CN108281628B - Zinc-cobalt sulfide/nitrogen-doped carbon composite material and preparation method and application thereof - Google Patents

Zinc-cobalt sulfide/nitrogen-doped carbon composite material and preparation method and application thereof Download PDF

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CN108281628B
CN108281628B CN201810012293.3A CN201810012293A CN108281628B CN 108281628 B CN108281628 B CN 108281628B CN 201810012293 A CN201810012293 A CN 201810012293A CN 108281628 B CN108281628 B CN 108281628B
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zinc
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cobalt sulfide
doped carbon
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CN108281628A (en
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麦立强
韦秀娟
张延博
安琴友
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Wuhan University of Technology WUT
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Abstract

The invention belongs to the technical field of nano materials and electrochemistry, and particularly relates to a preparation method of a zinc-cobalt sulfide/nitrogen-doped carbon composite material with a yolk shell structure, which can be used as a long-life and high-rate lithium ion battery cathode active material and has a yolk shell structure with a zinc-cobalt sulfide as an inner core and nitrogen-doped carbon as an outer shell, wherein the size of the yolk shell structure is 100-200 nanometers, the size of the zinc-cobalt sulfide is 80-100 nanometers, and the thickness of the carbon outer shell is 10-20 nanometers. The invention has the beneficial effects that: the method utilizes the advantages of the metal organic framework, obtains the target product only by three steps of precursor preparation, carbon coating and vulcanization calcination, has high yield of the prepared material, good stability and strong repeatability, and makes an effort for exploring a high-rate characteristic nano material with excellent large-scale synthesis performance.

Description

Zinc-cobalt sulfide/nitrogen-doped carbon composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of nano materials and electrochemistry, and particularly relates to a preparation method of a zinc-cobalt sulfide/nitrogen-doped carbon composite material with a yolk shell structure, wherein the material can be used as a long-life and high-rate lithium ion battery cathode active material.
Background
As global economic and environmental issues become more severe, it is important to develop energy efficient and environmentally friendly devices. Lithium ion batteries are considered to be the most potential energy storage system because of their advantages of high energy density, high safety, environmental friendliness, small memory effect, low self-discharge rate, and the like. Lithium ion batteries have been widely used in portable electronic devices such as mobile phones and notebook computers. However, in order to meet the current demands for large-scale energy storage and transportation, the capacity, rate capability and service life of lithium ion batteries still need to be further improved. Among negative electrode materials, transition metal chalcogenides have attracted much attention from researchers because of their advantages such as higher specific capacity and low cost. However, the key problems restricting the wide application are: low conductivity and ion diffusion rate; the rapid capacity decay is caused by the structural pulverization caused by the huge volume change in the lithium ion intercalation and deintercalation process.
These problems can be effectively solved in terms of material structure and composition, such as reducing the size of the material to the nanometer level to shorten the ion diffusion distance and thus improve the electrochemical performance and battery life thereof. The porous material is designed and constructed, so that the volume change caused by the insertion and the removal of lithium ions can be effectively relieved, the stability of the material structure is improved, and the cycling stability and the service life of the battery are further improved. The conductive carbon has high conductivity, and can improve the charge transfer rate of the electrode material. The bimetal has a synergistic effect, so that the electrochemical performance of the material can be improved.
Disclosure of Invention
The invention aims to solve the technical problem that the preparation method of the zinc-cobalt sulfide/nitrogen-doped carbon composite material with the yolk shell structure is provided aiming at the prior art, has simple process, meets the requirement of green chemistry and has excellent electrochemical performance.
The technical scheme adopted by the invention for solving the technical problems is as follows: the zinc-cobalt sulfide/nitrogen-doped carbon composite material has an egg yolk shell structure with zinc-cobalt sulfide as an inner core and nitrogen-doped carbon as an outer shell, and has the size of 100-200 nanometers, wherein the size of the zinc-cobalt sulfide is 80-100 nanometers, and the thickness of the carbon outer shell is 10-20 nanometers.
According to the scheme, the zinc-cobalt sulfide/nitrogen-doped carbon composite material is formed by Zn0.754Co0.246S and CoS are the major phases.
