CN113328061B - Preparation method of positive pole piece of lithium-sulfur battery - Google Patents
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Abstract
A preparation method of a positive pole piece of a lithium-sulfur battery belongs to the technical field of lithium ion batteries. The method is characterized in that foamed nickel is used as a current collector, carbon nano tubes are prepared on the foamed nickel by a chemical vapor deposition method, and then sulfur is carried to obtain the lithium ion battery positive pole piece which is free of adhesive and has a three-dimensional conductive network. The preparation method is simple and efficient in process, and the prepared positive pole piece has high specific capacity, good first coulombic efficiency and excellent cycle performance, and is suitable for the lithium-sulfur battery with high energy density.
Description
Technical Field
The invention belongs to the field of lithium ion battery preparation, and particularly relates to a preparation method of a lithium-sulfur battery positive pole piece.
Background
Currently, due to the urgent need for high-energy, high-power density and high-safety lithium ion batteries, lithium sulfur batteries are widely spotlighted with their high theoretical specific capacity (1675 mAh/g) and theoretical energy density (2600 Wh/kg), as well as the use of low-cost, high-abundance, non-toxic sulfur. Although lithium-sulfur batteries have these advantages, in practical applications, the conductivity of the active material sulfur is low, and is affected by electrochemical irreversibility (also called "shuttle effect") caused by high solubility of lithium polysulfide in organic electrolyte, and the volume change of the positive electrode during battery cycling results in low utilization rate of sulfur, low battery charging efficiency, fast capacity fading, and much lower actual capacity and cycle life of the battery than theoretical values.
The carbon nano tube directly growing on the foamed nickel substrate is used for the anode of the lithium-sulfur battery after being loaded with sulfur, the carbon nano tube is a typical one-dimensional nano material and has unique mechanical strength, large specific surface area and high conductivity, and the active substance sulfur and the intermediate lithium polysulfide are fixed on the anode through the special structural characteristics of the carbon nano tube, so that the problems of low conductivity, shuttle effect and the like of the lithium-sulfur battery are solved, and the electrochemical performance of the lithium-sulfur battery is enhanced. The foam nickel as a foam metal material has porous structural characteristics, good catalytic activity and electrical conductivity, can be used as a substrate and a catalyst for the growth of the carbon nano tube, and can also be used as a current collector material of a battery. The invention prepares the binder-free positive pole piece integrating the active substance, the conductive agent and the current collector, omits the steps of coating, drying and the like in the traditional battery manufacturing, and is suitable for the stable high-energy density lithium-sulfur battery.
Disclosure of Invention
The invention aims to provide a method for preparing a stable and high-energy-density positive pole piece of a lithium-sulfur battery.
In order to achieve the purpose, the invention adopts the following technical scheme.
The invention relates to a preparation method of a lithium-sulfur battery positive pole piece, which is characterized in that foam nickel is used as a current collector, a carbon nano tube is prepared on the foam nickel by a chemical vapor deposition method, and then sulfur is carried to obtain the lithium-sulfur battery positive pole piece which is free of adhesive and has a three-dimensional conductive network.
(1) Cutting the foamed nickel into a foamed nickel wafer with a certain size, immersing the cut foamed nickel wafer into an acetone solvent for ultrasonic treatment, taking out the foamed nickel wafer, putting the foamed nickel wafer into an acetic acid or hydrochloric acid solvent for ultrasonic treatment, then putting the foamed nickel wafer into ethanol or deionized water for ultrasonic cleaning for 5-15 min, and removing lipids and oxides on the surface of the foamed nickel wafer and the acetone, acetic acid or hydrochloric acid solvent remained on the surface of the foamed nickel wafer.
The ultrasonic cleaning time in the ethanol or the deionized water is preferably 10 min.
(2) Placing the foamed nickel wafer dried in the nitrogen atmosphere as a substrate and a catalyst in a quartz boat or a porcelain boat, then coating the foamed nickel wafer with a carbon source compound according to the mass ratio of the foamed nickel to the carbon source compound of 1: 3-1: 10, heating to the reaction temperature of 700-900 ℃ in the hydrogen atmosphere of 50 sccm, reacting for 20-50 min at a constant temperature in the reducing atmosphere, and finally reducing to the room temperature in the argon atmosphere of 30 sccm to obtain the foamed nickel wafer loaded with the carbon nano tubes.
Preferably: the mass ratio of the foamed nickel to the carbon source compound is 1: 5.
Preferably: reacting at 800 deg.C under reducing atmosphere for 30 min.
