CN110676442B - Method for preparing sulfur/carbon @ metal oxide nanotube lithium-sulfur battery positive electrode material by utilizing atomic layer deposition technology - Google Patents

Method for preparing sulfur/carbon @ metal oxide nanotube lithium-sulfur battery positive electrode material by utilizing atomic layer deposition technology Download PDF

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CN110676442B
CN110676442B CN201910782018.4A CN201910782018A CN110676442B CN 110676442 B CN110676442 B CN 110676442B CN 201910782018 A CN201910782018 A CN 201910782018A CN 110676442 B CN110676442 B CN 110676442B
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sulfur
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lithium
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蔡玉荣
马丹阳
蔡泽玮
张茜
王广舒
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Zhejiang University of Technology ZJUT
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
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    • H01M4/625—Carbon or graphite
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a method for preparing a sulfur/carbon @ metal oxide nanotube lithium-sulfur battery positive electrode material by utilizing an atomic layer deposition technology. The method is characterized in that magnesium acetate is added into polyacrylonitrile spinning solution, a polyacrylonitrile film containing magnesium oxide is obtained through electrostatic spinning, magnesium oxide-doped carbon fiber is obtained through carbonization, zinc oxide is deposited on the surface of the fiber through atomic layer deposition, a carbon/magnesium oxide @ zinc oxide composite material is obtained, and a carbon/magnesium oxide @ zinc oxide sulfur-loaded material is obtained through hot melting sulfur loading and is applied to a lithium sulfur battery positive electrode material. The method utilizes the atomic layer deposition method in the process of preparing the lithium-sulfur battery cathode material, is beneficial to controlling the thickness and the uniformity of the wrapping layer, simultaneously realizes one-step doping of the cathode material, provides the preparation method of the composite material with simple process, and obtains the lithium-sulfur battery cathode material with good cycling stability and high specific capacity.

Description

Method for preparing sulfur/carbon @ metal oxide nanotube lithium-sulfur battery positive electrode material by utilizing atomic layer deposition technology
Technical Field
The invention relates to a preparation method of a battery material, in particular to a method for preparing a sulfur/carbon @ metal oxide nanotube lithium-sulfur battery positive electrode material by utilizing an atomic layer deposition technology, and belongs to the field of preparation of lithium-sulfur batteries.
Background
In recent years, with lithium ion batteries, the demand for high energy density of energy storage devices has gradually become unsatisfied. The elemental sulfur has rich reserves, low price and environmental protection, and has high theoretical energy density (2600Wh kg-1) and theoretical specific capacity (1675mAh g-1) and becomes a hotspot of current research.
Currently, the commercialization of lithium sulfur batteries needs to overcome the following disadvantages: firstly, elemental sulfur has poor conductivity (5 multiplied by 10 < -30 > Scm < -1 >, 25 ℃) and is not beneficial to electron transmission; secondly, the volume of the elemental sulfur used as the positive electrode material of the lithium-sulfur battery is easy to expand (approximately equal to 80%); third, during the charging and discharging process, the polysulfide intermediate is easily dissolved in the electrolyte to cause the loss of active materials, and the shuttle effect is easily formed to cause the capacity loss. Therefore, the stability and the capacity of the positive electrode material of the lithium-sulfur battery are improved, and the method has important significance.
Currently, there is a wide range of interest in using electron conducting hosts to absorb polysulfides, such as carbon/sulfur materials, polymer/sulfur materials, metal oxide materials, and lithium sulfide. Particularly, the carbon negative electrode material mainly comprising graphite and amorphous carbon materials is introduced, so that the capacity of the lithium-sulfur battery is remarkably improved. However, the interaction between the carbon material and the polysulfide is weak, so that the loss of the polysulfide cannot be avoided, metal oxides such as Al2O3, SiO2, TiO2, MnO2 and the like can effectively absorb the polysulfide and improve the electron transmission efficiency, and meanwhile, the volume expansion of the positive electrode material in the charge-discharge process can be effectively inhibited by preparing a core-shell structure. In the field of preparation of lithium-sulfur battery cathode materials, chinese patent (CN 106654231B) "a lithium-sulfur battery cathode material and a preparation method thereof" uses zinc oxide and dopamine to prepare a dopamine/flower-like zinc oxide composite material in a composite manner, then carries out carbon treatment to obtain a three-dimensional flower-like carbon structure, carries sulfur with the structure as a carrier, and finally wraps a layer of conductive polymer PDA on the obtained carbon-sulfur composite material to obtain the lithium-sulfur battery cathode material; in chinese patent (CN 109742359 a) "lithium-sulfur battery positive electrode material, its preparation method, positive electrode sheet and lithium-sulfur battery", a composite material in which at least two metal sulfides are tightly embedded on the surface of graphene is prepared, forming a conductive network structure, and providing a channel for rapid transmission of electrons and ions.