The preparation method of the zinc-cobalt sulfide/nitrogen-doped carbon composite material comprises the following steps:
1) dissolving a zinc source and a cobalt source in methanol, and stirring until the zinc source and the cobalt source are completely dissolved;
2) dissolving dimethyl imidazole in methanol, and stirring until the dimethyl imidazole is completely dissolved;
3) dripping the solution obtained in the step 1) into the solution obtained in the step 2), and stirring for reaction;
4) centrifugally separating, washing and drying the product obtained in the step 3) to obtain a precursor;
5) dissolving tris (hydroxymethyl) aminomethane in absolute ethyl alcohol, and stirring until the tris (hydroxymethyl) aminomethane is completely dissolved;
6) adding the precursor obtained in the step 4) into the solution obtained in the step 5), and stirring until the precursor is completely dissolved;
7) adding dopamine hydrochloride into the solution obtained in the step 6), and stirring for reaction;
8) centrifugally separating, washing and drying the product obtained in the step 7) to obtain a Co-Zn-ZIF67@ C precursor;
9) mixing the Co-Zn-ZIF67@ C precursor obtained in the step 8) with sublimed sulfur, and calcining to obtain the zinc-cobalt sulfide/nitrogen-doped carbon composite material with the yolk shell structure.
According to the scheme, the zinc source in the step 1) is zinc nitrate hexahydrate, and the using amount is 1-2 mmol; the cobalt source is cobalt nitrate hexahydrate, and the dosage is 3-4 mmol; the amount of methanol is 30-50 ml.
According to the scheme, the dosage of the dimethyl imidazole in the step 2) is 11-13 mmol; the amount of methanol is 30-50 ml.
According to the scheme, the stirring reaction time in the step 3) is 20-30 hours.
According to the scheme, the dosage of the tris (hydroxymethyl) aminomethane in the step 5) is 1-2 mmol; the consumption of the absolute ethyl alcohol is 80-120 ml;
according to the scheme, the dosage of the precursor in the step 6) is 80-100 mg; the dopamine hydrochloride in the step 7) is 40-60mg, and the stirring reaction time is 3-4 hours.
According to the scheme, the mass ratio of the Co-Zn-ZIF67@ C precursor to the sulfur hydride in the step 9) is 1: 2; the calcination temperature is 500-700 ℃, the calcination atmosphere is flowing nitrogen, and the calcination time is 2-5 hours.
The zinc cobalt sulfide/nitrogen-doped carbon composite material is applied as a long-life and high-rate lithium ion battery cathode active material.
The invention has the beneficial effects that: the method utilizes the advantages of the metal organic framework, obtains the target product only by three steps of precursor preparation, carbon coating and vulcanization calcination, has high yield of the prepared material, good stability and strong repeatability, and makes an effort for exploring a high-rate characteristic nano material with excellent large-scale synthesis performance. The invention only adopts simple coprecipitation and calcination methods, has simple process, meets the requirements of green chemistry, has short manufacturing period and low requirements on equipment, and has great application potential. The invention shortens the diffusion distance of lithium ions and electrons, buffers the volume change in the circulation process, and further effectively improves the electrochemical performance of the material. When the material is used as a lithium ion battery cathode material, the concentration of the material is 200mA g-1When the test is carried out under the current density, the first discharge specific capacity can reach 1193mAh g-1The discharge specific capacity is still as high as 782mAh g after the circulation for 250 times-1And excellent cycle performance is shown. At 1000mA g-1The result of constant current discharge test under high current density shows that the first discharge specific capacity can reach 1154mAh g-1The specific discharge capacity is still kept at 701mAh g after 100 times of circulation-1After circulating for 300 times, the specific discharge capacity is still as high as 668mAh g-1And has good long-life performance. In the test of multiplying power performance under different current densities from small to large, the material has good capacity retention rate under different current densities in a circulating way. Test results show that the zinc-cobalt sulfide/nitrogen-doped carbon composite material with the yolk shell structure has excellent high-capacity and high-rate characteristics, and is a potential application material of a lithium ion battery with high energy density and high power density.
