CN110707383A - Preparation method and use method of amorphous vanadium oxide/carbon fiber material for lithium-sulfur battery - Google Patents
Preparation method and use method of amorphous vanadium oxide/carbon fiber material for lithium-sulfur battery Download PDFInfo
- Publication number
- CN110707383A CN110707383A CN201911005717.4A CN201911005717A CN110707383A CN 110707383 A CN110707383 A CN 110707383A CN 201911005717 A CN201911005717 A CN 201911005717A CN 110707383 A CN110707383 A CN 110707383A
- Authority
- CN
- China
- Prior art keywords
- lithium
- vanadium oxide
- carbon fiber
- sulfur battery
- fiber material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
A preparation method and a use method of an amorphous vanadium oxide/carbon fiber material for a lithium-sulfur battery belong to the field of lithium-sulfur batteries. The preparation method comprises the steps of adding the dimethyl formamide into the weighed vanadyl acetylacetonate, carrying out magnetic stirring for a certain time, adding the 4-4 diaminodiphenyl ether after the materials are fully dissolved, carrying out ultrasonic treatment for a certain time, adding the pyromellitic dianhydride in several times under the condition of mechanical stirring, stirring for a certain time to obtain a precursor solution, carrying out high-temperature treatment after electrostatic spinning, converting the precursor solution into a nanofiber mesh containing amorphous vanadium oxide through high-temperature carbonization and the like, and using the nanofiber mesh as an addition layer of the lithium-sulfur battery. The fiber interlayer plays a good limiting role in an intermediate product of the lithium-sulfur battery and provides good conductivity, a binder and a conductive agent are not required to be added during preparation of the interlayer, and subsequent battery performance tests also prove that the interlayer greatly improves the performance of the lithium-sulfur battery.
Description
Technical Field
The invention belongs to the field of lithium-sulfur batteries; in particular to a preparation method and a use method of an amorphous vanadium oxide/carbon fiber material for a lithium-sulfur battery.
Background
In recent years, excessive exploitation and use of non-renewable energy such as fossil fuel by human has caused serious environmental pollution and global warming, so that development of renewable clean energy technology is a big problem in the 21 st century before scientists. Lithium ion batteries with high energy density and long cycle life have been widely used in mobile phones, computers and new energy vehicles for the past 20 years. However, as the cost increases due to shortage of lithium resources and the demand for technical parameters such as specific capacity and cycle performance of lithium ion batteries is higher, scientists have been working on developing more ideal secondary batteries in which the theoretical energy density of lithium sulfur batteries (2600 Wh kg) is higher-1) Is much higher than the prior commercial lithium ion battery (500 Wh.kg)-1) And the sulfur element is high in content in the earth crust, low in price and free of pollution to the environment, so that the lithium ion battery is regarded as the most ideal substitute battery for the lithium ion in the future.
However, lithium-sulfur batteries still face a few challenges, and the most critical problem is that lithium polysulfide generated during discharge is dissolved in the electrolyte, so that the utilization rate of the active material sulfur is greatly reduced, and the cycle performance of the battery is reduced. Many materials have been developed to support sulfur in the positive electrode, including carbon materials, metal oxides, etc., which solve the problem of polysulfide dissolution to some extent. However, addition of these carbons or metal compounds lowers the energy density of the electrode, and thus more and more people have come to pay attention to the bare sulfur cathode in recent years.
Disclosure of Invention
The invention aims to provide a preparation method and a use method of an amorphous vanadium oxide/carbon fiber material for a lithium-sulfur battery.
The invention is realized by the following technical scheme:
a method for preparing amorphous vanadium oxide/carbon fiber material for lithium-sulfur battery, comprising the following steps:
step 3, performing electrostatic spinning on the precursor solution prepared in the step 2 to obtain polymer fibers for later use;
step 4, putting the polymer fiber prepared in the step 3 into a tube furnace for heat treatment at 5 ℃ for min-1The temperature is raised to the range of 250-300 ℃ and kept for 1-2h, and then the temperature is raised for 5-10 ℃ min under the protection of argon gas-1Is raised to the range of 650-900 ℃ and kept for 1-2h, and then is heated for 5-10 ℃ min-1The speed is reduced to 300 ℃, and finally, the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery is prepared by annealing to normal temperature.
