CN112542579A - Conductive Janus film, preparation method and application of conductive Janus film in preparation of lithium-sulfur battery anode - Google Patents
Conductive Janus film, preparation method and application of conductive Janus film in preparation of lithium-sulfur battery anode Download PDFInfo
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Abstract
The invention provides a conductive Janus film which comprises the following raw materials: 0.1-0.6 g of multi-walled carbon nano-tube, 10-40 ml of concentrated sulfuric acid solution, 5-10 ml of concentrated nitric acid solution, 200-500 ml of deionized water, 2-8 ml of organosilane coupling agent, 1-3 g of anionic surfactant, 0.01-0.06 g of polytetrafluoroethylene, 1-3 ml of azomethyl pyrrolidone solution, 1-3 mg of sublimed sulfur, CS20.1-0.5 ml of solution and 0.5-1 ml of isopropanol solution; the preparation method comprises the following steps: 1) preparing oxidized multi-walled carbon nanotubes, 2) preparing ammonium carbon nanotubes, 3) preparing anionic carbon nanotubes, 4) preparing flexible carbon nanotubes, 5) preparing a sulfur @ carbon nanotube composite material, and 6) preparing a conductive Janus film; the invention is applicable to lithium sulfurThe positive electrode of the battery has the beneficial effects of obviously improving the specific discharge capacity, the electrochemical performance and the cycle performance of the lithium-sulfur battery, and is suitable for the field of Janus films.
Description
Technical Field
The invention relates to the technical field of Janus films, in particular to a conductive Janus film, a preparation method and application thereof in preparation of a lithium-sulfur battery anode.
Background
The lithium-sulfur battery is a lithium battery with sulfur as the positive electrode and metal lithium as the negative electrode. Because sulfur is a non-conductive substance, a sulfur simple substance is generally compounded with a conductive carbon material to improve the conductivity of the conventional lithium sulfur battery, but an unmodified carbon material can only be used as a conductive matrix, the shuttle effect of the carbon material on polysulfide anions and the volume expansion effect of an electrode in the lithium sulfur battery are limited, and the capacity and the cycle life of the prepared battery are usually very poor. Therefore, the development of the flexible positive electrode material with ion selectivity and good conductivity is expected to solve the problems of the lithium-sulfur battery and improve the electrochemical performance of the battery.
In the prior art, Janus films are commonly used in the fields of oil-water separation, separation of mist and water in air, bubblers and the like. There is no study relating to the application of Janus membranes to positive electrodes of lithium sulfur batteries.
Disclosure of Invention
Aiming at the defects in the related technology, the technical problem to be solved by the invention is as follows: provided is a conductive Janus film for a positive electrode of a lithium-sulfur battery, which can significantly improve the specific discharge capacity, electrochemical performance and cycle performance of the lithium-sulfur battery.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a conductive Janus film comprising the following raw materials: 0.1-0.6 g of multi-walled carbon nano-tube, 10-40 ml of concentrated sulfuric acid solution, 5-10 ml of concentrated nitric acid solution, 200-500 ml of deionized water, 2-8 ml of organosilane coupling agent, 1-3 g of anionic surfactant, 0.01-0.06 g of polytetrafluoroethylene, 1-3 ml of azomethyl pyrrolidone solution, 1-3 mg of sublimed sulfur, CS2 0.1-0.5 ml of solution and 0.5-1 ml of isopropanol solution.
Preferably, the organosilane coupling agent is a methanol or ethanol solution of 3- (trimethoxysilylpropyl) dimethyloctadecyl ammonium chloride.
Preferably, the anionic surfactant is sodium nonylphenol polyoxyethylene ether sulfate.