Drawings
FIG. 1 is an X-ray diffraction spectrum (XRD) of a zinc cobalt sulfide/nitrogen-doped carbon composite material of example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of a Zn-Co sulfide/N-doped carbon composite material according to example 1 of the present invention;
FIG. 3 is a Transmission Electron Micrograph (TEM) of a zinc cobalt sulfide/nitrogen-doped carbon composite of example 1 of the present invention;
FIG. 4 is a Transmission Electron Micrograph (TEM) and an energy dispersive X-ray spectroscopy Elemental Distribution (EDX) of a zinc cobalt sulfide/nitrogen-doped carbon composite material according to example 1 of the present invention;
FIG. 5 shows a zinc cobalt sulfide/N-doped carbon composite material at 200mA g in example 1 of the present invention-1A battery cycle performance plot at current density;
FIG. 6 shows the zinc cobalt sulfide/N-doped carbon composite material of example 1 of the present invention at 1000mA g-1A battery cycle performance plot at current density;
fig. 7 is a graph of cell cycle rate performance at different current densities for the zinc cobalt sulfide/nitrogen-doped carbon composite of example 1 of the present invention.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1: the preparation method of the zinc-cobalt sulfide/nitrogen-doped carbon composite material with the yolk shell structure comprises the following steps:
1) dissolving 1mmol of zinc nitrate hexahydrate and 3mmol of cobalt nitrate hexahydrate in 40ml of methanol, and stirring until complete dissolution;
2) dissolving 12mmol of dimethyl imidazole in 40ml of methanol, and stirring until the dimethyl imidazole is completely dissolved;
3) slowly dropwise adding the solution obtained in the step 1) into the solution obtained in the step 2), and stirring and reacting for 24 hours;
4) centrifugally separating the product obtained in the step 3), washing the product for 3 times by using absolute ethyl alcohol, and drying the product in an oven at the temperature of 60-80 ℃ to obtain a precursor;
5) dissolving 1mmol of tris (hydroxymethyl) aminomethane in 100ml of absolute ethanol, and stirring until the tris (hydroxymethyl) aminomethane is completely dissolved;
6) adding 80mg of the precursor obtained in the step 4) into the solution obtained in the step 5), and stirring until the precursor is completely dissolved;
7) adding 40mg of dopamine hydrochloride into the solution obtained in the step 6), and stirring for reacting for 3 hours;
8) centrifugally separating the product obtained in the step 7), washing the product for 3 times by using absolute ethyl alcohol, and drying the product in a drying oven at the temperature of 60-80 ℃ to obtain a carbon-coated precursor;
9) mixing the carbon-coated precursor obtained in the step 8) with sublimed sulfur according to the mass ratio of 1: 2, calcining in a tubular furnace at 600 ℃ in a flowing nitrogen atmosphere for 2 hours to obtain the zinc-cobalt sulfide/nitrogen-doped carbon composite material with the yolk shell structure.
The product of this example, a zinc cobalt sulfide/nitrogen-doped carbon composite of yolk shell structure, was used as an example, and its structure was determined by X-ray diffractometry. As shown in FIG. 1, the X-ray diffraction pattern (XRD) showed that the characteristic peak of the zinc-cobalt sulfide/nitrogen-doped carbon composite material having a yolk shell structure was well matched with Zn0.754Co0.246The standard card of the S crystal phase (JCPDS:01-089-2874) and the standard card of the CoS crystal phase (JCPDS:03-065-3418) are matched, and the Zn is proved0.754Co0.246S and CoS are the major phases. As shown in FIG. 2, the Field Emission Scanning Electron Microscopy (FESEM) test shows that the size of the yolk shell structure is 100-200 nm, and the shape is very uniform. As shown in fig. 3, the yolk shell structure of the material can be clearly seen by Transmission Electron Microscopy (TEM) test, in which the size of the zinc cobalt sulfide core is 80-100 nm and the thickness of the carbon shell is 10-20 nm. As shown in FIG. 4, the TEM-EDX element distribution diagram shows that the cobalt, zinc and sulfur elements in the composite material are mainly distributed at the structural core, and the carbon and nitrogen elements are uniformly distributed;
as shown in FIG. 5, when the material is used as a negative electrode material of a lithium ion battery, the amount of the material is 200mA g-1When the test is carried out under the current density, the first discharge specific capacity can reach 1193mAh g-1The discharge specific capacity is still as high as 782mAh g after the circulation for 250 times-1And excellent cycle performance is shown. As shown in FIG. 6, at 1000mA g-1The result of constant current discharge test under high current density shows that the first discharge specific capacity can reach 1154mAh g-1The specific discharge capacity is still kept at 701mAh g after 100 times of circulation-1After circulating for 300 times, the specific discharge capacity can reach 668mAh g-1And has good long-life performance. As shown in FIG. 7, in the rate performance test of different current densities from small to large, the material has good capacity retention rate under different current densities. The results show that the zinc-cobalt sulfide of the yolk shell structureThe nitrogen-doped carbon composite material has excellent high-capacity and high-rate characteristics, and is a potential application material of a high-energy-density and high-power-density lithium ion battery.
