CN113036097B - Sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material and preparation method thereof - Google Patents

Sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material and preparation method thereof Download PDF

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CN113036097B
CN113036097B CN202110153758.9A CN202110153758A CN113036097B CN 113036097 B CN113036097 B CN 113036097B CN 202110153758 A CN202110153758 A CN 202110153758A CN 113036097 B CN113036097 B CN 113036097B
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electrode material
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高晓艳
张孝杰
李东
洪坤
张强华
潘颖韬
桂应梅
李明鲜
吉华玉
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Huaiyin Institute of Technology
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Abstract

The invention relates to a sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material and a preparation method thereof, which sequentially comprises the following steps of S1: inorganic nickel salt and hexamethylenetetramine are mixed according to a molar ratio of 1: (1-7) respectively dissolving in a solvent to obtain an inorganic nickel salt solution and a hexamethylenetetramine solution; s2: uniformly mixing an inorganic nickel salt solution and a hexamethylenetetramine solution in a dropwise manner, and then standing and growing for 12-50h at 80-160 ℃ to obtain a primary product containing the nickel-based metal organic framework template; s3: and (5) centrifugally separating the initial product containing the nickel-based metal organic framework template at 2000-4000r/min, and respectively cleaning the initial product for 3 times by using deionized water and absolute ethyl alcohol to obtain the clean nickel-based metal organic framework template. The composite electrode material prepared by the invention has high energy storage specific capacity, good cycle stability, simple preparation method and low cost, and is easy to realize industrial large-scale application.

Description

Sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material and preparation method thereof
Technical Field
The invention relates to a sulfur vacancy nitrogen-doped carbon-coated nickel sulfide composite electrode material, and also relates to a circular electrode prepared by adopting the nitrogen-doped carbon-coated sulfur vacancy composite electrode material and applied to a sodium ion battery, belonging to the technical field of negative electrode materials of the sodium ion battery.
Background
Due to the excessive consumption of non-renewable energy sources, the reasonable development and utilization of renewable clean energy sources such as wind energy, solar energy, geothermal energy and the like are imperative. However, various renewable energy sources are restricted by regional and environmental factors and have serious randomness and intermittency. Therefore, it is important to realize optimal management and large-scale storage of energy. Since the commercialization of lithium ion batteries, lithium ion batteries have been the mainstream in the field of energy storage, which greatly assists the storage and utilization of clean energy. However, due to the uneven distribution and limited reserves of lithium resources, the cost of lithium ion batteries is rapidly increasing, and therefore, an energy storage device based on abundant resources is required to be found to partially replace the lithium ion batteries.
Because of abundant sodium resource reserves and relatively low raw material cost, the sodium ion battery becomes a potential choice of a new generation of large-scale energy storage technology. However, due to the high standard electrode potential of sodium and the large radius of sodium ions, the conventional electrode material for lithium ion batteries cannot meet the application requirements of sodium ion batteries. Therefore, there is an urgent need to develop advanced electrode materials having high specific capacity and rapid sodium ion transport kinetics. Transition metal chalcogenides are widely used in sodium ion batteries due to their open framework structure and good electrochemical performance. The nickel sulfide as a typical metal sulfide has the advantages of large interlayer spacing and the like, so that when the nickel sulfide is used as a negative electrode material of a sodium ion battery, rapid sodium ion transmission can be realized. However, the low conductivity and large volume expansion effect of nickel sulfide lead to poor specific capacity, rate capability and cycle life. The lamellar structure material belongs to the category of two-dimensional materials, and is a research hotspot in recent years due to excellent physicochemical properties, unique characteristics such as thermoelectricity, conductivity, superconductivity and the like, and the conventional preparation technology at present comprises chemical vapor deposition, redox intercalation stripping, ultrasonic stripping and the like. However, the technologies have the defects of low preparation efficiency, complex process, difficulty in large-scale industrial preparation and the like. Therefore, how to effectively improve the cycling stability and rate capability of the metal sulfide negative electrode material, especially the electrode material with a lamellar structure, is an important subject in the research and development field.