The invention also provides a preparation method of the conductive Janus film, which comprises the following steps:
1) preparing oxidized multi-wall carbon nanotubes: adding a multi-walled carbon nanotube into a concentrated sulfuric acid solution and a concentrated nitric acid solution, uniformly dispersing to obtain a solution 1, carrying out pre-oxidation reflux treatment for 8 hours at the temperature of 60 ℃, and then diluting the solution 1 to the concentration of 0.2-1.0 g/L by using deionized water; carrying out suction filtration separation on the diluted solution 1 by using a nylon filter membrane with the aperture of 0.22 mu m, and washing a filter cake until the pH value of a washing liquid is 7; vacuum drying the filter cake for 24h at 70 ℃ to obtain the oxidized multi-walled carbon nanotube rich in carboxyl and hydroxyl;
2) preparing an ammonium carbon nanotube: mixing the prepared oxidized multi-walled carbon nanotube and an organosilane coupling agent together to obtain a solution 2, and carrying out ultrasonic dispersion on the solution 2 for 30 min; then carrying out water bath reaction for 2h at the temperature of 60 ℃, continuously stirring in the water bath reaction process, and then carrying out vacuum drying for 48h at the temperature of 70 ℃ to obtain an ammonium multi-walled carbon nanotube;
3) preparing the anionic carbon nanotube: adding an ammonium multi-walled carbon nanotube and an anionic surfactant into 30-50 wt% of absolute ethyl alcohol, and carrying out water bath reaction at the temperature of 60 ℃ for 24 hours to obtain an anionic carbon nanotube;
4) preparing flexible carbon nanotubes: adding the multi-walled carbon nanotube or the oxidized multi-walled carbon nanotube prepared in the step 1) and polytetrafluoroethylene into a N-methyl pyrrolidone solution, uniformly stirring to form a slurry, coating the slurry into a film layer with uniform thickness, and performing vacuum drying at the temperature of 70 ℃ for 24 hours to prepare a flexible carbon nanotube thin layer;
5) preparing a sulfur @ carbon nanotube composite material: dissolving sublimed sulfur in CS2Obtaining a solution 3 in a solvent, and dripping the solution 3 on the flexible carbon nanotube thin layer prepared in the step 4) to prepare the sulfur @ carbon nanotube composite material;
6) preparing a conductive Janus film: adding the anionic carbon nano tube prepared in the step 3) into an isopropanol solution, uniformly stirring to form a solution 4, dripping the solution 4 on the sulfur @ carbon nano tube composite material by using a dropper, and drying in vacuum for 24 hours at the temperature of 70 ℃ to obtain the flexible sulfur-carbon composite material with ion selectivity, namely the conductive Janus film.
Preferably, the organosilane coupling agent is a methanol or ethanol solution of 3- (trimethoxysilylpropyl) dimethyloctadecyl ammonium chloride.
Preferably, the anionic surfactant is sodium nonylphenol polyoxyethylene ether sulfate.
The invention also provides application of the conductive Janus film in preparation of the positive electrode of the lithium-sulfur battery.
The invention has the beneficial technical effects that:
1. a conductive Janus film comprising the following raw materials: 0.1-0.6 g of multi-walled carbon nano-tube, 10-40 ml of concentrated sulfuric acid solution, 5-10 ml of concentrated nitric acid solution, 200-500 ml of deionized water, 2-8 ml of organosilane coupling agent, 1-3 g of anionic surfactant, 0.01-0.06 g of polytetrafluoroethylene, 1-3 ml of azomethyl pyrrolidone solution, 1-3 mg of sublimed sulfur, CS2 0.1-0.5 ml of solution and 0.5-1 ml of isopropanol solution.
The conductive Janus film prepared from the raw materials is used as the positive electrode of the lithium-sulfur battery, so that the discharge specific capacity, the electrochemical performance and the cycle performance of the lithium-sulfur battery can be remarkably improved, and the problems of poor sulfur conductivity, shuttle effect of multi-sulfur anions and volume expansion effect of an electrode are solved by compounding the sublimed sulfur and the multi-walled carbon nano tube.
2. The organosilane coupling agent is a methanol or ethanol solution of 3- (trimethoxysilylpropyl) dimethyloctadecyl ammonium chloride; the anionic surfactant is sodium nonylphenol polyoxyethylene ether sulfate.
The organosilane coupling agent and the anionic surfactant adopted by the invention have lower cost and are environment-friendly.
3. A method of making a conductive Janus film comprising the steps of: 1) preparing oxidized multi-walled carbon nanotubes; 2) preparing an ammonium carbon nanotube; 3) preparing the anionic carbon nanotube: 4) preparing flexible carbon nanotubes; 5) preparing a sulfur @ carbon nanotube composite material; 6) conductive Janus films were prepared.