The preparation method of the electrode plate comprises the following steps of adopting the zinc cobalt sulfide/nitrogen-doped carbon composite material with the yolk shell structure as an active material, acetylene black as a conductive agent and carboxymethyl cellulose as a binder, fully mixing the active material, the acetylene black and the carboxymethyl cellulose according to the mass ratio of 7:2:1, carrying out ultrasonic treatment, carrying out oscillation once every twenty minutes, continuing the ultrasonic treatment for two hours, uniformly coating the active material, the acetylene black and the carboxymethyl cellulose on a copper foil, drying the copper foil in an oven at 70 ℃ for 6 hours, punching the copper foil into a wafer by using a punching machine for later use, and using 1M L iPF6The lithium ion battery is dissolved in Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl carbonate (EMC) (volume ratio is 1:1:1) to be used as electrolyte, a lithium sheet is used as a counter electrode, Celgard 2325 is a diaphragm, and CR 2016 type stainless steel is used as a battery shell to assemble the button type lithium ion battery.
Example 2:
1) dissolving 1mmol of zinc nitrate hexahydrate and 4mmol of cobalt nitrate hexahydrate in 50ml of methanol, and stirring until complete dissolution;
2) dissolving 12mmol of dimethyl imidazole in 40ml of methanol, and stirring until the dimethyl imidazole is completely dissolved;
3) slowly dropwise adding the solution obtained in the step 1) into the solution obtained in the step 2), and stirring and reacting for 25 hours;
4) centrifugally separating the product obtained in the step 3), washing the product for 3 times by using absolute ethyl alcohol, and drying the product in an oven at the temperature of 60-80 ℃ to obtain a precursor;
5) dissolving 1mmol of tris (hydroxymethyl) aminomethane in 100ml of absolute ethanol, and stirring until the tris (hydroxymethyl) aminomethane is completely dissolved;
6) adding 80mg of the precursor obtained in the step 4) into the solution obtained in the step 5), and stirring until the precursor is completely dissolved;
7) adding 40mg of dopamine hydrochloride into the solution obtained in the step 6), and stirring for reacting for 3 hours;
8) centrifugally separating the product obtained in the step 7), washing the product for 3 times by using absolute ethyl alcohol, and drying the product in a drying oven at the temperature of 60-80 ℃ to obtain a carbon-coated precursor;
9) mixing the carbon-coated precursor obtained in the step 8) with sublimed sulfur according to the mass ratio of 1: 2, calcining in a tubular furnace at 600 ℃ in a flowing nitrogen atmosphere for 2 hours to obtain the zinc-cobalt sulfide/nitrogen-doped carbon composite material with the yolk shell structure.
The product of the invention is a composite material consisting of zinc cobalt sulfide and nitrogen-doped carbon, has a hollow porous structure and has the size of 100-200 nanometers. Taking the yolk shell structure composite material obtained in the example as an example, 1000mA g-1The test result of constant current charging and discharging shows that the first discharging specific capacity can reach 1137mAh g-1The specific discharge capacity after 100 cycles is 697mAh g-1。
Example 3:
1) dissolving 2mmol of zinc nitrate hexahydrate and 3mmol of cobalt nitrate hexahydrate in 50ml of methanol, and stirring until complete dissolution;
2) dissolving 12mmol of dimethyl imidazole in 40ml of methanol, and stirring until the dimethyl imidazole is completely dissolved;
3) slowly dropwise adding the solution obtained in the step 1) into the solution obtained in the step 2), and stirring and reacting for 25 hours;
4) centrifugally separating the product obtained in the step 3), washing the product for 3 times by using absolute ethyl alcohol, and drying the product in an oven at the temperature of 60-80 ℃ to obtain a precursor;
5) dissolving 1mmol of tris (hydroxymethyl) aminomethane in 100ml of absolute ethanol, and stirring until the tris (hydroxymethyl) aminomethane is completely dissolved;
6) adding 80mg of the precursor obtained in the step 4) into the solution obtained in the step 5), and stirring until the precursor is completely dissolved;
7) adding 40mg of dopamine hydrochloride into the solution obtained in the step 6), and stirring for reacting for 3 hours;
8) centrifugally separating the product obtained in the step 7), washing the product for 3 times by using absolute ethyl alcohol, and drying the product in a drying oven at the temperature of 60-80 ℃ to obtain a carbon-coated precursor;
9) mixing the carbon-coated precursor obtained in the step 8) with sublimed sulfur according to the mass ratio of 1: 2, calcining in a tubular furnace at 600 ℃ in a flowing nitrogen atmosphere for 2 hours to obtain the zinc-cobalt sulfide/nitrogen-doped carbon composite material with the yolk shell structure.
