sulfur battery positive electrode material comprises the following steps: mixing the following components in percentage by mass of 70: and (3) performing high-energy ball milling on 30 sulfur powder and the carbon nitrogen nano tube for 2 hours, then putting the prepared powder into a 200ml reaction kettle, heating to 155 ℃, and preserving heat for 12 hours to obtain the lithium-sulfur battery cathode material.
Comparative example 1
The comparative example is a nitrogen-doped carbon nanotube, and the preparation method of the carbon nanotube comprises the following steps: and (3) placing the commercial carbon nano tube in an ammonia atmosphere, and sintering for 5h at 500 ℃ to obtain the nitrogen-doped carbon nano tube.
Comparative example 2
The comparative example is a lithium-sulfur battery cathode material, which comprises sulfur powder and the nitrogen-doped carbon nanotube in the comparative example 1, wherein the mass ratio of the sulfur powder to the nitrogen-doped carbon nanotube is 70: 30.
the preparation method of the lithium-sulfur battery positive electrode material comprises the following steps: mixing the following components in percentage by mass of 70: and (3) performing high-energy ball milling on 30 sulfur powder and the nitrogen-doped carbon nano tube for 2 hours, then putting the prepared powder into a 200ml reaction kettle, heating to 155 ℃, and preserving heat for 12 hours to obtain the lithium-sulfur battery anode material.
Control test
A lithium sulfur battery was assembled using the positive electrode materials for lithium sulfur batteries provided in example 2 and comparative example 2, respectively.
The lithium-sulfur battery comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate is prepared by grinding a conductive agent, a binder and positive materials respectively provided in example 2 and comparative example 2 into slurry by NMP, coating the slurry on an aluminum foil, and drying the slurry at 60 ℃ for 12 hours; the negative plate is a lithium foil, the diaphragm adopts a Celegard2400 polypropylene film, the electrolyte consists of three components of lithium salt, solvent and additive, wherein the volume ratio of dimethyl ethane (DME) to 1, 3-Dioxolane (DOL) is 1:1 to form a mixed solvent, and respectively dissolving lithium salt lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) and additive lithium nitrate in the mixed solvent, wherein the concentrations are respectively 1.0mol/L and 0.1 mol/L. The electrolyte is formed by mixing 1.0mol/L LiTFS solution and 0.1mol/L LiNO3 solution, and the volume ratio of the LiTFS solution to the LiNO3 solution is 1: 1; the above components are assembled in a 2032 type button cell in a structure of positive plate/diaphragm/negative plate, and the whole cell assembly process is completed in a glove box.
After the assembly was completed, the cycle performance of each group of lithium sulfur batteries was tested at 1C, and the test results are shown in fig. 5 and 6.
As can be seen from fig. 5, the cycle number of the lithium-sulfur battery obtained by using the positive electrode material composition of the lithium-sulfur battery provided in example 2 can reach 500 times, and after 500 cycles, the specific capacity of the lithium-sulfur battery is still maintained above 400 mAh/g.
As can be seen from fig. 6, the specific capacity of the lithium sulfur battery obtained using the positive electrode material composition for lithium sulfur battery provided in comparative example 2 was reduced to about 400mAh/g at a cycle number of about 10 cycles. When the cycle times are 100 times, the specific capacity is almost reduced to be less than 100 mAh/g.
In addition, as can be seen from fig. 5 and 6, the initial specific charge/discharge capacity of the lithium-sulfur battery obtained by using the positive electrode material composition of the lithium-sulfur battery provided in example 2 can reach 1400mAh/g, while the initial specific charge/discharge capacity of the lithium-sulfur battery obtained by using the positive electrode material composition of the lithium-sulfur battery provided in comparative example 2 is about 1000 mAh/g.
In summary, on one hand, the positive electrode material of the lithium-sulfur battery prepared by the carbon and nitrogen material provided by the invention in the battery has higher nitrogen content, so that the capacity of adsorbing lithium polysulfide is improved, and the amount of the lithium polysulfide dissolved in electrolyte is reduced; on the other hand, the carbon-nitrogen material provided by the invention is the carbon-nitrogen nano tube in the battery, and the carbon-nitrogen nano tube can block the polysulfide lithium compound to a certain extent due to the tubular structure of the carbon-nitrogen nano tube, so that the chance of dissolving the polysulfide lithium compound in the electrolyte is reduced, and the amount of the lithium polysulfide compound dissolved in the electrolyte is reduced; based on the two aspects, the carbon-nitrogen material provided by the invention is used as the positive electrode material of the lithium-sulfur battery, and compared with the carbon material doped with nitrogen as the positive electrode material of the lithium-sulfur battery, the cycle stability of the lithium-sulfur battery is obviously improved. In addition, the carbon and nitrogen improve the conductivity of the sulfur powder due to the addition of the carbon and nitrogen material, so that the initial charge-discharge specific capacity of the lithium-sulfur battery is improved.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (1)

1. The preparation method of the carbon and nitrogen material is characterized by comprising the following steps:
placing the mixture of the catalyst and the melamine in an inert atmosphere for sintering to obtain the carbon-nitrogen material;
the catalyst is nickel chloride;
the mass ratio of the nickel chloride to the melamine is 1-3: 7-9;
the sintering temperature is 450-700 ℃, and the sintering time is 3-5 h;
the chemical formula of the carbon-nitrogen material is CnN（1-n）Wherein the value range of n is 0.3<n<0.6, the mass percent of nitrogen atoms in the carbon and nitrogen material reaches more than 40 percent;
the carbon and nitrogen material is carbon and nitrogen nano-tubes.
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