Disclosure of Invention
The invention aims to provide a sulfur vacancy nitrogen-doped carbon-coated nickel sulfide composite electrode material and a preparation method thereof, and provides the sulfur vacancy nitrogen-doped carbon-coated nickel sulfide composite electrode material, wherein sulfur vacancies exist in nitrogen-doped carbon-coated sulfur vacancy nickel sulfide particles in the composite electrode material, and can effectively improve the excitation of excessive electrons around metal atoms, so that the center of negative charges is formed to attract sodium ions, and the rapid transmission of the sodium ions is promoted; in addition, the material can also be used as a charge carrier, so that the conductivity is greatly improved; and provides additional reactive sites for redox reactions to increase capacitance, has high specific capacity and good cycling stability, and can effectively solve the problems in the background art.
In order to achieve the purpose, the invention adopts the technical scheme that:
a sulfur vacancy nitrogen-doped carbon-coated nickel sulfide composite electrode material is characterized in that nitrogen-doped carbon-coated nickel sulfide exists in a sheet structure, the size of the sheet structure is 300-800nm, the sheet structure is composed of 20-80nm nickel sulfide particles, sulfur vacancies exist in the particles, and the nitrogen-doped carbon-coated nickel sulfide nanosheet composite material is prepared by heat treatment of a metal organic framework.
A preparation method of a sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material sequentially comprises the following steps,
s1: inorganic nickel salt and hexamethylenetetramine are mixed according to a molar ratio of 1: (1-7) respectively dissolving in a solvent to obtain an inorganic nickel salt solution and a hexamethylenetetramine solution;
s2: uniformly mixing an inorganic nickel salt solution and a hexamethylenetetramine solution in a dropwise manner, and then standing and growing for 12-50h at 80-160 ℃ to obtain a primary product containing the nickel-based metal organic framework template;
s3: centrifuging at 2000-4000r/min to separate the initial product containing the nickel-based metal organic framework template, and respectively cleaning for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean nickel-based metal organic framework template;
s4: and (3) mixing the clean nickel-based metal organic framework template obtained in the step S3 with a sulfur source in a mass ratio of 1: (1-6) and adding 1-5% of oxidant, mixing, placing in a tube furnace, under the protection of high-purity argon, raising the temperature to 400-750 ℃ at the temperature-raising rate of 1-15 ℃/min, and keeping the temperature for 4-10h to perform pyrolysis reaction;
s5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material.
Preferably, the inorganic nickel salt in S1 is nickel chloride, nickel acetate, nickel nitrate or nickel sulfate.
Further, the concentration of the nickel salt solution in the S1 is 10-500 mmol L-1The concentration of the hexamethylene tetramine solution is 30-1000 mmol L-1。
Preferably, the solvent in S1 is one or more of deionized water, ethanol, methanol, and acetone.
Further, the sulfur source in S4 is thiourea or sublimed sulfur.
Preferably, the oxidant in S4 is one of sodium nitrate and ammonium nitrate or a mixture thereof.
Compared with the prior art, the invention has the following beneficial effects:
in the pyrolysis process of the nickel-based metal organic framework template, due to the decomposition of organic ligands into small molecule gases such as CO, CO2, NH3, H2O and the like, a porous structure is formed in the electrode material, and the structure can effectively promote the gap diffusion of sodium ions in the electrode material;
the sodium ion transmission rate in the nickel sulfide electrode material can be greatly improved by constructing a proper amount of sulfur vacancies in the crystal structure of the sulfur vacancy nitrogen-doped carbon-coated nickel sulfide composite electrode material to provide efficient vacancy diffusion. And a porous conductive network is formed, so that the conductivity of the electrode material is improved, and the charge transfer resistance is reduced. The volume expansion effect of sodium ions in the process of de-intercalation in the electrode material is relieved, so that the sulfur vacancy nitrogen doped carbon-coated nickel sulfide electrode material obtained based on the method can show good electrochemical performance when being used as a sodium ion battery cathode material;
there are two forms of ion transport in the electrode material: interstitial diffusion and vacancy diffusion. The rapid transmission of sodium ions can be realized only by optimizing and regulating two forms of ion transmission, and the performance of the sodium ion battery can be comprehensively improved. The invention utilizes the metal organic framework to regulate and control the gap diffusion and vacancy diffusion of the nickel sulfide electrode material, and improves the transmission dynamics of sodium ions in the nickel sulfide electrode material. The metal organic framework is used as a crystal material consisting of metal ions and organic ligands through self-assembly, and has the advantages of high porosity, large specific surface area, adjustable structure and function and the like, so that the metal organic framework becomes an energy storage material with great development potential;
the preparation method is simple, low in cost and easy to realize industrial large-scale application;
the nickel-based metal organic framework template prepared by the invention is of a three-dimensional sheet structure, the surface is smooth, and the size, the size and the length are 1-2 mu m;
a round electrode manufactured by adopting the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material is assembled into a CR2025 button cell in a glove box with water and oxygen contents of less than 0.5ppm by taking a metal sodium sheet as a reference electrode and a counter electrode and Whatman GF/D as a diaphragm. The electrolyte component is a mixed solvent (mass ratio of 1:1: 1) of 1M NaClO4 dissolved in ethylene carbonate, diethyl carbonate and ethyl methyl carbonate. The CR2025 button cell is charged and discharged at constant current (0.005-3.0V) by a blue cell tester CT2001A, the current density is 200mA/g, and the sodium storage capacity is up to 280-320 mAh/g; after 300 times of cyclic charge and discharge, the capacity retention rate is higher than 93%, and the cyclic stability is better.