The preparation method provided by the invention is simple, and the reaction conditions are mild and easy to operate. The prepared conductive Janus film is used as the positive electrode of the lithium-sulfur battery, so that the discharge specific capacity, the electrochemical performance and the cycle performance of the lithium-sulfur battery are remarkably improved, and the problems of poor sulfur conductivity, shuttle effect of multi-sulfur anions and volume expansion effect of an electrode are solved.
4. An application of a conductive Janus film in preparing a positive electrode of a lithium-sulfur battery.
The invention adopts the conductive Janus film as the anode of the lithium-sulfur battery, and provides a new application of the conductive Janus film. The existing Janus film is commonly used in the fields of oil-water separation, separation of mist and water in air, a bubbler and the like.
In order to better understand the essence of the present invention, the advantages of the prepared conductive Janus films and their role in lithium sulfur batteries will be illustrated below by examining the internal charge transfer resistance, cycling performance at 0.2C current density, and electrochemical performance at different current densities of conventional lithium sulfur batteries as well as lithium sulfur batteries prepared according to the present invention.
It should be noted that: the conventional lithium-sulfur battery is a lithium-sulfur battery prepared by using a conventional lithium-sulfur battery cathode material, and the lithium-sulfur battery prepared by the invention is a lithium-sulfur battery prepared by using the conductive Janus film provided by the invention as a cathode material.
Fig. 1 is an impedance spectrum of a lithium-sulfur battery, in which the internal charge transfer resistance, ion diffusion resistance, and battery internal resistance of a conventional lithium-sulfur battery and a lithium-sulfur battery prepared according to the present invention are measured, and it can be seen from fig. 1 that the curves of the impedance spectrum are composed of a semicircular arc of a high frequency region, the diameter of which represents the charge transfer resistance, and an oblique line of a low frequency region, the oblique line representing the ion diffusion resistance, and the intersection point of the left side of the semicircular arc and the horizontal axis represents the battery internal resistance; by comparison, the lithium-sulfur battery prepared by the invention has smaller internal resistance and charge transfer resistance than the traditional lithium-sulfur battery. Therefore, the lithium-sulfur battery prepared by the invention has better conductivity and can accelerate the transmission speed of electrons in the circulation process.
FIG. 2 is a current density of 0.2C for a lithium sulfur batteryAccording to the electrochemical performance curve chart under the temperature, by detecting the cycle performance of the conventional lithium-sulfur battery and the lithium-sulfur battery prepared by the invention under the current density of 0.2C, the specific discharge capacity of the first circle of the conventional lithium-sulfur battery is 1364.2 mAh g as can be seen from the graph in fig. 2-1The first circle of the lithium-sulfur battery prepared by the invention has specific discharge capacity of 1496.1 mAh g-1(ii) a After 100 cycles of charge and discharge, the specific discharge capacity of the traditional lithium-sulfur battery is 789.2 mAh g-1The specific discharge capacity of the lithium-sulfur battery prepared by the invention is 1012.4 mAh g-1. Therefore, the lithium-sulfur battery prepared by the method has better cycle performance and more excellent electrochemical performance.
FIG. 3 is a graph showing electrochemical performance of lithium-sulfur batteries at different current densities, and it can be seen from FIG. 3 that the specific discharge capacities of conventional lithium-sulfur batteries are 734.5, 645.8, 439.6, 279.3 and 117.6mAh g at current densities of 0.5C, 1C, 2C, 3C and 4C when the conventional lithium-sulfur batteries and the lithium-sulfur batteries prepared according to the present invention are subjected to charge and discharge tests at current densities of 0.5C, 1C, 2C, 3C and 4C-1The specific discharge capacity of the lithium-sulfur battery prepared by the invention is 914.3, 841.9, 771.5, 719.3 and 671.5mAh g at the current density of 0.5C, 1C, 2C, 3C and 4C respectively-1(ii) a When the current density returns to 0.5C again, the specific discharge capacity of the conventional lithium-sulfur battery is 651.1 mAh g-1The specific discharge capacity of the lithium-sulfur battery prepared by the invention is 814.3 mAh g-1. Therefore, the lithium-sulfur battery prepared by the invention has higher battery capacity, higher sulfur utilization rate and lower shuttling effect under different current densities.