(3) And (3) according to the mass ratio of the sublimed sulfur to the loaded carbon nano tube of 5: 1-20: 1, grinding the sublimed sulfur, uniformly paving the ground sublimed sulfur at the bottom of a flat-bottom glass tube with the diameter of 10 mm and the height of 10 mm, placing the foamed nickel wafer loaded with the carbon nano tube prepared in the step (2) at the opening of a quartz glass tube, preserving the heat in a tube furnace for 1 h-5 h under the condition of 350 ℃ and 30 sccm argon atmosphere, and then cooling to room temperature to obtain the sulfur-loaded lithium-sulfur battery positive pole piece.
The heat preservation in the tubular furnace is preferably carried out for 3 hours.
Further, the surface density of the foamed nickel in the step (1) is 265 g/m2~480 g/m2(preferably 350 g/m)2) (ii) a Acetone for degreasing, acetic acid or hydrochloric acid for etching, ethanol or deionized water for cleaning, and sequentially performing ultrasonic treatment.
Further, the carbon source compound in the step (2) is at least one of melamine, imidazole, ferrocene, dicyandiamide or glucose, preferably melamine; the reducing atmosphere is a hydrogen-argon mixed gas, and the flow ratio of the hydrogen to the argon is 1: 5-1: 10 (preferably 1: 5), wherein the flow of the hydrogen is 5 sccm-50 sccm, preferably 10 sccm.
Further, the mass ratio of the sublimed sulfur to the supported carbon nanotubes in the step (3) is preferably 10: 1.
Compared with the prior art, the invention has the following beneficial effects.
(1) The invention does not use adhesive in the preparation of the electrode, has simple and efficient process and improves the preparation process of the electrode.
(2) The carbon nano tube prepared by the method has the advantages of large specific surface area, high porosity and high conductivity, and improves the loading rate of the sulfur simple substance serving as an active substance, thereby improving the energy density of the lithium-sulfur battery.
Drawings
FIG. 1 is a diagram of an experimental apparatus for preparing carbon nanotube/nickel foam.
FIG. 2 is a diagram of an experimental apparatus for preparing sulfur/carbon nanotube/nickel foam.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
The methods described in the following examples are conventional methods unless otherwise specified; the material reagents, unless otherwise specified, are commercially available.
Example 1.
And (3) carrying out ultrasonic treatment on the foamed nickel wafer cut into a wafer of 12 mm by using acetone, acetic acid and ethanol in sequence, wherein the ultrasonic treatment is carried out for 10 min in each step. Drying the cleaned foam nickel sheet in a nitrogen atmosphere, using the dried foam nickel sheet as a carbon nano tube growth substrate and a catalyst, coating the foam nickel sheet with melamine according to a mass ratio of 1:5, placing the coated foam nickel sheet in a quartz boat or a porcelain boat, using an experimental device as shown in figure 1, heating to 800 ℃ at a hydrogen flow rate of 50 sccm by a chemical vapor deposition method, keeping the temperature in a tubular furnace for 30 min under a reducing atmosphere condition of hydrogen and argon =1:5 (10 sccm:50 sccm), after the growth process is finished, reducing the argon flow rate of 30 sccm in the tubular furnace to room temperature, taking out a sample, and obtaining the foam nickel sheet with the carbon nano tube.
Weighing sublimed sulfur and loaded carbon nano tubes according to the mass ratio of 10:1, uniformly paving the ground sublimed sulfur and loaded carbon nano tubes at the bottom of a flat-bottom glass tube with the diameter of 10 mm and the height of 10 mm, covering the prepared carbon nano tube/foamed nickel wafer on a quartz glass tube opening, preserving heat for 3h in a tubular furnace at 350 ℃, using an experimental device as shown in figure 2, reducing the temperature to room temperature in the whole process under the condition of argon flow rate of 30 sccm, and taking out the wafer to obtain the sulfur/carbon nano tube/foamed nickel integrated anode (S: C =5: 1) after sulfur loading. The obtained sulfur-loaded positive electrode piece, the diaphragm, the lithium piece and the electrolyte are assembled into a lithium sulfur battery, and a charge and discharge test is carried out at a multiplying power of 0.2C, and the obtained results are shown in Table 1.
Example 2.