Drawings
FIG. 1 is a scanning electron micrograph of a sulfur-vacancy nitrogen-doped carbon-coated nickel sulfide composite material prepared in example 1 of the present invention;
FIG. 2 is a graph of the cycle performance of a sodium ion battery of a sulfur vacancy nitrogen doped carbon coated nickel sulfide composite prepared in example 1 of the present invention;
fig. 3 is a graph of the rate capability of a sodium ion battery made from the sulfur-vacancy nitrogen-doped carbon-coated nickel sulfide composite material prepared in example 2 of the invention;
FIG. 4 is a graph of the sodium ion battery cycle performance of the nickel sulfide material prepared in comparative example 1 of the present invention;
fig. 5 is a graph of the rate cycling performance of a sodium ion battery of the nickel sulfide material prepared in comparative example 1 of the present invention.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
Example 1
The preparation method of the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material sequentially comprises the following steps:
s1: dissolving 5mmol of nickel acetate in 20mL of deionized water to obtain a nickel acetate solution; dissolving 5mmol of hexamethylenetetramine in 20mL of ethanol to obtain a hexamethylenetetramine solution;
s2: uniformly mixing a nickel acetate solution and a hexamethylenetetramine solution in a dropwise manner, and then standing and growing for 20 hours at 100 ℃ to obtain an initial product containing the nickel-based metal organic framework template;
s3: centrifugally separating a primary product containing the nickel-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean nickel-based metal organic framework template; as shown in fig. 1, the nickel-based metal organic framework template prepared in example 1 has a flower-like structure and a smooth surface.
S4: mixing the clean nickel-based metal organic framework template obtained in the step S3 with thiourea in a mass ratio of 1: 4, under the protection of high-purity argon, raising the temperature to 600 ℃ at a temperature rise rate of 3 ℃/min, and keeping the temperature for 6 hours to carry out pyrolysis reaction;
s5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material.
Example 2
The preparation method of the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material sequentially comprises the following steps:
s1: dissolving 10mmol of nickel nitrate in 40mL of deionized water to obtain a nickel acetate solution; dissolving 30mmol of hexamethylenetetramine in 40mL of methanol to obtain a hexamethylenetetramine solution;
s2: uniformly mixing a nickel nitrate solution and a hexamethylenetetramine solution in a dropwise manner, and then standing and growing for 24 hours at 80 ℃ to obtain an initial product containing the nickel-based metal organic framework template;
s3: centrifugally separating a primary product containing the nickel-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean nickel-based metal organic framework template;
s4: and (3) mixing the clean nickel-based metal organic framework template obtained in the step S3 with sublimed sulfur according to the mass ratio of 1: 5, after mixing, under the protection of high-purity argon, raising the temperature to 750 ℃ at a temperature rise rate of 5 ℃/min, and keeping the temperature for 8 hours to carry out pyrolysis reaction;
s5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material.
