CN112563466B - Lithium-sulfur battery anode nanofiber composite material and preparation method and application thereof - Google Patents
Lithium-sulfur battery anode nanofiber composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a lithium-sulfur battery anode nanofiber composite material as well as a preparation method and application thereof, wherein the method comprises the following steps: preparation of porous NiCo by electrostatic spinning method 2 O 4 a/C nanofiber precursor; mixing the porous NiCo 2 O 4 Oxidizing and carbonizing the/C nanofiber precursor to obtain the porous NiCo 2 O 4 a/C nanofiber; mixing the porous NiCo 2 O 4 the/C nano-fiber is subjected to high-temperature sulfurizing treatment to obtain porous NiCo 2 O 4 a/C @ S nanofiber composite. Porous NiCo of the invention 2 O 4 the/C @ S nanofiber composite material has good stability, and simultaneously, the composite material as a positive electrode material of a lithium-sulfur battery shows good electrochemical performance.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a lithium-sulfur battery anode nano fiber composite material and a preparation method and application thereof.
Background
The lithium-sulfur battery has high energy density, low price and abundant raw material reserves, has huge application potential on electric vehicles and large energy storage devices, but a positive electrode sulfur material of the lithium-sulfur battery can form intermediate-phase polysulfide during charging and discharging processes, the polysulfide is easily dissolved in electrolyte and can shuttle to a negative electrode to lose electrochemical activity, so that the electrochemical performance is quickly attenuated, and the characteristics are limitedOne of the important limiting factors for large-scale application of lithium sulfur batteries. Researchers explore a large number of sulfur fixing methods and sulfur fixing materials, and research finds that the binary metal oxide NiCo 2 O 4 、NiFe 2 O 4 The materials can effectively adsorb polysulfide without being dissolved, so that the stability of the electrode material is ensured, the coulombic efficiency of the material is improved, but the problem of polysulfide dissolution is not completely solved so far, and the industrialization of the lithium-sulfur battery is far from the important point.
In conclusion, the existing preparation method of the electrode material of the lithium-sulfur battery is complex, and the prepared electrode material has the problems of poor chemical stability and rapid capacity fading.
Disclosure of Invention
Therefore, the invention provides a lithium-sulfur battery anode nanofiber composite material and a preparation method and application thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a preparation method of a lithium-sulfur battery anode nanofiber composite material, which comprises the following steps: preparation of porous NiCo by electrostatic spinning method 2 O 4 a/C nanofiber precursor; mixing the porous NiCo 2 O 4 Oxidizing and carbonizing the/C nanofiber precursor to obtain the porous NiCo 2 O 4 a/C nanofiber;
mixing the porous NiCo 2 O 4 the/C nano-fiber is subjected to high-temperature sulfurizing treatment to obtain porous NiCo 2 O 4 the/C @ S nanofiber composite material is the lithium-sulfur battery positive electrode nanofiber composite material.
Preferably, the solution used for electrospinning is prepared by the following steps:
adding polyvinyl acetate into deionized water, stirring for 30min at 60 ℃ until the polyvinyl acetate is completely dissolved to obtain a polyvinyl acetate solution with the mass fraction of 5% -50%, then adding nickel acetate and cobalt acetate into the polyvinyl acetate solution, and stirring for 30min until the polyvinyl acetate is completely dissolved;
wherein the mass ratio of the nickel acetate to the polyvinyl acetate is 0.01-1, and the molar ratio of the nickel acetate to the cobalt acetate is 1: 2.
Preferably, the polyvinyl acetate has a molecular weight of 10000-1000000.
Preferably, the electrospinning conditions are:
voltage of 5-50kV and roller receiving speed of 0-100r min -1 Push-injection pushing speed of 0.1-10mL h -1 The distance between the needle head of the electrostatic spinning and the receiver is 5-30cm, and the electrostatic spinning time is 1-100 h.
Preferably, the oxidation treatment conditions are:
mixing the porous NiCo 2 O 4 The precursor of the/C nano-fiber is prepared at the temperature of 1-10 ℃ for min -1 The temperature rising speed is gradually increased to 150-300 ℃, and the temperature is kept for 0.5-5 h.