And (3) carrying out ultrasonic treatment on the foamed nickel wafer cut into a wafer of 12 mm by using acetone, acetic acid and ethanol in sequence, wherein the ultrasonic treatment is carried out for 10 min in each step. Drying the cleaned foam nickel sheet in a nitrogen atmosphere, using the dried foam nickel sheet as a carbon nano tube growth substrate and a catalyst, coating the foam nickel sheet with dicyandiamide according to the mass ratio of 1:3, placing the coated foam nickel sheet in a quartz boat or a porcelain boat, using an experimental device as shown in figure 1, heating the coated foam nickel sheet to 700 ℃ by using a chemical vapor deposition method at the hydrogen flow rate of 50 sccm, keeping the temperature in a tubular furnace for 30 min under the reducing atmosphere condition of hydrogen and argon =1:5 (10 sccm:50 sccm) after the temperature reaches 700 ℃, reducing the argon flow rate of 30 sccm in the tubular furnace to room temperature after the growth process is finished, taking out a sample, and obtaining the foam nickel sheet with the carbon nano tube.
Weighing sublimed sulfur and loaded carbon nano tubes according to the mass ratio of 10:1, uniformly paving the ground sublimed sulfur and loaded carbon nano tubes at the bottom of a flat-bottom glass tube with the diameter of 10 mm and the height of 10 mm, covering the prepared carbon nano tube/foamed nickel wafer on a quartz glass tube opening, preserving heat for 3h in a tubular furnace at 350 ℃, using an experimental device as shown in figure 2, reducing the temperature to room temperature in the whole process under the condition of argon flow rate of 30 sccm, and taking out the wafer to obtain the sulfur/carbon nano tube/foamed nickel integrated anode (S: C =5: 1) after sulfur loading. The obtained sulfur-loaded positive electrode piece, the diaphragm, the lithium piece and the electrolyte are assembled into a lithium sulfur battery, and a charge and discharge test is carried out at a multiplying power of 0.2C, and the obtained results are shown in Table 1.
Example 3.
And (3) carrying out ultrasonic treatment on the foamed nickel wafer cut into a wafer of 12 mm by using acetone, acetic acid and ethanol in sequence, wherein the ultrasonic treatment is carried out for 10 min in each step. Drying the cleaned foam nickel sheet in a nitrogen atmosphere, using the dried foam nickel sheet as a carbon nano tube growth substrate and a catalyst, coating the foam nickel sheet with glucose according to a mass ratio of 1:4, placing the coated foam nickel sheet in a quartz boat or a porcelain boat, using an experimental device as shown in figure 1, heating to 900 ℃ at a hydrogen flow rate of 50 sccm by using a chemical vapor deposition method, keeping the temperature in a tubular furnace for 30 min under a reducing atmosphere condition of hydrogen and argon =1:5 (10 sccm:50 sccm) after the temperature reaches 900 ℃, reducing the argon flow rate of 30 sccm in the tubular furnace to room temperature after the growth process is finished, taking out a sample, and obtaining the foam nickel sheet with the carbon nano tube.
Weighing sublimed sulfur and loaded carbon nano tubes according to the mass ratio of 10:1, uniformly paving the ground sublimed sulfur and loaded carbon nano tubes at the bottom of a flat-bottom glass tube with the diameter of 10 mm and the height of 10 mm, covering the prepared carbon nano tube/foamed nickel wafer on a quartz glass tube opening, preserving heat for 3h in a tubular furnace at 350 ℃, using an experimental device as shown in figure 2, reducing the temperature to room temperature in the whole process under the condition of argon flow rate of 30 sccm, and taking out the wafer to obtain the sulfur/carbon nano tube/foamed nickel integrated anode (S: C =5: 1) after sulfur loading. The obtained sulfur-loaded positive electrode piece, the diaphragm, the lithium piece and the electrolyte are assembled into a lithium sulfur battery, and a charge and discharge test is carried out at a multiplying power of 0.2C, and the obtained results are shown in Table 1.
Example 4.
And (3) carrying out ultrasonic treatment on the foamed nickel pressed wafer cut into a 12 mm wafer by using acetone, acetic acid and ethanol in sequence, wherein the ultrasonic treatment is carried out for 10 min in each step. Drying the cleaned foam nickel sheet in a nitrogen atmosphere, using the dried foam nickel sheet as a carbon nano tube growth substrate and a catalyst, coating the foam nickel sheet with ferrocene according to the mass ratio of 1:5, placing the coated foam nickel sheet in a quartz boat or a porcelain boat, using an experimental device as shown in figure 1, heating to 800 ℃ at the hydrogen flow rate of 50 sccm by using a chemical vapor deposition method, keeping the temperature in a tubular furnace for 30 min under the reducing atmosphere condition of hydrogen and argon =1:5 (10 sccm:50 sccm) after reaching 800 ℃, reducing the argon flow rate of 30 sccm in the tubular furnace to room temperature after the growth process is finished, taking out a sample, and obtaining the foam nickel sheet with the carbon nano tube.