The invention relates to a preparation method of an amorphous vanadium oxide/carbon fiber material for a lithium-sulfur battery, wherein in the step 1, the material-liquid ratio of vanadyl acetylacetonate, dimethylformamide, 4-4 diaminodiphenyl ether and pyromellitic dianhydride is 1.0-1.2g, 10-15ml, 1.0-1.2g and 1.08-1.2 g.
The invention relates to a preparation method of an amorphous vanadium oxide/carbon fiber material for a lithium-sulfur battery, which is characterized in that in step 2, the magnetic stirring time of adding dimethylformamide into vanadyl acetylacetonate is 10-20min, the ultrasonic time is 15-20min, and the mechanical stirring time is 20-30 min.
The invention relates to a preparation method of an amorphous vanadium oxide/carbon fiber material for a lithium-sulfur battery, in step 3, electrostatic spinning is carried out at 35 ℃, the applied voltage is 17kV, and the flow rate is 0.4 ml.h-1The humidity was 40% and the distance between the metal nozzle and the aluminum foil collector was 14 cm.
The invention relates to a preparation method of an amorphous vanadium oxide/carbon fiber material for a lithium-sulfur battery, and the heat treatment process in the step 4 isAt 5 ℃ for min-1The temperature is raised to be within the range of 300 ℃ and kept for 1h, and then the temperature is raised for 10 min under the protection of argon gas-1Is raised to a temperature in the range of 900 ℃ for 2h and subsequently at 5 ℃ for min-1The rate of the annealing is reduced to 300 ℃, and finally the annealing is carried out to normal temperature.
According to the method for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery is prepared into a circular interlayer and is arranged between a diaphragm and a positive electrode of the lithium-sulfur battery.
The use method of the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, which is prepared by the preparation method of the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, comprises the steps of taking sublimed sulfur powder as an active substance of a positive electrode, taking Super-P as a conductive agent and PVDF as a binder, manually grinding the active substance in a mortar for 20 minutes, adding 5% NMP solution, magnetically stirring the mixture for 6 hours until black uniform pasty slurry is obtained, uniformly coating the slurry on an aluminum sheet with the diameter of 12mm by using a glass rod, and drying the aluminum sheet in a vacuum oven at the temperature of 60 ℃ for 24 hours to obtain the positive electrode.
According to the using method of the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, which is prepared by the preparation method of the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, the mass ratio of the sublimed sulfur powder to the Super-P, PVDF is 7:2: 1.
The method for using the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, which is prepared by the preparation method of the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, is characterized in that the diaphragm is a pp film.
The invention relates to a method for preparing an amorphous vanadium oxide/carbon fiber material for a lithium-sulfur battery, which is used for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, and the method for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery into a circular interlayer is to cut the amorphous vanadium oxide/carbon fiber material into 16mm black circular sheets by using a small punching machine.
According to the preparation method of the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, 4-4 diaminodiphenyl ether and pyromellitic dianhydride are subjected to polycondensation reaction in the step 2 to form soluble high-molecular-weight polyamide acid (PAA), and the mass ratio of the two materials is calculated theoretically to be 1: 1, the molecular weight of the obtained polyamic acid is maximum, but a slight amount of water is removed during the reaction, so that the content of pyromellitic anhydride is slightly increased, and finally the maximum viscosity is reached.
According to the preparation method of the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, the nanofiber prepared by the electrostatic spinning technology in the step 3 not only has a high specific surface area and good electrochemical performance, but also has excellent mechanical performance, and the nanofiber serving as an addition layer between a lithium-sulfur battery diaphragm and a sulfur positive electrode can well inhibit the dissolution of polysulfide, so that the high performance of the lithium-sulfur battery is realized.
In the preparation method of the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, in the step 4, the polyamic acid polymer fiber is converted into the light yellow Polyimide (PI, Polyimide) fiber through gradual imidization reaction in the heating process within the range of 250-300 ℃.
The invention relates to a preparation method of an amorphous vanadium oxide/carbon fiber material for a lithium-sulfur battery, which utilizes vanadyl acetylacetonate and polyamic acid as electrostatic spinning precursors, converts the electrostatic spinning precursors into a nanofiber mesh containing amorphous vanadium oxide through steps of high-temperature carbonization and the like, and uses the nanofiber mesh as an addition layer of the lithium-sulfur battery. The fiber interlayer plays a good limiting role on an intermediate product (polysulfide) of the lithium-sulfur battery and provides good conductivity, a binder and a conductive agent are not required to be added when the interlayer is prepared, and subsequent battery performance tests prove that the interlayer greatly improves the performance of the lithium-sulfur battery.