Drawings
FIG. 1 is an impedance spectrum of a lithium sulfur battery;
FIG. 2 is a graph of electrochemical performance of a lithium sulfur battery at a current density of 0.2C;
FIG. 3 is a graph of electrochemical performance of lithium sulfur batteries at different current densities;
10 is the impedance profile of a conventional lithium sulfur battery; 20 is an impedance spectrum of the lithium-sulfur battery provided by the invention; 30 is the coulombic efficiency of the conventional lithium sulfur battery at a current density of 0.2C; 40 is the coulombic efficiency of the lithium-sulfur battery provided by the invention under the current density of 0.2C; 50 is a discharge performance curve chart of the conventional lithium-sulfur battery under the current density of 0.2C; 60 is a discharge performance curve diagram of the lithium-sulfur battery provided by the invention under the current density of 0.2C; 70 is a graph of electrochemical performance of a conventional lithium sulfur battery at different current densities; 80 is a graph of electrochemical performance of lithium sulfur batteries provided by the present invention at different current densities.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments, and it is obvious that the described embodiments are some embodiments, but not all embodiments, of the present invention; 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.
Example one
A conductive Janus film comprising the following raw materials: 0.1g of multi-wall carbon nano-tube, 20ml of concentrated sulfuric acid solution, 8ml of concentrated nitric acid solution, 200ml of deionized water, 2ml of organosilane coupling agent, 1g of anionic surfactant, 0.02g of polytetrafluoroethylene, 2ml of nitrogen methyl pyrrolidone solution, 1mg of sublimed sulfur and CS2 0.1ml of the solution and 0.3ml of an isopropanol solution.
Further, the organosilane coupling agent is a methanol solution of 3- (trimethoxysilylpropyl) dimethyloctadecyl ammonium chloride.
Further, the anionic surfactant is sodium nonylphenol polyoxyethylene ether sulfate.
Specifically, the concentration of the concentrated sulfuric acid is 70 wt%.
Specifically, the concentration of the concentrated nitric acid is 68 wt%.
Specifically, the concentration of the 3- (trimethoxysilylpropyl) dimethyloctadecyl ammonium chloride is 30% methanol solution.
Specifically, the concentration of the azomethylpyrrolidone solution is 99%.
Specifically, theThe CS2 The concentration of the solution was 98%.
A preparation method of a conductive Janus film comprises the following steps:
1) preparing oxidized multi-wall carbon nanotubes: adding a multi-walled carbon nanotube into a concentrated sulfuric acid solution and a concentrated nitric acid solution, uniformly dispersing to obtain a solution 1, carrying out pre-oxidation reflux treatment for 8 hours at the temperature of 60 ℃, and then diluting the solution 1 to the concentration of 0.2-1.0 g/L by using deionized water;
carrying out suction filtration separation on the diluted solution 1 by using a nylon filter membrane with the aperture of 0.22 mu m, and washing a filter cake until the pH value of a washing liquid is 7; vacuum drying the filter cake for 24h at 70 ℃ to obtain the oxidized multi-walled carbon nanotube rich in carboxyl and hydroxyl;
2) preparing an ammonium carbon nanotube: mixing the prepared oxidized multi-walled carbon nanotube and an organosilane coupling agent together to obtain a solution 2, and carrying out ultrasonic dispersion on the solution 2 for 30 min; then carrying out water bath reaction for 2h at the temperature of 60 ℃, continuously stirring in the water bath reaction process, and then carrying out vacuum drying for 48h at the temperature of 70 ℃ to obtain an ammonium multi-walled carbon nanotube;
3) preparing the anionic carbon nanotube: adding an ammonium multi-walled carbon nanotube and an anionic surfactant into 30-50 wt% of absolute ethyl alcohol, and carrying out water bath reaction at the temperature of 60 ℃ for 24 hours to obtain an anionic carbon nanotube;
4) preparing flexible carbon nanotubes: adding the oxidized multi-walled carbon nano-tube prepared in the step 1) and polytetrafluoroethylene into a N-methyl pyrrolidone solution, uniformly stirring to form slurry, coating the slurry into a film layer with uniform thickness, and performing vacuum drying for 24 hours at the temperature of 70 ℃ to prepare a flexible carbon nano-tube thin layer;
5) preparing a sulfur @ carbon nanotube composite material: dissolving sublimed sulfur in CS2Obtaining a solution 3 in a solvent, and dripping the solution 3 on the flexible carbon nanotube thin layer prepared in the step 4) to prepare the sulfur @ carbon nanotube composite material;
6) preparing a conductive Janus film: adding the anionic carbon nano tube prepared in the step 3) into an isopropanol solution, uniformly stirring to form a solution 4, dripping the solution 4 on the sulfur @ carbon nano tube composite material by using a dropper, and drying in vacuum for 24 hours at the temperature of 70 ℃ to obtain the flexible sulfur-carbon composite material with ion selectivity, namely the conductive Janus film.