The product of the invention is a composite material consisting of zinc cobalt sulfide and nitrogen-doped carbon, has a hollow porous structure and has the size of 100-200 nanometers. Taking the yolk shell structure composite material obtained in the example as an example, 1000mA g-1The test result of constant current charging and discharging shows that the first discharging specific capacity can reach 1120mAh g-1And the specific discharge capacity after 100 cycles is 689mAh g-1。
Example 4:
1) dissolving 1mmol of zinc nitrate hexahydrate and 3mmol of cobalt nitrate hexahydrate in 40ml of methanol, and stirring until complete dissolution;
2) dissolving 12mmol of dimethyl imidazole in 40ml of methanol, and stirring until the dimethyl imidazole is completely dissolved;
3) slowly dropwise adding the solution obtained in the step 1) into the solution obtained in the step 2), and stirring and reacting for 24 hours;
4) centrifugally separating the product obtained in the step 3), washing the product for 3 times by using absolute ethyl alcohol, and drying the product in an oven at the temperature of 60-80 ℃ to obtain a precursor;
5) dissolving 1mmol of tris (hydroxymethyl) aminomethane in 100ml of absolute ethanol, and stirring until the tris (hydroxymethyl) aminomethane is completely dissolved;
6) adding 90mg of the precursor obtained in the step 4) into the solution obtained in the step 5), and stirring until the precursor is completely dissolved;
7) adding 40mg of dopamine hydrochloride into the solution obtained in the step 6), and stirring for reacting for 3 hours;
8) centrifugally separating the product obtained in the step 7), washing the product for 3 times by using absolute ethyl alcohol, and drying the product in a drying oven at the temperature of 60-80 ℃ to obtain a carbon-coated precursor;
9) mixing the carbon-coated precursor obtained in the step 8) with sublimed sulfur according to the mass ratio of 1: 2, calcining in a tubular furnace at 600 ℃ in a flowing nitrogen atmosphere for 2 hours to obtain the zinc-cobalt sulfide/nitrogen-doped carbon composite material with the yolk shell structure.
The inventionThe product is a composite material consisting of zinc cobalt sulfide and nitrogen-doped carbon, has a hollow porous structure and has the size of 100-200 nanometers. Taking the yolk shell structure composite material obtained in the example as an example, 1000mA g-1The test result of constant current charging and discharging shows that the first discharging specific capacity can reach 1135mAh g-1And the specific discharge capacity after 100 cycles is 690mAh g-1。
Example 5:
1) dissolving 1mmol of zinc nitrate hexahydrate and 3mmol of cobalt nitrate hexahydrate in 40ml of methanol, and stirring until complete dissolution;
2) dissolving 12mmol of dimethyl imidazole in 40ml of methanol, and stirring until the dimethyl imidazole is completely dissolved;
3) slowly dropwise adding the solution obtained in the step 1) into the solution obtained in the step 2), and stirring and reacting for 24 hours;
4) centrifugally separating the product obtained in the step 3), washing the product for 3 times by using absolute ethyl alcohol, and drying the product in an oven at the temperature of 60-80 ℃ to obtain a precursor;
5) dissolving 1mmol of tris (hydroxymethyl) aminomethane in 100ml of absolute ethanol, and stirring until the tris (hydroxymethyl) aminomethane is completely dissolved;
6) adding 80mg of the precursor obtained in the step 4) into the solution obtained in the step 5), and stirring until the precursor is completely dissolved;
7) adding 40mg of dopamine hydrochloride into the solution obtained in the step 6), and stirring for reacting for 3 hours;
8) centrifugally separating the product obtained in the step 7), washing the product for 3 times by using absolute ethyl alcohol, and drying the product in a drying oven at the temperature of 60-80 ℃ to obtain a carbon-coated precursor;
9) mixing the carbon-coated precursor obtained in the step 8) with sublimed sulfur according to the mass ratio of 1: 2, placing the mixture in a tubular furnace for calcination at 550 ℃ under the condition that the calcination atmosphere is flowing nitrogen and the calcination time is 3 hours to obtain the zinc-cobalt sulfide/nitrogen-doped carbon composite material with the yolk shell structure.