Preferably, the carbonization conditions are as follows:
oxidizing the porous NiCo treated by oxidation 2 O 4 the/C nanofiber precursor is put in inert gas at the temperature of 1-20 ℃ for min -1 The temperature is raised to 500 ℃ and 1000 ℃, and the temperature is kept constant for 0.5 to 10 hours.
Preferably, the high-temperature sulfurizing treatment process comprises the following steps:
mixing sulfur nanoparticles with the porous NiCo 2 O 4 Mixing the/C nanofibers, placing in a sealed container, and keeping at 1-20 deg.C for min under inert atmosphere -1 The temperature is increased to 300 ℃, and the constant temperature is kept for 5-30 h.
Preferably, the size of the sulfur nanoparticles is 50-1000nm, and the sulfur nanoparticles and the porous NiCo 2 O 4 The mass ratio of the/C nano fibers is 0.1-100.
The lithium-sulfur battery positive electrode nanofiber composite material prepared by the method also belongs to the protection scope of the invention.
The invention also provides application of the lithium-sulfur battery anode nanofiber composite material in any one of the following processes, (1) preparing a battery or a battery electrode material; (2) preparing an energy storage element; (3) an electronic device is prepared.
The invention has the following advantages:
the invention takes polyvinyl acetate, nickel acetate and cobalt acetate as raw materials to carry out electrostatic spinning,preparation of porous NiCo 2 O 4 the/C nano-fiber is subjected to high-temperature sulfurization to generate sulfur nano-particles in situ in the nano-fiber, and the porous NiCo is prepared 2 O 4 the/C @ S nanofiber composite material.
The porous NiCo prepared by the invention 2 O 4 the/C @ S nano-fiber composite material takes a carbon skeleton as a matrix and NiCo 2 O 4 The nano particles are uniformly dispersed in the carbon matrix, so that a good sulfur fixing effect can be achieved, a large number of pores are distributed in the composite material, the sulfur nano particles are attached to the pores, the rich pore structure in the composite material provides a space for volume expansion of sulfur in the charging and discharging process on one hand, and provides a rapid channel for transmission of lithium ions on the other hand, and the NiCo has the advantages of high sulfur solubility, high sulfur-absorbing capacity and high sulfur-absorbing capacity 2 O 4 The nano particles can effectively adsorb polysulfide and ensure the stability of the composite material, so the porous NiCo of the invention can be used as the anode material of a lithium-sulfur battery 2 O 4 the/C @ S nanofiber composite material shows good electrochemical performance.
The preparation method is simple in preparation process, low in cost, capable of being copied and applied on a large scale and wide in application potential.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.
The structures, ratios, sizes, and the like shown in the present specification are only used for matching with the contents disclosed in the specification, so that those skilled in the art can understand and read the present invention, and do not limit the conditions for implementing the present invention, so that the present invention has no technical significance, and any structural modifications, changes in the ratio relationship, or adjustments of the sizes, without affecting the functions and purposes of the present invention, shall fall within the scope covered by the technical contents disclosed in the present invention.
FIG. 1 is a schematic representation of a porous NiCo prepared by the method of the present invention 2 O 4 A/C nanofiber precursor and porous NiCo 2 O 4 SEM pictures of/C @ S nano-fibers, wherein (a, b) are porous NiCo 2 O 4 a/C nanofiber precursor; (c, d) is porous NiCo 2 O 4 the/C @ S nano fiber.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The polyvinyl acetate high molecular material with the molecular weight of 500000 and the sulfur nano-particles with the particle size of 100nm are adopted in the embodiment of the invention, and other medicines are directly purchased analytical pure medicines and are not subjected to other treatment. The electrostatic spinning equipment adopted by the invention has the following types: and the high-voltage electrostatic spinning machine TL-Pro-BM.
Example 1 preparation of a lithium-sulfur Battery cathode nanofiber composite
The preparation method of the lithium-sulfur battery anode nanofiber composite material comprises the following steps:
step one, preparing an electrostatic spinning solution
Adding polyvinyl acetate into deionized water, stirring for 30min at 60 ℃ to completely dissolve the polyvinyl acetate to obtain a polyvinyl acetate solution with the mass percentage of 15%, then adding a proper amount of nickel acetate and cobalt acetate into the polyvinyl acetate solution, and stirring for 30min to completely dissolve the polyvinyl acetate solution to obtain an electrostatic spinning solution, wherein in the solution, the mass ratio of the nickel acetate to the polyvinyl acetate is 1:20, and the molar ratio of the nickel acetate to the cobalt acetate is 1: 2.