Disclosure of Invention
In order to solve the problems of poor elemental sulfur conductivity, serious charge and discharge capacity loss and the like of the conventional lithium-sulfur battery, the invention provides a method for preparing a sulfur/carbon @ metal oxide nanotube lithium-sulfur battery positive electrode material by utilizing an atomic layer deposition technology, the material can effectively solve the problems of loss of active sulfur and shuttle effect of the lithium-sulfur battery positive electrode material, the cycling stability of the battery is improved, and the related preparation method is simple and effective.
In order to achieve the purpose, the technical scheme of the invention adopts the following steps:
1) mixing polyacrylonitrile, magnesium salt and N, N-dimethylformamide solution, stirring at room temperature for 10h to obtain precursor polymer solution, pouring the solution into a disposable injector, and spinning at high pressure of 13.5kV, low pressure of-2.5 kV and rotation speed of 200rpm for 8h to obtain a membrane;
2) pre-oxidizing the film obtained in the step 1) in air for 3h, and then treating the film for 3h in a nitrogen atmosphere to obtain nano fibers;
3) reacting with diethyl zinc and H under the environment of 1800Pa and 100 DEG C2Taking O as a reactant, taking the nanofiber obtained in the step 2) as a substrate, and growing a ZnO coating layer with the thickness of 40nm through certain ALD (atomic layer deposition) circulation to obtain the nanofiber wrapped by zinc oxide;
4) mixing the zinc oxide-coated nanofiber obtained in the step 3) with sulfur according to a certain proportion, carrying sulfur in an argon atmosphere to obtain a sulfur-containing nanofiber, cooling to room temperature, washing sulfur adsorbed on the surface with a certain volume of carbon disulfide/alcohol solution, and drying the obtained product at 60 ℃ for 6 hours to obtain the sulfur/carbon @ metal oxide nanotube lithium-sulfur battery positive electrode material.
The molecular weight of the polyacrylonitrile is 150000, the concentration of the polyacrylonitrile in the mixed solution is 13.6 wt%, and the magnesium salt is selected from magnesium acetate, and the concentration of the magnesium salt in the mixed solution is 5.4 wt%; the pre-oxidation temperature is 230 ℃, and the treatment temperature under the nitrogen atmosphere is 900 ℃; the ratio of the zinc oxide coated nanofiber to sulfur is 3:7, carrying sulfur under the argon atmosphere for 12 hours at 155 ℃; the volume ratio of the carbon disulfide to the alcohol solution is 1: 9.
the certain ALD cycles are 200, 250, 300 and 350 cycles.
The composite material is a nitrogen-rich material, and can realize one-step doping of magnesium oxide and easy control of the thickness of a zinc oxide wrapping layer, and the thickness of the composite material is about 40-70 nm.
The carbon-magnesium oxide/sulfur @ zinc oxide composite material provided by the invention is prepared by adopting the method.
The invention also provides a lithium-sulfur battery positive plate, which comprises a current collector and a coating material arranged on the surface of the current collector, wherein the coating material comprises the carbon-magnesium oxide/sulfur @ zinc oxide composite material, a binder and a conductive agent.
The invention also provides a lithium-sulfur battery, which comprises a positive plate made of the carbon-magnesium oxide/sulfur @ zinc oxide composite material.