Weighing sublimed sulfur and loaded carbon nano tubes according to the mass ratio of 15:1, uniformly paving the ground sublimed sulfur and loaded carbon nano tubes at the bottom of a flat-bottom glass tube with the diameter of 10 mm and the height of 10 mm, covering the prepared carbon nano tube/foamed nickel wafer on a quartz glass tube opening, preserving heat for 3h in a tubular furnace at 350 ℃, using an experimental device as shown in figure 2, reducing the temperature to room temperature in the whole process under the condition of argon flow rate of 30 sccm, and taking out the wafer to obtain the sulfur/carbon nano tube/foamed nickel integrated anode (S: C =7: 1) after sulfur loading. The obtained sulfur-loaded positive electrode piece, the diaphragm, the lithium piece and the electrolyte are assembled into a lithium sulfur battery, and a charge and discharge test is carried out at a multiplying power of 0.2C, and the obtained results are shown in Table 1.
Example 5.
And (3) carrying out ultrasonic treatment on the foamed nickel wafer cut into a wafer of 12 mm by using acetone, acetic acid and ethanol in sequence, wherein the ultrasonic treatment is carried out for 10 min in each step. Drying the cleaned foam nickel sheet in a nitrogen atmosphere, using the dried foam nickel sheet as a carbon nano tube growth substrate and a catalyst, coating the foam nickel sheet with melamine according to a mass ratio of 1:10, placing the coated foam nickel sheet in a quartz boat or a porcelain boat, using an experimental device as shown in figure 1, heating to 900 ℃ by using a chemical vapor deposition method at a hydrogen flow rate of 50 sccm, keeping the temperature in a tubular furnace for 30 min under a reducing atmosphere condition of hydrogen and argon =1:5 (10 sccm:50 sccm) after the temperature reaches 900 ℃, reducing the argon flow rate of 30 sccm in the tubular furnace to room temperature after the growth process is finished, taking out a sample, and obtaining the foam nickel sheet with the carbon nano tubes.
Weighing sublimed sulfur and loaded carbon nano tubes according to the mass ratio of 20:1, uniformly paving the ground sublimed sulfur and loaded carbon nano tubes at the bottom of a flat-bottom glass tube with the diameter of 10 mm and the height of 10 mm, covering the prepared carbon nano tube/foamed nickel wafer on a quartz glass tube opening, preserving heat for 3h in a tubular furnace at 350 ℃, using an experimental device as shown in figure 2, reducing the temperature to room temperature in the whole process under the condition of argon flow rate of 30 sccm, and taking out the wafer to obtain the sulfur/carbon nano tube/foamed nickel integrated anode (S: C =9: 1) after sulfur loading. The obtained sulfur-loaded positive electrode piece, the diaphragm, the lithium piece and the electrolyte are assembled into a lithium sulfur battery, and a charge and discharge test is carried out at a multiplying power of 0.2C, and the obtained results are shown in Table 1.
Example 6.
And (3) carrying out ultrasonic treatment on the foamed nickel wafer cut into a wafer of 12 mm by using acetone, acetic acid and ethanol in sequence, wherein the ultrasonic treatment is carried out for 10 min in each step. Drying the cleaned foam nickel sheet in a nitrogen atmosphere, using the dried foam nickel sheet as a carbon nano tube growth substrate and a catalyst, coating the foam nickel sheet with imidazole according to a mass ratio of 1:5, placing the coated foam nickel sheet in a quartz boat or a porcelain boat, using an experimental device as shown in figure 1, heating to 800 ℃ at a hydrogen flow rate of 50 sccm by a chemical vapor deposition method, keeping the temperature in a tubular furnace for 30 min under a reducing atmosphere condition of hydrogen and argon =1:5 (10 sccm:50 sccm), after the growth process is finished, reducing the argon flow rate of 30 sccm in the tubular furnace to room temperature, taking out a sample, and obtaining the foam nickel sheet with the carbon nano tube.