Step two, porous NiCo 2 O 4 Preparation of/C nanofiber precursor
Preparation of porous NiCo 2 O 4 In the/C nanofiber precursor process, the electrostatic spinning conditions are as follows:
voltage of 16kV and roller receiving speed of 30r min -1 Push speed of 1mL h -1 The distance between a needle head of electrostatic spinning and a receiver is 15cm, the electrostatic spinning time is 10 hours, and porous NiCo is obtained 2 O 4 the/C nanofiber precursor is shown in figure 1, and (a and b) are porous NiCo 2 O 4 a/C nanofiber precursor.
Step three, porous NiCo 2 O 4 Oxidation treatment of/C nanofiber precursor
For the porous NiCo prepared in the second step 2 O 4 The conditions for the oxidation treatment of the/C nanofiber precursor are as follows:
in air atmosphere at 5 deg.C for min -1 Gradually raising the temperature to 250 ℃ at the temperature raising speed, and keeping the temperature for 2 hours at constant temperature to obtain oxidized porous NiCo 2 O 4 a/C nanofiber precursor.
Step four, oxidizing the porous NiCo 2 O 4 Carbonization treatment of/C nanofiber precursor
For the porous NiCo after the step of the three-oxidation 2 O 4 The carbonization conditions of the/C nanofiber precursor are as follows: oxidizing the oxidized porous NiCo 2 O 4 the/C nanofiber precursor is put in inert gas at 5 ℃ for min -1 The temperature rising speed is gradually raised to 600 ℃, the temperature is kept for 3 hours, and porous NiCo is obtained after cooling 2 O 4 a/C nanofiber.
Step five, porous NiCo 2 O 4 C nano-fiber sulfurizing treatment
Mixing porous NiCo 2 O 4 the/C nano-fiber and the sulfur nano-particles are fully mixed and then placed in a closed container, and porous NiCo is added 2 O 4 The mass ratio of the/C nano-fiber to the sulfur nano-particle is 1:3, and the temperature is 10 ℃ for min under the inert atmosphere -1 The temperature rise speed is gradually increased to 300 ℃, and the temperature is kept for 12 hours to obtain the porous NiCo 2 O 4 the/C @ S nano-fiber composite material is shown in figure 1, and (C, d) are porous NiCo 2 O 4 and/C @ S nano-fibers.
Electrochemical test results: the porous NiCo prepared in this example was used 2 O 4 the/C @ S nanofiber composite material is used as a lithium sulfur battery anode to be assembled into a button half battery, and the test result is as follows: at 0.1A g -1 Under the current density, the reversible specific capacity of the first loop is 790mAh g -1 The coulombic efficiency of the first circle is 85 percent, and the reversible specific capacity is 711mAh g after the circulation is carried out for 200 times -1 The capacity retention rate was 90%, the rate performance was that the current density was 2.0A g -1 Reversible specific capacity 682mAh g -1 。
Example 2 preparation of a lithium-sulfur Battery cathode nanofiber composite
The preparation method of the lithium-sulfur battery cathode nanofiber composite material comprises the following steps:
step one, preparing an electrostatic spinning solution
Adding a proper amount of polyvinyl acetate into deionized water, stirring for 30min at 60 ℃ to completely dissolve the polyvinyl acetate to obtain a polyvinyl acetate solution with the mass percentage of 15%, then adding a proper amount of nickel acetate and cobalt acetate into the polyvinyl acetate solution, and stirring for 30min to completely dissolve the polyvinyl acetate solution, wherein the mass ratio of the nickel acetate to the polyvinyl acetate is 1:20, and the molar ratio of the nickel acetate to the cobalt acetate is 1: 2.
Step two, porous NiCo 2 O 4 Preparation of/C nanofiber precursor
Preparation of porous NiCo 2 O 4 The conditions for electrospinning of the/C nanofiber precursor were:
voltage of 16kV and receiving speed of roller of 30r min -1 Push speed 1mL h -1 The distance between a needle head of electrostatic spinning and a receiver is 15cm, the electrostatic spinning time is 10 hours, and porous NiCo is obtained 2 O 4 a/C nanofiber precursor.