According to the preparation method, the polyacrylonitrile film doped with the magnesium acetate is obtained through an electrostatic spinning technology, the carbon nanofiber doped with the magnesium oxide is obtained through carbonization, the carbon-magnesium oxide @ zinc oxide composite material is obtained through wrapping the carbon nanofiber through an atomic layer deposition technology, the anode material of the lithium-sulfur battery is obtained after sulfur is loaded, the preparation method is simple, and the cost is low. The magnesium oxide doping is beneficial to improving the adsorption effect on polysulfide, inhibiting shuttle of polysulfide, and wrapping a zinc oxide layer to obtain a core-shell structure which is beneficial to limiting the volume expansion of a positive electrode material in the charging and discharging processes of a lithium-sulfur battery, and zinc oxide can provide more active sites for polysulfide and reduce the loss of polysulfide.
The invention has the beneficial effects that:
according to the invention, magnesium oxide is introduced in the process of preparing the carbon fiber, so that one-step doping is realized, the adsorption effect on polysulfide is improved, and the complexity of the preparation of the composite material is reduced; the prepared nanofiber is wrapped by the atomic layer deposition technology, the operation is simple, the coating layer is uniform, and the thickness is easy to control. Through the doping and coating effects, the loss of active substances in the charging/discharging process is reduced, and the electrochemical performance of the lithium-sulfur battery is improved.
Drawings
Fig. 1 is an SEM image of the zinc oxide-coated nanofiber composite prepared in example 1.
Figure 2 is an SEM image of the carbon-magnesium oxide/sulfur @ zinc oxide nanofiber composite prepared in example 1.
Fig. 3 is a cycle performance diagram of the carbon-magnesium oxide/sulfur and carbon-magnesium oxide/sulfur @ zinc oxide nanofiber composite material prepared in example 1 as a lithium sulfur battery cathode material at a rate of 0.5C.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
1) Mixing 1.5g of polyacrylonitrile with the molecular weight of 150000, 0.6g of magnesium acetate and 11g of N, N-dimethylformamide solution, stirring at room temperature for 10h to prepare a precursor polymer solution, then pouring the solution into a disposable injector, and spinning for 8h at the high pressure of 13.5kV, the low pressure of-2.5 kV and the rotating speed of 200rpm to obtain a membrane;
2) pre-oxidizing the film obtained in the step 1) in air at 230 ℃ for 3h, and then treating the film at 900 ℃ for 3h in a nitrogen atmosphere to obtain nano fibers;
3) reacting with diethyl zinc and H under the environment of 1800Pa and 100 DEG C2Taking O as a reactant, taking the nanofiber obtained in the step 2) as a substrate, and growing a ZnO coating layer with the thickness of 40nm through 200-circle ALD (atomic layer deposition) circulation to obtain the nanofiber coated by zinc oxide;
4) mixing the zinc oxide-coated nanofiber obtained in the step 3) with sulfur according to the weight ratio of 3:7, carrying sulfur at 155 ℃ for 12h under the argon atmosphere to obtain sulfur-containing nanofiber, cooling to room temperature, and washing sulfur adsorbed on the surface with carbon disulfide/alcohol solution with the volume ratio of 1: 9. And drying the obtained product at 60 ℃ for 6h to obtain the sulfur/carbon @ metal oxide nanotube lithium-sulfur battery positive electrode material.
Example 2:
1) mixing 1.5g of polyacrylonitrile with the molecular weight of 150000, 0.6g of magnesium acetate and 11g of N, N-dimethylformamide solution, stirring at room temperature for 10h to prepare a precursor polymer solution, then pouring the solution into a disposable injector, and spinning for 8h at the high pressure of 13.5kV, the low pressure of-2.5 kV and the rotating speed of 200rpm to obtain a membrane;
2) pre-oxidizing the film obtained in the step 1) in air at 230 ℃ for 3h, and then treating the film at 900 ℃ for 3h in a nitrogen atmosphere to obtain nano fibers;
3) reacting with diethyl zinc and H under the environment of 1800Pa and 100 DEG C2O is taken as a reactant, and the sodium obtained in the step 2) is usedTaking the rice fiber as a substrate, and growing a ZnO coating layer with the thickness of 50nm through 250 cycles of ALD (atomic layer deposition) circulation to obtain the nanofiber coated by the zinc oxide;
4) mixing the zinc oxide-coated nanofiber obtained in the step 3) with sulfur according to the weight ratio of 3:7, carrying sulfur at 155 ℃ for 12h under the argon atmosphere to obtain sulfur-containing nanofiber, cooling to room temperature, and washing sulfur adsorbed on the surface with carbon disulfide/alcohol solution with the volume ratio of 1: 9. And drying the obtained product at 60 ℃ for 6h to obtain the sulfur/carbon @ metal oxide nanotube lithium-sulfur battery positive electrode material.