The invention relates to a preparation method of amorphous vanadium oxide/carbon fiber material for lithium-sulfur batteries, which is to obtain amorphous oxygenAnd assembling the vanadium oxide interlayer and the pure sulfur electrode into a button lithium-sulfur battery, and testing the electrochemical performance. The rate performance measured indicates: the first-coil discharge capacity of the battery under the current density of 0.1C is up to 1236mA h.g-1And the capacity is maintained at 700mA h.g under the large current density of 2C-1The above; the amorphous vanadium oxide carbon fiber interlayer provided by the invention has a good inhibition effect on the shuttle effect of the lithium-sulfur battery, and the battery has excellent rate performance. Meanwhile, the service life of the button lithium-sulfur battery obtained by the invention is tested, and the result shows that the capacity of the button lithium-sulfur battery can still be maintained at 769mA h g after the button lithium-sulfur battery is charged and discharged for 700 times under the high current density of 1C-1(1C 1675 mA/g). The amorphous vanadium oxide carbon fiber interlayer provided by the invention has higher research value on improving the electrochemical performance of the lithium-sulfur battery.
Drawings
FIG. 1 is a process flow diagram of a method of preparing an amorphous vanadium oxide/carbon fiber material for a lithium sulfur battery according to the present invention;
FIG. 2 is a schematic diagram of a sandwich structure of a lithium sulfur button cell using the amorphous vanadium oxide/carbon fiber material for a lithium sulfur battery according to the present invention;
fig. 3 is a 2200 SEM picture of an amorphous vanadium oxide/carbon fiber material for a lithium sulfur battery prepared by a method according to an embodiment;
FIG. 4 is a SEM image of amorphous vanadium oxide/carbon fiber material prepared by the method of one embodiment at a magnification of 5000 for a lithium sulfur battery;
FIG. 5 is a SEM image of amorphous vanadium oxide/carbon fiber material prepared by the method of one embodiment for a lithium sulfur battery at a magnification of 50000 times;
FIG. 6 is a photograph of the elemental distribution of an amorphous vanadium oxide/carbon fiber material for a lithium sulfur battery prepared by a method according to one embodiment;
FIG. 7 is a 8000 XTEM image of an amorphous vanadium oxide/carbon fiber material for a lithium sulfur battery prepared by the method of one embodiment;
FIG. 8 is a transmission electron micrograph of 20000 times amorphous vanadium oxide/carbon fiber material for a lithium sulfur battery prepared by a method according to an embodiment;
FIG. 9 is an X-ray diffraction pattern of an amorphous vanadium oxide/carbon fiber material for a lithium sulfur battery prepared by a method according to one embodiment;
FIG. 10 is an XPS spectrum of an amorphous vanadium oxide/carbon fiber material for a lithium sulfur battery prepared by a method according to one embodiment;
FIG. 11 is a graph of charge and discharge curves of amorphous vanadium oxide/carbon fiber material for lithium sulfur batteries according to embodiment two at times 1, 100, 300, 500, and 700;
FIG. 12 is a graph of rate performance of an amorphous vanadium oxide/carbon fiber material for a lithium sulfur battery according to embodiment two;
fig. 13 is a graph of the previous 700 cycles of the amorphous vanadium oxide/carbon fiber material according to the second embodiment for a lithium-sulfur battery at a charge-discharge current density of 1C.
Detailed Description
The first embodiment is as follows:
a method for preparing amorphous vanadium oxide/carbon fiber material for lithium-sulfur battery, comprising the following steps:
step 3, performing electrostatic spinning on the precursor solution prepared in the step 2 to obtain polymer fibers for later use;
step 4, putting the polymer fiber prepared in the step 3 into a tube furnace for heat treatment at 5 ℃ for min-1At a rate of increasing the temperature toKeeping the temperature within the range of 250-300 ℃ for 1-2h, and then keeping the temperature at 5-10 ℃ for min under the protection of argon-1Is raised to the range of 650-900 ℃ and kept for 1-2h, and then is heated for 5-10 ℃ min-1The speed is reduced to 300 ℃, and finally, the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery is prepared by annealing to normal temperature.