Step three, porous NiCo 2 O 4 Oxidation treatment of/C nanofiber precursor
For the porous NiCo prepared in the second step 2 O 4 The oxidation treatment conditions of the/C nanofiber precursor are as follows:
mixing porous NiCo 2 O 4 Placing the/C nanofiber precursor in air atmosphere at 5 ℃ for min -1 The temperature rising speed is gradually increased to 250 ℃, and the temperature is kept for 2 hours at constant temperature to obtain oxidized porous NiCo 2 O 4 a/C nanofiber precursor.
Step four, oxidizing the porous NiCo 2 O 4 Carbonization treatment of/C nanofiber precursor
For oxidized porous NiCo 2 O 4 The carbonization conditions of the/C nanofiber precursor are as follows:
oxidizing NiCo 2 O 4 Putting the/C nanofiber precursor in inert gas at 5 ℃ for min -1 The temperature rising speed is gradually raised to 600 ℃, the temperature is kept for 3 hours, and porous NiCo is obtained after cooling 2 O 4 a/C nanofiber.
Step five, porous NiCo 2 O 4 C nano-fiber sulfurizing treatment
Mixing porous NiCo 2 O 4 the/C nano-fiber and the sulfur nano-particles are fully mixed and then placed in a closed container, and porous NiCo is added 2 O 4 The mass ratio of the/C nano-fiber to the sulfur nano-particle is 1:1, and the temperature is 10 ℃ for min under inert atmosphere -1 The temperature rise speed is gradually increased to 300 ℃, and the temperature is kept for 12 hours to obtain the porous NiCo 2 O 4 a/C @ S nanofiber composite.
Electrochemical test results: the porous NiCo prepared in this example was added 2 O 4 the/C @ S nanofiber composite material is used as a lithium sulfur battery anode to be assembled into a button half battery, and the test result is as follows: at 0.1A g -1 The reversible specific capacity of the first loop is 685mAh g under the current density -1 The coulombic efficiency of the first circle is 89%, and after 200 times of circulation, the reversible specific capacity is 630mAh g -1 The capacity retention rate was 92%, and the rate performance was 2.0A g -1 Reversible specific capacity of 602mAh g -1 。
Example 3 preparation of a lithium-sulfur Battery cathode nanofiber composite
The preparation method of the lithium-sulfur battery cathode nanofiber composite material comprises the following steps:
step one, preparing an electrostatic spinning solution
Adding polyvinyl acetate into deionized water, stirring for 30min at 60 ℃ to completely dissolve the polyvinyl acetate to obtain a polyvinyl acetate solution with the mass percentage of 15%, then adding a proper amount of nickel acetate and cobalt acetate into the polyvinyl acetate solution, and stirring for 30min to completely dissolve the polyvinyl acetate solution, wherein the mass ratio of the nickel acetate to the polyvinyl acetate is 1:40, and the molar ratio of the nickel acetate to the cobalt acetate is 1: 2.
Step two, porous NiCo 2 O 4 Preparation of/C nanofiber precursor
Preparation of porous NiCo 2 O 4 The conditions for electrospinning of the/C nanofiber precursor were:
voltage of 16kV and receiving speed of roller of 30r min -1 Push speed of 1mL h -1 The distance between a needle head of electrostatic spinning and a receiver is 15cm, the electrostatic spinning time is 10 hours, and porous NiCo is obtained 2 O 4 a/C nanofiber precursor.
Step three, porous NiCo 2 O 4 Oxidation treatment of/C nanofiber precursor
For porous NiCo 2 O 4 The conditions for oxidation treatment of the/C nanofiber precursor are as follows:
mixing porous NiCo 2 O 4 the/C nanofiber precursor is in air atmosphere at 5 ℃ for min -1 The temperature rising speed is gradually increased to 250 ℃, and the temperature is kept for 2 hours at constant temperature to obtain oxidized porous NiCo 2 O 4 a/C nanofiber precursor.
Step four, oxidizing the porous NiCo 2 O 4 Carbonization treatment of/C nanofiber precursor
For oxidized porous NiCo 2 O 4 The carbonization conditions of the/C nanofiber precursor are as follows:
under inert gas at 5 deg.C for min -1 The temperature rising speed is gradually raised to 600 ℃, the temperature is kept for 3 hours, and porous NiCo is obtained after cooling 2 O 4 a/C nanofiber.