Example two
A conductive Janus film comprising the following raw materials: 0.2g of multi-wall carbon nano-tube, 10ml of concentrated sulfuric acid solution, 10ml of concentrated nitric acid solution, 250ml of deionized water, 4ml of organosilane coupling agent, 2g of anionic surfactant, 0.04g of polytetrafluoroethylene, 3ml of nitrogen methyl pyrrolidone solution, 2mg of sublimed sulfur and CS2 0.25ml of the solution and 1ml of an isopropanol solution.
Example one was repeated following the same procedure.
EXAMPLE III
A conductive Janus film comprising the following raw materials: 0.3g of multi-wall carbon nano-tube, 40ml of concentrated sulfuric acid solution, 5ml of concentrated nitric acid solution, 500ml of deionized water, 6ml of organosilane coupling agent, 3g of anionic surfactant, 0.06g of polytetrafluoroethylene, 1ml of nitrogen methyl pyrrolidone solution, 3mg of sublimed sulfur and CS2 0.5ml of the solution and 0.5ml of an isopropanol solution.
Example one was repeated following the same procedure.
Example four
A conductive Janus film comprising the following raw materials: 0.2g of multi-wall carbon nano-tube, 20ml of concentrated sulfuric acid solution, 8ml of concentrated nitric acid solution, 200ml of deionized water, 8ml of organosilane coupling agent, 3g of anionic surfactant, 0.04g of polytetrafluoroethylene, 2ml of nitrogen methyl pyrrolidone solution, 1mg of sublimed sulfur and CS2 0.3ml of the solution and 0.3ml of an isopropanol solution.
Further, the organosilane coupling agent is a methanol solution of 3- (trimethoxysilylpropyl) dimethyloctadecyl ammonium chloride.
Further, the anionic surfactant is sodium nonylphenol polyoxyethylene ether sulfate.
Specifically, the concentration of the concentrated sulfuric acid is 70 wt%.
Specifically, the concentration of the concentrated nitric acid is 68 wt%.
Specifically, the concentration of the 3- (trimethoxysilylpropyl) dimethyloctadecyl ammonium chloride is 50% of methanol solution.
Specifically, the concentration of the azomethylpyrrolidone solution is 99%.
In particular, the CS2 The concentration of the solution was 98%.