Example 3
The preparation method of the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material sequentially comprises the following steps:
s1: dissolving 10mmol of nickel chloride in 50mL of deionized water to obtain a nickel acetate solution; dissolving 70mmol of hexamethylenetetramine in 100mL of acetone to obtain a hexamethylenetetramine solution;
s2: uniformly mixing a nickel chloride solution and a hexamethylenetetramine solution in a dropwise manner, and then standing and growing for 15 hours at 150 ℃ to obtain an initial product containing the nickel-based metal organic framework template;
s3: centrifugally separating a primary product containing the nickel-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean nickel-based metal organic framework template;
s4: mixing the clean nickel-based metal organic framework template obtained in the step S3 with thiourea in a mass ratio of 1: 6, under the protection of high-purity argon, raising the temperature to 400 ℃ at a temperature rise rate of 10 ℃/min, and keeping the temperature for 10 hours to carry out pyrolysis reaction;
s5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material.
Example 4
The preparation method of the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material sequentially comprises the following steps:
s1: nickel nitrate and hexamethylenetetramine are mixed according to a molar ratio of 1: 5, respectively dissolving the nickel nitrate solution and the hexamethylenetetramine solution in an ethanol solvent to obtain a nickel nitrate solution and a hexamethylenetetramine solution;
s2: uniformly mixing a nickel nitrate solution and a hexamethylenetetramine solution in a dropwise manner, and then standing and growing for 12 hours at 160 ℃ to obtain an initial product containing the nickel-based metal organic framework template;
s3: centrifugally separating a primary product containing the nickel-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean nickel-based metal organic framework template;
s4: and (3) mixing the clean nickel-based metal organic framework template obtained in the step S3 with sublimed sulfur according to the mass ratio of 1: 3, under the protection of high-purity argon, raising the temperature to 600 ℃ at a temperature rise rate of 15 ℃/min, and keeping the temperature for 5 hours to carry out pyrolysis reaction;
s5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material.
Example 5
The preparation method of the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material sequentially comprises the following steps:
s1: nickel chloride and hexamethylenetetramine are mixed according to a molar ratio of 1: 7, respectively dissolving the nickel chloride solution and the hexamethylene tetramine solution in a methanol solvent to obtain a nickel chloride solution and a hexamethylene tetramine solution;
s2: uniformly mixing a nickel chloride solution and a hexamethylenetetramine solution in a dropwise manner, and then standing and growing for 50 hours at 120 ℃ to obtain an initial product containing the nickel-based metal organic framework template;
s3: centrifugally separating a primary product containing the nickel-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean nickel-based metal organic framework template;
s4: mixing the clean nickel-based metal organic framework template obtained in the step S3 with thiourea in a mass ratio of 1: 4, under the protection of high-purity argon, raising the temperature to 500 ℃ at a temperature rise rate of 10 ℃/min, and keeping the temperature for 10 hours to carry out pyrolysis reaction;
s5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material.
Example 6
The preparation method of the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material sequentially comprises the following steps:
s1: nickel sulfate and hexamethylenetetramine are mixed according to a molar ratio of 1: 6, respectively dissolving the nickel sulfate and the hexamethylenetetramine in deionized water to obtain nickel sulfate and hexamethylenetetramine solutions;
s2: uniformly mixing nickel sulfate and a hexamethylenetetramine solution in a dropwise manner, and then standing and growing for 30 hours at 150 ℃ to obtain an initial product containing the nickel-based metal organic framework template;
s3: centrifugally separating a primary product containing the nickel-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean nickel-based metal organic framework template;
s4: and (3) mixing the clean nickel-based metal organic framework template obtained in the step S3 with sublimed sulfur according to the mass ratio of 1:1, under the protection of high-purity argon, raising the temperature to 750 ℃ at a temperature rise rate of 15 ℃/min, and keeping the temperature for 9 hours to carry out pyrolysis reaction;
s5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material.
Example 7
The invention discloses a preparation method of a sulfur vacancy nitrogen doped carbon-coated nickel sulfide composite electrode material, which sequentially comprises the following steps of:
s1: nickel acetate and hexamethylenetetramine are mixed according to a molar ratio of 1: 4, respectively dissolving the nickel acetate and the hexamethylenetetramine in an ethanol solvent to obtain nickel acetate and hexamethylenetetramine solutions;
s2: uniformly mixing a nickel acetate solution and a hexamethylenetetramine solution in a dropwise manner, and then standing and growing for 18 hours at 130 ℃ to obtain an initial product containing the nickel-based metal organic framework template;
s3: centrifugally separating a primary product containing the nickel-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean nickel-based metal organic framework template;
s4: and (3) mixing the clean nickel-based metal organic framework template obtained in the step S3 with sublimed sulfur according to the mass ratio of 1: 5, after mixing, under the protection of high-purity argon, raising the temperature to 500 ℃ at a temperature rise rate of 8 ℃/min, and keeping the temperature for 4 hours to carry out pyrolysis reaction;
s5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the sulfur vacancy nitrogen-doped carbon-coated nickel sulfide composite electrode material.