Step five, porous NiCo 2 O 4 C nano-fiber sulfurizing treatment
Mixing porous NiCo 2 O 4 the/C nano-fiber and the sulfur nano-particle are fully mixed and then placed in a closed container, and porous NiCo 2 O 4 The mass ratio of the/C nano-fiber to the sulfur nano-particle is 1:3, and the temperature is 10 ℃ for min under the inert atmosphere -1 The temperature rise speed is gradually increased to 300 ℃, and the temperature is kept for 12 hours to obtain the porous NiCo 2 O 4 a/C @ S nanofiber composite.
Electrochemical test results: the porous NiCo prepared in this example was used 2 O 4 the/C @ S nanofiber composite material is used as a lithium sulfur battery anode to be assembled into a button half battery, and the test result is as follows: at 0.1A g -1 The reversible specific capacity of the first loop is 850mAh g under the current density -1 The coulombic efficiency of the first circle is 84 percent, and the reversible specific capacity after 200 times of circulation is 730mAh g -1 The capacity retention rate was 85.8%, and the rate capability was 2.0A g -1 Reversible specific capacity 721mAh g -1 。
Example 4 preparation of a lithium-sulfur Battery cathode nanofiber composite
The preparation method of the lithium-sulfur battery cathode nanofiber composite material comprises the following steps:
step one, preparing an electrostatic spinning solution
Adding polyvinyl acetate into deionized water, stirring for 30min at 60 ℃ to completely dissolve the polyvinyl acetate to obtain a polyvinyl acetate solution with the mass percentage of 15%, then adding a proper amount of nickel acetate and cobalt acetate into the polyvinyl acetate solution, and stirring for 30min until the polyvinyl acetate is completely dissolved. Wherein the mass ratio of the nickel acetate to the polyvinyl acetate is 1:20, and the molar ratio of the nickel acetate to the cobalt acetate is 1: 2.
Step two, porous NiCo 2 O 4 Preparation of/C nanofiber precursor
Preparation of porous NiCo 2 O 4 The conditions of electrostatic spinning of the/C nanofiber precursor are as follows:
voltage of 16kV and roller receiving speed of 30r min -1 Push speed 1mL h -1 ElectrospunThe distance between the needle and the receiver is 15cm, the electrostatic spinning time is 10h, and the porous NiCo is obtained 2 O 4 a/C nanofiber precursor.
Step three, porous NiCo 2 O 4 Oxidation treatment of/C nanofiber precursor
For porous NiCo 2 O 4 The conditions for the oxidation treatment of the/C nanofiber precursor are as follows:
at 5 deg.C for min in air atmosphere -1 Gradually raising the temperature to 250 ℃, keeping the temperature for 2 hours at constant temperature to obtain oxidized porous NiCo 2 O 4 a/C nanofiber precursor.
Step four, oxidizing the porous NiCo 2 O 4 Carbonization treatment of/C nanofiber precursor
For oxidized porous NiCo 2 O 4 The carbonization conditions of the/C nanofiber precursor are as follows:
in inert gas at 5 deg.C for min -1 The temperature rising speed is gradually raised to 600 ℃, the temperature is kept for 3 hours, and porous NiCo is obtained after cooling 2 O 4 a/C nanofiber.
Step five, porous NiCo 2 O 4 C nano-fiber sulfurizing treatment
Mixing porous NiCo 2 O 4 the/C nano-fiber and the sulfur nano-particles are fully mixed and then placed in a closed container, and porous NiCo is added 2 O 4 The mass ratio of the/C nano-fiber to the sulfur nano-particle is 10:1, and the mixture is heated at 10 ℃ for min in inert atmosphere -1 The temperature rise speed is gradually increased to 300 ℃, and the temperature is kept for 12 hours to obtain the porous NiCo 2 O 4 a/C @ S nanofiber composite.