Example 3:
1) mixing 1.5g of polyacrylonitrile with the molecular weight of 150000, 0.6g of magnesium acetate and 11g of N, N-dimethylformamide solution, stirring at room temperature for 10h to prepare a precursor polymer solution, then pouring the solution into a disposable injector, and spinning for 8h at the high pressure of 13.5kV, the low pressure of-2.5 kV and the rotating speed of 200rpm to obtain a membrane;
2) pre-oxidizing the film obtained in the step 1) in air at 230 ℃ for 3h, and then treating the film at 900 ℃ for 3h in a nitrogen atmosphere to obtain nano fibers;
3) reacting with diethyl zinc and H under the environment of 1800Pa and 100 DEG C2Taking O as a reactant, taking the nanofiber obtained in the step 2) as a substrate, and growing a ZnO coating layer with the thickness of 60nm through 300-circle ALD (atomic layer deposition) circulation to obtain the nanofiber coated by zinc oxide;
4) mixing the zinc oxide-coated nanofiber obtained in the step 3) with sulfur according to the weight ratio of 3:7, carrying sulfur at 155 ℃ for 12h under the argon atmosphere to obtain sulfur-containing nanofiber, cooling to room temperature, and washing sulfur adsorbed on the surface with carbon disulfide/alcohol solution with the volume ratio of 1: 9. And drying the obtained product at 60 ℃ for 6h to obtain the sulfur/carbon @ metal oxide nanotube lithium-sulfur battery positive electrode material.
Example 4:
1) mixing 1.5g of polyacrylonitrile with the molecular weight of 150000, 0.6g of magnesium acetate and 11g of N, N-dimethylformamide solution, stirring at room temperature for 10h to prepare a precursor polymer solution, then pouring the solution into a disposable injector, and spinning for 8h at the high pressure of 13.5kV, the low pressure of-2.5 kV and the rotating speed of 200rpm to obtain a membrane;
2) pre-oxidizing the film obtained in the step 1) in air at 230 ℃ for 3h, and then treating the film at 900 ℃ for 3h in a nitrogen atmosphere to obtain nano fibers;
3) reacting with diethyl zinc and H under the environment of 1800Pa and 100 DEG C2Taking O as a reactant, taking the nanofiber obtained in the step 2) as a substrate, and growing a ZnO coating layer with the thickness of 70nm through 350-circle ALD (atomic layer deposition) circulation to obtain the nanofiber coated by zinc oxide;
4) mixing the zinc oxide-coated nanofiber obtained in the step 3) with sulfur according to the weight ratio of 3:7, carrying sulfur at 155 ℃ for 12h under the argon atmosphere to obtain sulfur-containing nanofiber, cooling to room temperature, and washing sulfur adsorbed on the surface with carbon disulfide/alcohol solution with the volume ratio of 1: 9. And drying the obtained product at 60 ℃ for 6h to obtain the sulfur/carbon @ metal oxide nanotube lithium-sulfur battery positive electrode material.
Table 1 shows the characterization results of the morphology and size of the carbon-magnesia/sulfur @ zinc oxide nanofibers prepared in example 1, example 2, example 3 and example 4. From the data in Table 1, it is clear that the carbon-magnesia/sulfur @ zinc oxide nanofiber zinc oxide coating layers prepared according to examples 1,2, 3 and 4 have thicknesses of 40nm, 50nm, 60nm and 70nm, respectively. The carbon-magnesium oxide/sulfur @ zinc oxide nano fibers with different sizes can be obtained by adopting the preparation method disclosed by the invention, and the diameters of the carbon-magnesium oxide/sulfur @ zinc oxide nano fibers are distributed between 40nm and 70 nm. The carbon-magnesium oxide/sulfur @ zinc oxide nanofibers prepared in examples 1,2, 3 and 4 were used as positive electrode materials of lithium-sulfur batteries, and electrochemical tests were performed on the carbon-magnesium oxide/sulfur @ zinc oxide nanofibers, which were prepared in example 2 and had a 50nm coating thickness, as positive electrode materials of lithium-sulfur batteries, and the batteries obtained were the best in cycle performance, the first cycle discharge capacity at 0.5C rate was 1130.513mAh g-1, the carbon-magnesium oxide/sulfur @ zinc oxide nanofibers, which were prepared in example 4 and had a 70nm coating thickness, as positive electrode materials of lithium-sulfur batteries, were the worst in cycle performance, and the first cycle discharge capacity at 0.5C rate was 989.476mAh g-1.