Example 8
The preparation method of the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material sequentially comprises the following steps:
s1: nickel sulfate and hexamethylenetetramine are mixed according to a molar ratio of 1: 6, respectively dissolving the nickel sulfate solution and the hexamethylene tetramine solution in an acetone solvent to obtain a nickel sulfate solution and a hexamethylene tetramine solution;
s2: uniformly mixing a nickel sulfate solution and a hexamethylenetetramine solution in a dropwise manner, and then standing and growing for 24 hours at 140 ℃ to obtain an initial product containing the nickel-based metal organic framework template;
s3: centrifugally separating a primary product containing the nickel-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean nickel-based metal organic framework template;
s4: mixing the clean nickel-based metal organic framework template obtained in the step S3 with thiourea in a mass ratio of 1: 6, under the protection of high-purity argon, heating to 700 ℃ at a heating rate of 14 ℃/min, and keeping the temperature for 6 hours to carry out pyrolysis reaction;
s5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material.
Example 9
The preparation method of the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material sequentially comprises the following steps:
s1: nickel nitrate and hexamethylenetetramine are mixed according to a molar ratio of 1: 4, respectively dissolving the nickel nitrate solution and the hexamethylenetetramine solution in an ethanol solvent to obtain a nickel nitrate solution and a hexamethylenetetramine solution;
s2: uniformly mixing a nickel nitrate solution and a hexamethylenetetramine solution in a dropwise manner, and then standing and growing for 40 hours at 110 ℃ to obtain an initial product containing the nickel-based metal organic framework template;
s3: centrifugally separating a primary product containing the nickel-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean nickel-based metal organic framework template;
s4: mixing the clean nickel-based metal organic framework template obtained in the step S3 with thiourea in a mass ratio of 1: 5, after mixing, under the protection of high-purity argon, heating to 600 ℃ at a heating rate of 13 ℃/min, and keeping the temperature for 7 hours to carry out pyrolysis reaction;
s5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material.
Example 10
The sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material prepared in examples 1 to 9, the binder carboxymethylcellulose sodium and the conductive agent Super-P were dispersed in deionized water at a mass ratio of 75: 15: 10 to prepare a slurry, which was uniformly coated on a 9 μm thick copper foil, and vacuum-dried for 12 hours to prepare a circular electrode having a diameter of 14 mm.
A metal sodium sheet is used as a reference electrode and a counter electrode, Whatman GF/D is used as a diaphragm, and the CR2025 button cell is assembled in a glove box with the water and oxygen contents of less than 0.5 ppm. The electrolyte component is a mixed solvent of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate in which 1M NaClO4 is dissolved in a mass ratio of 1:1: 1. The CR2025 button cell is subjected to constant-current charging and discharging through a blue battery tester CT2001A, the voltage value is 0.005-3V, the current density is 200mA/g, the cycle performance of charging and discharging 300 times of the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material is tested, and the electrochemical performance results of each electrode material are shown in Table 1. The assembled cell of example 2 was cycled for 10 cycles at current densities of 0.1, 0.2, 0.5, 1.0, 2.0, 5.0, and 10.0A/g, and then returned to 0.1A/g for rate capability testing.
TABLE 1
Examples Sodium storage capacity (mAh/g) at a current density of 200mA/g Capacity retention (%) of battery cycled 300 times
1 318 93.8
2 327 92.5
3 328 94.3
4 280 95.4
5 298 96.1
6 313 93.9
7 350 96.5
8 309 95.2
9 314 94.8
The sodium ion battery was cycled 100 times at a current density of 200mA/g using the CR2025 button cell assembled in example 1. The obtained result is shown in fig. 2, the sodium ion battery cycle performance of the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material prepared in example 1 is 200mA/g, the sodium storage capacity after 100 times is 310 mAh/g, and the sodium ion battery has good cycle stability. The assembled CR2025 button cells of example 2 were cycled charge and discharge 5 cycles at current densities of 0.1, 0.2, 0.5, 1.0, 2.0, and 5.0A/g, and then returned to 0.1A/g for rate capability testing, with the results shown in fig. 3. The results show that when the current density is returned to 0.1A/g from 5.0A/g, the sodium storage performance of the battery can be returned to the initial value, and the electrode material has good rate performance.