A preparation method of a conductive Janus film comprises the following steps:
1) preparing oxidized multi-wall carbon nanotubes: adding 1g of multi-walled carbon nano tube into a concentrated sulfuric acid solution and a concentrated nitric acid solution, uniformly dispersing to obtain a solution 1, carrying out pre-oxidation reflux treatment for 8 hours at the temperature of 60 ℃, and then diluting the solution 1 to the concentration of 0.2-1.0 g/L by using deionized water;
carrying out suction filtration separation on the diluted solution 1 by using a nylon filter membrane with the aperture of 0.22 mu m, and washing a filter cake until the pH value of a washing liquid is 7; vacuum drying the filter cake for 24h at 70 ℃ to obtain the oxidized multi-walled carbon nanotube rich in carboxyl and hydroxyl;
2) preparing an ammonium carbon nanotube: mixing the prepared oxidized multi-walled carbon nanotube and an organosilane coupling agent together to obtain a solution 2, and carrying out ultrasonic dispersion on the solution 2 for 30 min; then carrying out water bath reaction for 2h at the temperature of 60 ℃, continuously stirring in the water bath reaction process, and then carrying out vacuum drying for 48h at the temperature of 70 ℃ to obtain an ammonium multi-walled carbon nanotube;
3) preparing the anionic carbon nanotube: adding an ammonium multi-walled carbon nanotube and an anionic surfactant into 30-50 wt% of absolute ethyl alcohol, and carrying out water bath reaction at the temperature of 60 ℃ for 24 hours to obtain an anionic carbon nanotube;
4) preparing flexible carbon nanotubes: adding 1g of multi-walled carbon nano tube and polytetrafluoroethylene into a N-methyl pyrrolidone solution, uniformly stirring to form slurry, coating the slurry into a film layer with uniform thickness, and performing vacuum drying at the temperature of 70 ℃ for 24 hours to prepare a flexible carbon nano tube thin layer;
5) preparing a sulfur @ carbon nanotube composite material: dissolving sublimed sulfur in CS2Obtaining a solution 3 in a solvent, and dripping the solution 3 on the flexible carbon nanotube thin layer prepared in the step 4) to prepare the sulfur @ carbon nanotube composite material;
6) preparing a conductive Janus film: adding the anionic carbon nano tube prepared in the step 3) into an isopropanol solution, uniformly stirring to form a solution 4, dripping the solution 4 on the sulfur @ carbon nano tube composite material by using a dropper, and drying in vacuum for 24 hours at the temperature of 70 ℃ to obtain the flexible sulfur-carbon composite material with ion selectivity, namely the conductive Janus film.
EXAMPLE five
A conductive Janus film comprising the following raw materials: 0.4g of multi-wall carbon nano-tube, 10ml of concentrated sulfuric acid solution, 10ml of concentrated nitric acid solution, 250ml of deionized water, 8ml of organosilane coupling agent, 2.5g of anionic surfactant, 0.01g of polytetrafluoroethylene, 3ml of nitrogen methyl pyrrolidone solution, 2mg of sublimed sulfur and CS2 0.5ml of the solution and 1ml of an isopropanol solution.
Example four was repeated following the same procedure. But 0.2g of multi-walled carbon nanotubes were added in step 1); the amount of the multi-walled carbon nanotubes added in step 4) was 0.2 g.
EXAMPLE six
A conductive Janus film comprising the following raw materials: 0.6g of multi-wall carbon nano-tube, 40ml of concentrated sulfuric acid solution, 5ml of concentrated nitric acid solution, 500ml of deionized water, 6ml of organosilane coupling agent, 3g of anionic surfactant, 0.06g of polytetrafluoroethylene, 1ml of nitrogen methyl pyrrolidone solution, 3mg of sublimed sulfur and CS2 0.1ml of the solution and 0.5ml of an isopropanol solution.
Example four was repeated following the same procedure. But 0.3g of multi-walled carbon nanotubes were added in step 1); the amount of the multi-walled carbon nanotubes added in step 4) was 0.3 g.
The conductive Janus film prepared from the raw materials is used as the positive electrode of the lithium-sulfur battery, so that the discharge specific capacity, the electrochemical performance and the cycle performance of the lithium-sulfur battery can be remarkably improved, and the problems of poor sulfur conductivity, shuttle effect of multi-sulfur anions and volume expansion effect of an electrode are solved by compounding the sublimed sulfur and the multi-walled carbon nano tube.
The organosilane coupling agent and the anionic surfactant adopted by the invention have lower cost and are environment-friendly.
The preparation method provided by the invention is simple, and the reaction conditions are mild and easy to operate.
An application of a conductive Janus film in preparing a positive electrode of a lithium-sulfur battery. The invention adopts the conductive Janus film as the anode of the lithium-sulfur battery, and provides a new application of the conductive Janus film. The existing Janus film is commonly used in the fields of oil-water separation, separation of mist and water in air, a bubbler and the like.
In the description of the present invention, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
In the foregoing embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
It will be appreciated that the relevant features of the method, apparatus and system described above are referred to one another. In addition, "first", "second", and the like in the above embodiments are for distinguishing the embodiments, and do not represent merits of the embodiments.