TABLE 1
Figure BDA0002176896430000051
The above description is only a part of the embodiments of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and does not represent all technical solutions under the concept of the present invention. It should be noted that those skilled in the art, upon being motivated by this patent conception and specific embodiment, may recognize numerous additions and modifications which may be made without departing from the principles of the present invention, such as insubstantial modifications of determining different catalyst and oxidant amounts, different temperatures, etc., based on different wastewater and contaminant concentrations, and such modifications and refinements are considered to be within the scope of the present invention.

Claims (4)

1. A method for preparing a sulfur/carbon @ metal oxide nanotube lithium-sulfur battery positive electrode material by utilizing an atomic layer deposition technology is characterized by comprising the following steps of:
1) mixing polyacrylonitrile, magnesium salt and N, N-dimethylformamide solution, stirring at room temperature for 10h to obtain precursor polymer solution, pouring the solution into a disposable injector, and spinning at high pressure of 13.5kV, low pressure of-2.5 kV and rotation speed of 200rpm for 8h to obtain a membrane;
2) pre-oxidizing the film obtained in the step 1) in air for 3h, and then treating the film for 3h in a nitrogen atmosphere to obtain nano fibers;
3) under the environment of 1800Pa and 100 ℃, taking diethyl zinc and H2O as reactants and the nanofiber obtained in the step 2) as a substrate, and growing a ZnO coating layer with the thickness of 40nm through a certain ALD cycle to obtain the nanofiber wrapped by zinc oxide;
4) mixing the zinc oxide-coated nanofiber obtained in the step 3) with sulfur according to a certain proportion, carrying sulfur in an argon atmosphere to obtain a sulfur-containing nanofiber, cooling to room temperature, washing sulfur adsorbed on the surface with a certain volume of carbon disulfide/alcohol solution, and drying the obtained product at 60 ℃ for 6 hours to obtain the sulfur/carbon @ metal oxide nanotube lithium-sulfur battery positive electrode material.
2. The method for preparing the sulfur/carbon @ metal oxide nanotube lithium sulfur battery positive electrode material by utilizing the atomic layer deposition technology as claimed in claim 1, wherein the method comprises the following steps: the molecular weight of the polyacrylonitrile is 150000, the concentration of the polyacrylonitrile in the mixed solution is 13.6 wt%, and the magnesium salt is selected from magnesium acetate, and the concentration of the magnesium salt in the mixed solution is 5.4 wt%; the pre-oxidation temperature is 230 ℃, and the treatment temperature under the nitrogen atmosphere is 900 ℃; the ratio of the zinc oxide coated nanofiber to sulfur is 3:7, carrying sulfur under the argon atmosphere for 12 hours at 155 ℃; the volume ratio of the carbon disulfide to the alcohol solution is 1: 9.
3. the method for preparing the sulfur/carbon @ metal oxide nanotube lithium sulfur battery positive electrode material by utilizing the atomic layer deposition technology as claimed in claim 1, wherein the method comprises the following steps: the certain ALD cycles are 200, 250, 300 and 350 cycles.
4. The method for preparing the sulfur/carbon @ metal oxide nanotube lithium sulfur battery positive electrode material by utilizing the atomic layer deposition technology as claimed in claim 1, wherein the method comprises the following steps: the anode material of the lithium-sulfur battery is a nitrogen-rich material, and can realize one-step doping of magnesium oxide and easy control of the thickness of a zinc oxide coating layer, and the thickness of the anode material is 40-70 nm.
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