Comparative example 1
Nickel acetate and hexamethylenetetramine are mixed according to a molar ratio of 1: 3, dissolving the mixture in an absolute ethyl alcohol solvent respectively to obtain nickel acetate and a hexamethylenetetramine solution; and then uniformly mixing the two solutions, adding thiourea with the mass being 3 times of that of the nickel acetate, and standing and growing for 10 hours at 120 ℃ to obtain a primary product containing the nickel sulfide-based organic framework template. And (3) placing the initial product in a tube furnace, under the protection of high-purity argon, raising the temperature to 700 ℃ at the temperature rise rate of 13 ℃/min, and keeping the temperature for 5 hours for carrying out pyrolysis reaction to obtain the electrode material. The materials were assembled into sodium ion batteries according to the method of example 10, and subjected to cycle and rate performance tests, with the results shown in fig. 4 and 5. The result shows that the cycling stability and rate capability of the electrode material prepared by the method are far lower than the performance of the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material disclosed by the invention.
Comparative example 2
At present, enterprises and research and development institutions at home and abroad, such as Liaoning starry sky sodium-electricity battery limited company, Zhongke sea sodium science and technology limited company, Japan electric nitre, British Faradion company and the like commercialize sodium-ion batteries, the sodium storage performance of the cathode material is 250 mAh/g, and the difference is certain compared with the sodium storage performance of the invention. Therefore, the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material prepared by the invention has good sodium storage performance.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (5)

1. A preparation method of a sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material is characterized by comprising the following steps: the nitrogen-doped carbon-coated nickel sulfide in the composite electrode material exists in a sheet structure, the size of the sheet structure is 300-800nm, the sheet structure is composed of nickel sulfide particles with the size of 20-80nm, sulfur vacancies exist in the particles, and the nitrogen-doped carbon-coated nickel sulfide nanosheet composite material is prepared by heat treatment of a metal organic framework;
the method specifically comprises the following steps of,
s1: inorganic nickel salt and hexamethylenetetramine are mixed according to a molar ratio of 1: (1-7) are dissolved inObtaining inorganic nickel salt solution and hexamethylenetetramine solution in a solvent; the concentration of the nickel salt solution is 10-500 mmol L-1 The concentration of the hexamethylene tetramine solution is 30-1000 mmol L-1 ；
S2: uniformly mixing an inorganic nickel salt solution and a hexamethylenetetramine solution in a dropwise manner, and then standing and growing for 12-50h at 80-160 ℃ to obtain a primary product containing the nickel-based metal organic framework template;
s3: centrifuging at 2000-4000r/min to separate the initial product containing the nickel-based metal organic framework template, and respectively cleaning for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean nickel-based metal organic framework template;
s4: and (3) mixing the clean nickel-based metal organic framework template obtained in the step S3 with a sulfur source in a mass ratio of 1: (1-6) and adding 1-5% of oxidant, mixing, placing in a tube furnace, under the protection of high-purity argon, raising the temperature to 400-750 ℃ at the temperature-raising rate of 1-15 ℃/min, and keeping the temperature for 4-10h to perform pyrolysis reaction;
s5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material.
2. The method for preparing the sulfur-vacancy nitrogen-doped carbon-coated nickel sulfide composite electrode material according to claim 1, wherein the method comprises the following steps: the inorganic nickel salt in the S1 is nickel chloride, nickel acetate, nickel nitrate or nickel sulfate.
3. The method for preparing the sulfur-vacancy nitrogen-doped carbon-coated nickel sulfide composite electrode material according to claim 1, wherein the method comprises the following steps: the solvent in the S1 is one or more of deionized water, ethanol, methanol and acetone.
4. The method for preparing the sulfur-vacancy nitrogen-doped carbon-coated nickel sulfide composite electrode material as claimed in claim 1, wherein the sulfur source in S4 is thiourea or sublimed sulfur.
5. The method for preparing the sulfur-vacancy nitrogen-doped carbon-coated nickel sulfide composite electrode material as claimed in claim 1, wherein the method comprises the following steps: and the oxidant in the S4 is one or a mixture of sodium nitrate and ammonium nitrate.
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