Electrochemical test results: the porous NiCo prepared in this example was used 2 O 4 the/C @ S nanofiber composite material is used as a lithium sulfur battery anode to be assembled into a button half battery, and the test result is as follows: at 0.1A g -1 The reversible specific capacity of the first loop is 356mAh g under the current density -1 The coulombic efficiency of the first circle is 93 percent, and the reversible specific capacity is 341mAh g after the circulation is carried out for 200 times -1 The capacity retention rate was 96%, and the rate performance was that the current density was 2.0A g -1 Is reversibleSpecific capacity 320mAh g -1 。
Example 5 preparation of a lithium-sulfur Battery cathode nanofiber composite
The preparation method of the lithium-sulfur battery cathode nanofiber composite material comprises the following steps:
step one, preparing an electrostatic spinning solution
Adding polyvinyl acetate into deionized water, stirring for 30min at 60 ℃ to completely dissolve the polyvinyl acetate to obtain a polyvinyl acetate solution with the mass percentage of 15%, then adding a proper amount of nickel acetate and cobalt acetate into the polyvinyl acetate solution, and stirring for 30min to completely dissolve the polyvinyl acetate solution, wherein the mass ratio of the nickel acetate to the polyvinyl acetate is 1:20, and the molar ratio of the nickel acetate to the cobalt acetate is 1: 2.
Step two, porous NiCo 2 O 4 Preparation of/C nanofiber precursor
Preparation of porous NiCo 2 O 4 The conditions for electrospinning of the/C nanofiber precursor were:
voltage of 16kV and receiving speed of roller of 30r min -1 Push speed 1mL h -1 The distance between a needle head of electrostatic spinning and a receiver is 15cm, the electrostatic spinning time is 10 hours, and porous NiCo is obtained 2 O 4 a/C nanofiber precursor.
Step three, porous NiCo 2 O 4 Oxidation treatment of/C nanofiber precursor
For porous NiCo 2 O 4 The conditions for oxidation treatment of the/C nanofiber precursor are as follows:
at 5 deg.C for min in air atmosphere -1 Gradually raising the temperature to 250 ℃, keeping the temperature for 2 hours at constant temperature to obtain oxidized porous NiCo 2 O 4 a/C nanofiber precursor.
Step four, oxidizing the porous NiCo 2 O 4 Carbonization treatment of/C nanofiber precursor
For oxidized porous NiCo 2 O 4 The carbonization conditions of the/C nanofiber precursor are as follows:
in an inert gas at 5 deg.Cmin -1 The temperature rising speed is gradually raised to 600 ℃, the temperature is kept for 3 hours, and porous NiCo is obtained after cooling 2 O 4 a/C nanofiber.
Step five, porous NiCo 2 O 4 C nano-fiber sulfurizing treatment
Mixing porous NiCo 2 O 4 the/C nano-fiber and the sulfur nano-particles are fully mixed and then placed in a closed container, and porous NiCo is added 2 O 4 The mass ratio of the/C nano-fiber to the sulfur nano-particle is 1:10, and the mixture is heated at 10 ℃ for min in inert atmosphere -1 The temperature rise speed is gradually increased to 300 ℃, and the temperature is kept for 12 hours to obtain the porous NiCo 2 O 4 a/C @ S nanofiber composite.
Electrochemical test results: porous NiCo prepared according to this example 2 O 4 the/C @ S nanofiber composite material is used as a lithium sulfur battery anode to be assembled into a button half battery, and the test result is as follows: at 0.1A g -1 The reversible specific capacity of the first circle is 1126mAh g under the current density -1 The coulombic efficiency of the first circle is 72 percent, and the reversible specific capacity after 200 times of circulation is 789mAh g -1 The capacity retention rate was 70%, the rate performance was that the current density was 2.0A g -1 Reversible specific capacity 691mAh g -1 。
Comparative example 1
The difference between the comparative example and the example 1 is that in the step one, the porous C @ S nanofiber composite is prepared by preparing the electrostatic spinning solution without adding nickel acetate and cobalt acetate.
Electrochemical test results: the porous C @ S nanofiber composite prepared according to the comparative example was at 0.1A g when used as a positive electrode material for a lithium sulfur battery -1 The reversible specific capacity of the first loop is 985mAh g under the current density -1 The coulombic efficiency of the first circle is 65 percent, and the reversible specific capacity after 200 times of circulation is 210mAh g -1 The capacity retention rate was 21.3%, and the rate capability was 2.0A g -1 Reversible specific capacity of 630mAh g -1 。
By comparing example 1 with comparative example 1, NiCo is known 2 O 4 The nanoparticles have good adsorption effect on sulfur to prevent polysulfide from shuttling toThe negative electrode is deactivated.