The product of the invention is a composite material consisting of zinc cobalt sulfide and nitrogen-doped carbon, has a hollow porous structure and has the size of 100-200 nanometers. Taking the yolk shell structure composite material obtained in the example as an example, 1000mA g-1The constant current charging and discharging test result shows thatThe first discharge specific capacity can reach 1140mAh g-1And the specific discharge capacity after 100 cycles is 687mAh g-1。

Claims (4)

1. A preparation method of a zinc cobalt sulfide/nitrogen-doped carbon composite material as a negative electrode active material of a lithium ion battery is disclosed, wherein the zinc cobalt sulfide/nitrogen-doped carbon composite material has a hollow structure with a zinc cobalt sulfide as an inner core and nitrogen-doped carbon as an outer shell, the size of the hollow structure is 100-200 nanometers, the size of the zinc cobalt sulfide is 80-100 nanometers, and the thickness of the carbon outer shell is 10-20 nanometers, and the preparation method comprises the following steps:
1) dissolving a zinc source and a cobalt source in methanol, and stirring until the zinc source and the cobalt source are completely dissolved; the zinc source is zinc nitrate hexahydrate, and the using amount is 1-2 mmol; the cobalt source is cobalt nitrate hexahydrate, and the dosage is 3-4 mmol; the amount of methanol is 30-50 ml;
2) dissolving dimethyl imidazole in methanol, and stirring until the dimethyl imidazole is completely dissolved; the dosage of the dimethyl imidazole is 11-13 mmol; the amount of methanol is 30-50 ml;
3) dripping the solution obtained in the step 1) into the solution obtained in the step 2), and stirring for reaction;
4) centrifugally separating, washing and drying the product obtained in the step 3) to obtain a precursor;
5) dissolving tris (hydroxymethyl) aminomethane in absolute ethyl alcohol, and stirring until the tris (hydroxymethyl) aminomethane is completely dissolved;
6) adding the precursor obtained in the step 4) into the solution obtained in the step 5), and stirring until the precursor is completely dissolved;
7) adding dopamine hydrochloride into the solution obtained in the step 6), and stirring for reaction;
8) centrifugally separating, washing and drying the product obtained in the step 7) to obtain a Co-Zn-ZIF67@ C precursor;
9) mixing the Co-Zn-ZIF67@ C precursor obtained in the step 8) with sublimed sulfur, and then calcining, wherein the mass ratio of the Co-Zn-ZIF67@ C precursor to sublimed sulfur is 1: 2; and (3) calcining at the temperature of 500-700 ℃, wherein the calcining atmosphere is flowing nitrogen, and the calcining time is 2-5 hours, thus obtaining the zinc-cobalt sulfide/nitrogen-doped carbon composite material with the hollow structure.
2. The preparation method of the lithium ion battery cathode active material zinc cobalt sulfide/nitrogen-doped carbon composite material according to claim 1, characterized by comprising the following steps: the stirring reaction time of the step 3) is 20-30 hours.
3. The preparation method of the lithium ion battery cathode active material zinc cobalt sulfide/nitrogen-doped carbon composite material according to claim 1, characterized by comprising the following steps: the dosage of the tris (hydroxymethyl) aminomethane in the step 5) is 1-2 mmol; the amount of anhydrous ethanol is 80-120 ml.
4. The preparation method of the lithium ion battery cathode active material zinc cobalt sulfide/nitrogen-doped carbon composite material according to claim 1, characterized by comprising the following steps: the dosage of the precursor in the step 6) is 80-100 mg; the dopamine hydrochloride in the step 7) is 40-60mg, and the stirring reaction time is 3-4 hours.
CN201810012293.3A 2018-01-05 2018-01-05 Zinc-cobalt sulfide/nitrogen-doped carbon composite material and preparation method and application thereof Active CN108281628B (en)

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