It can be clearly understood by those skilled in the art that, for convenience and brevity of description, the specific working processes of the system and the module described above may refer to the corresponding processes in the foregoing method embodiments, and are not described herein again.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. A conductive Janus film, characterized by: the method comprises the following raw materials: 0.1-0.6 g of multi-walled carbon nano-tube, 10-40 ml of concentrated sulfuric acid solution, 5-10 ml of concentrated nitric acid solution, 200-500 ml of deionized water, 2-8 ml of organosilane coupling agent, 1-3 g of anionic surfactant, 0.01-0.06 g of polytetrafluoroethylene, 1-3 ml of azomethyl pyrrolidone solution, 1-3 mg of sublimed sulfur, CS2 0.1-0.5 ml of solution and 0.5-1 ml of isopropanol solution.
2. A conductive Janus film, characterized by: the organosilane coupling agent is methanol or ethanol solution of 3- (trimethoxysilylpropyl) dimethyloctadecyl ammonium chloride.
3. A conductive Janus film, characterized by: the anionic surfactant is sodium nonylphenol polyoxyethylene ether sulfate.
4. A preparation method of a conductive Janus film is characterized by comprising the following steps: the method comprises the following steps:
1) preparing oxidized multi-wall carbon nanotubes: adding a multi-walled carbon nanotube into a concentrated sulfuric acid solution and a concentrated nitric acid solution, uniformly dispersing to obtain a solution 1, carrying out pre-oxidation reflux treatment for 8 hours at the temperature of 60 ℃, and then diluting the solution 1 to the concentration of 0.2-1.0 g/L by using deionized water;
carrying out suction filtration separation on the diluted solution 1 by using a nylon filter membrane with the aperture of 0.22 mu m, and washing a filter cake until the pH value of a washing liquid is 7; vacuum drying the filter cake for 24h at 70 ℃ to obtain the oxidized multi-walled carbon nanotube rich in carboxyl and hydroxyl;
2) preparing an ammonium carbon nanotube: mixing the prepared oxidized multi-walled carbon nanotube and an organosilane coupling agent together to obtain a solution 2, and carrying out ultrasonic dispersion on the solution 2 for 30 min; then carrying out water bath reaction for 2h at the temperature of 60 ℃, continuously stirring in the water bath reaction process, and then carrying out vacuum drying for 48h at the temperature of 70 ℃ to obtain an ammonium multi-walled carbon nanotube;
3) preparing the anionic carbon nanotube: adding an ammonium multi-walled carbon nanotube and an anionic surfactant into 30-50 wt% of absolute ethyl alcohol, and carrying out water bath reaction at the temperature of 60 ℃ for 24 hours to obtain an anionic carbon nanotube;
4) preparing flexible carbon nanotubes: adding the multi-walled carbon nanotube or the oxidized multi-walled carbon nanotube prepared in the step 1) and polytetrafluoroethylene into a N-methyl pyrrolidone solution, uniformly stirring to form a slurry, coating the slurry into a film layer with uniform thickness, and performing vacuum drying at the temperature of 70 ℃ for 24 hours to prepare a flexible carbon nanotube thin layer;
5) preparing a sulfur @ carbon nanotube composite material: dissolving sublimed sulfur in CS2Obtaining a solution 3 in a solvent, and dripping the solution 3 on the flexible carbon nanotube thin layer prepared in the step 4) to prepare the sulfur @ carbon nanotube composite material;
6) preparing a conductive Janus film: adding the anionic carbon nano tube prepared in the step 3) into an isopropanol solution, uniformly stirring to form a solution 4, dripping the solution 4 on the sulfur @ carbon nano tube composite material by using a dropper, and drying in vacuum for 24 hours at the temperature of 70 ℃ to obtain the flexible sulfur-carbon composite material with ion selectivity, namely the conductive Janus film.
5. The method of claim 4, wherein the conductive Janus film is prepared by: the organosilane coupling agent is methanol or ethanol solution of 3- (trimethoxysilylpropyl) dimethyloctadecyl ammonium chloride.
6. The method of claim 4, wherein the conductive Janus film is prepared by: the anionic surfactant is sodium nonylphenol polyoxyethylene ether sulfate.
7. An application of a conductive Janus film in preparing a positive electrode of a lithium-sulfur battery.
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