Examples 2 to 5 of the invention illustrate the conditioning of NiCo 2 O 4 The proportion of the nano particles to the sulfur nano particles can regulate and control the sulfur fixation effect and the overall theoretical specific capacity of the composite material.
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (6)
1. A preparation method of a nano-fiber composite material of a lithium-sulfur battery anode is characterized in that,
the method comprises the following steps: preparation of porous NiCo by electrostatic spinning method 2 O 4 a/C nanofiber precursor;
mixing the porous NiCo 2 O 4 Oxidizing and carbonizing the/C nanofiber precursor to obtain the porous NiCo 2 O 4 a/C nanofiber;
mixing the porous NiCo 2 O 4 the/C nano-fiber is subjected to high-temperature sulfurizing treatment to obtain porous NiCo 2 O 4 the/C @ S nanofiber composite material is the lithium-sulfur battery positive electrode nanofiber composite material;
the high-temperature sulfurizing treatment process comprises the following steps:
mixing sulfur nanoparticles with the porous NiCo 2 O 4 Mixing the/C nanofibers, placing in a sealed container, and keeping at 1-20 deg.C for min under inert atmosphere -1 Heating to 300 ℃, and keeping the temperature for 5-30 h;
the preparation process of the electrostatic spinning solution comprises the following steps:
adding polyvinyl acetate into deionized water, stirring for 30min at 60 ℃ until the polyvinyl acetate is completely dissolved to obtain a polyvinyl acetate solution with the mass fraction of 5% -50%, then adding nickel acetate and cobalt acetate into the polyvinyl acetate solution, and stirring for 30min until the polyvinyl acetate is completely dissolved;
wherein the mass ratio of the nickel acetate to the polyvinyl acetate is 0.01-1, and the molar ratio of the nickel acetate to the cobalt acetate is 1: 2;
the conditions of the oxidation treatment are as follows:
mixing the porous NiCo 2 O 4 The precursor of the/C nano-fiber is prepared at the temperature of 1-10 ℃ for min -1 The temperature rising speed is gradually increased to 150 ℃ and 300 ℃, and the temperature is kept for 0.5 to 5 hours;
the carbonization treatment conditions are as follows:
oxidizing the porous NiCo treated by the oxidation treatment 2 O 4 the/C nanofiber precursor is put in inert gas at the temperature of 1-20 ℃ for min -1 The temperature is raised to 500 ℃ and 1000 ℃, and the temperature is kept constant for 0.5 to 10 hours.
2. The method of preparing a lithium sulfur battery positive electrode nanofiber composite according to claim 1,
the polyvinyl acetate has a molecular weight of 10000-1000000.
3. The method of preparing a lithium sulfur battery positive electrode nanofiber composite according to claim 1,
the electrostatic spinning conditions are as follows:
voltage of 5-50kV and roller receiving speed of 0-100r min -1 And is not equal to 0, the push injection pushing speed is 0.1-10mL h -1 The distance between the needle head of the electrostatic spinning and the receiver is 5-30cm, and the electrostatic spinning time is 1-100 h.
4. The method of preparing a lithium sulfur battery positive electrode nanofiber composite according to claim 1,
the size of the sulfur nano-particles is 50-1000nm, and the sulfur nano-particles and the porous NiCo 2 O 4 The mass ratio of the/C nano fiber is 0.1-10.
5. The positive electrode nanofiber composite for the lithium-sulfur battery prepared by the method of any one of claims 1 to 4.
6. Use of the lithium sulfur battery positive electrode nanofiber composite of claim 5 in any one of,
(1) preparing an energy storage element;
(2) an electronic device is prepared.
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| CN1354529A (en) * | 2000-11-22 | 2002-06-19 | 三星Sdi株式会社 | Positive electrode of lithium-sulfur cell and lithium-sulfur cell including said positive electrode |
| CN105470484A (en) * | 2015-12-04 | 2016-04-06 | 厦门大学 | Preparation method of graphene/stannic oxide composite nanofiber membrane and application |
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| US9136526B2 (en) * | 2012-04-20 | 2015-09-15 | Korea Institute Of Energy Research | Method of manufacturing anode active material, and anode and lithium battery using the anode active material |
| US10312500B2 (en) * | 2016-01-06 | 2019-06-04 | Toyota Motor Engineering & Manufacturing North America, Inc. | Formation of slurry for high loading sulfur cathodes |
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