Weighing sublimed sulfur and loaded carbon nano tubes according to the mass ratio of 7:1, uniformly paving the ground sublimed sulfur and loaded carbon nano tubes at the bottom of a flat-bottom glass tube with the diameter of 10 mm and the height of 10 mm, covering the prepared carbon nano tube/foamed nickel wafer on a quartz glass tube opening, preserving heat for 3h in a tubular furnace at 350 ℃, using an experimental device as shown in figure 2, reducing the temperature to room temperature in the whole process under the condition of argon flow rate of 30 sccm, and taking out the wafer to obtain the sulfur/carbon nano tube/foamed nickel integrated anode (S: C =4: 1) after sulfur loading. The obtained sulfur-loaded positive electrode plate, a diaphragm, a lithium plate and an electrolyte are assembled into a lithium-sulfur battery, a charge-discharge test is carried out at the rate of 0.2C, and the obtained result is compared with the result of a comparative document Ni S, Yang X, Li T. publication of a porous NiS/Ni nanostructured electrode a dry chemical method and an item application in a lithium ion battery [ J ]. Journal of materials Chemistry, 2012, 22(6): 2395-.
TABLE 1 comparison of the charging and discharging test results of lithium-sulfur batteries prepared by pole pieces obtained in different examples with the performance of samples without carbon nanotubes in the literature
Claims (7)
1. A preparation method of a positive pole piece of a lithium-sulfur battery is characterized by comprising the following steps:
(1) cutting the foamed nickel into a foamed nickel wafer with a certain size, immersing the cut foamed nickel wafer into an acetone solvent for ultrasonic treatment, taking out the foamed nickel wafer, putting the foamed nickel wafer into an acetic acid or hydrochloric acid solvent for ultrasonic treatment, then putting the foamed nickel wafer into ethanol or deionized water for ultrasonic cleaning for 5-15 min, and removing lipids and oxides on the surface of the foamed nickel wafer and the acetone, acetic acid or hydrochloric acid solvent remained on the surface of the foamed nickel wafer;
(2) placing a foamed nickel wafer dried in a nitrogen atmosphere as a substrate and a catalyst in a quartz boat or a porcelain boat, then coating the foamed nickel wafer with a carbon source compound according to the mass ratio of the foamed nickel to the carbon source compound of 1: 3-1: 10, heating to the reaction temperature of 700-900 ℃ in a hydrogen atmosphere of 50 sccm, carrying out constant-temperature reaction for 20-50 min in a reducing atmosphere, and finally reducing to the room temperature in an argon atmosphere of 30 sccm to obtain a foamed nickel wafer loaded with carbon nano tubes;
(3) according to the mass ratio of sublimed sulfur to loaded carbon nano tubes of 5: 1-20: 1, grinding the sublimed sulfur, uniformly paving the ground sublimed sulfur at the bottom of a flat-bottom glass tube with the diameter of 10 mm and the height of 10 mm, placing the foamed nickel wafer loaded with the carbon nano tubes prepared in the step (2) at the opening of a quartz glass tube, preserving heat in a tube furnace for 1 h-5 h at 350 ℃ under the condition of 30 sccm argon atmosphere, and then cooling to room temperature to obtain a sulfur-loaded lithium-sulfur battery positive pole piece;
the surface density of the foamed nickel in the step (1) is 265 g/m2-480 g/m2;
The carbon source compound in the step (2) is at least one of melamine, imidazole, ferrocene, dicyandiamide or glucose; the reducing atmosphere is hydrogen-argon mixed gas, the flow ratio of the hydrogen to the argon is 1: 5-1: 10, and the gas flow is 10 sccm-200 sccm.
2. The method for preparing the positive pole piece of the lithium-sulfur battery as claimed in claim 1, wherein the areal density of the foamed nickel in the step (1) is preferably 350 g/m2。
3. The preparation method of the positive electrode plate of the lithium-sulfur battery according to claim 1, wherein the ultrasonic cleaning time in ethanol or deionized water in the step (1) is preferably 10 min.
4. The preparation method of the positive pole piece of the lithium-sulfur battery as claimed in claim 1, wherein the mass ratio of the foamed nickel and the carbon source compound in the step (2) is 1: 5; reacting at 800 deg.C under reducing atmosphere for 30 min.
5. The method for preparing the positive electrode plate of the lithium-sulfur battery as claimed in claim 1, wherein the reducing atmosphere in the step (2) is hydrogen-argon mixed gas, the flow ratio of hydrogen to argon is 1:5, and the gas flow is 60 sccm.
6. The method for preparing the positive pole piece of the lithium-sulfur battery as claimed in claim 1, wherein the mass ratio of the sublimed sulfur to the loaded carbon nanotubes in the step (3) is 10: 1.
7. The method for preparing the positive pole piece of the lithium-sulfur battery according to claim 1, wherein the tubular furnace in the step (3) is kept warm for 3 hours.
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