In the preparation method of the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, in the step 1, the material-to-liquid ratio of vanadyl acetylacetonate, dimethylformamide, 4-4 diaminodiphenyl ether and pyromellitic dianhydride is 1.0-1.2g, 10-15ml, 1.0-1.2g, 1.08-1.2 g.
In the preparation method of the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, in the step 2, the magnetic stirring time of adding the dimethylformamide into the vanadyl acetylacetonate is 10-20min, the ultrasonic time is 15-20min, and the mechanical stirring time is 20-30 min.
In the method for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery according to the embodiment, in the step 3, the electrostatic spinning condition is 35 ℃, the applied voltage is 17kV, and the flow rate is 0.4 ml.h-1The humidity was 40% and the distance between the metal nozzle and the aluminum foil collector was 14 cm.
In the method for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, the heat treatment process in the step 4 is performed at 5 ℃ for min-1The temperature is raised to be within the range of 300 ℃ and kept for 1h, and then the temperature is raised for 10 min under the protection of argon gas-1Is raised to a temperature in the range of 900 ℃ for 2h and subsequently at 5 ℃ for min-1The rate of the annealing is reduced to 300 ℃, and finally the annealing is carried out to normal temperature.
Fig. 3 to 5 are scanning electron microscope pictures of the amorphous vanadium oxide/carbon fiber material for lithium sulfur batteries at different magnifications, and it can be seen from the pictures that the nanofiber interlayer surface of the amorphous vanadium oxide/carbon fiber material for lithium sulfur batteries prepared by electrospinning is smooth, the diameter of the fiber is about 0.5 μm, and the size of the fiber is relatively uniform.
In the method for preparing an amorphous vanadium oxide/carbon fiber material for a lithium-sulfur battery according to the present embodiment, fig. 6 is a photograph of an element distribution of the amorphous vanadium oxide/carbon fiber material for a lithium-sulfur battery, fig. 6-b is a photograph of a carbon element distribution, fig. 6-c is a photograph of an oxygen element distribution, and fig. 6-d is a photograph of a vanadium element distribution, and it can be seen from the drawings that the distribution of each element is uniform.
Fig. 7 and 8 are transmission electron micrographs of amorphous vanadium oxide/carbon fiber materials for lithium sulfur batteries at different magnifications, and it can be seen from the transmission electron micrographs that the nanofiber interlayer of the amorphous vanadium oxide/carbon fiber material for lithium sulfur batteries prepared by electrospinning is smooth, the diameter of the fiber is about 0.5 μm, and no vanadium oxide crystal particles exist in the fiber.
Fig. 9 is an X-ray diffraction pattern of the prepared amorphous vanadium oxide/carbon fiber material for a lithium-sulfur battery, and as can be seen from fig. 9, the amorphous vanadium oxide/carbon fiber material for a lithium-sulfur battery is amorphous vanadium oxide carbon fiber.
Fig. 10 is an XPS spectrum of the amorphous vanadium oxide/carbon fiber material for a lithium sulfur battery, and peaks of binding energy at 523.98eV and 516.38eV are attributed to V2p from the XPS spectrum of fig. 104+And non-decomposed vanadyl acetylacetonate.
The second embodiment is as follows:
according to the method for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery is manufactured into a circular interlayer and is arranged between a diaphragm and a positive electrode of the lithium-sulfur battery.
According to the method for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, the method for using the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery comprises the steps of taking sublimed sulfur powder as a positive electrode active substance, Super-P as a conductive agent and PVDF as a binder, manually grinding the materials in a mortar for 20 minutes, adding 5% of NMP solution, magnetically stirring the materials for 6 hours until the materials are black and uniform paste-shaped slurry, uniformly coating the slurry on an aluminum sheet with the diameter of 12mm by using a glass rod, and drying the aluminum sheet in a vacuum oven at the temperature of 60 ℃ for 24 hours to obtain the positive electrode.
According to the using method of the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, which is prepared by the preparation method of the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, the mass ratio of the sublimed sulfur powder to the Super-P, PVDF is 7:2: 1.
The method for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery according to the embodiment is used for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, and the separator is a pp film.
The method for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery according to the embodiment is used for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery into the round interlayer, and the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery is cut into 16mm black round sheets by using a small punching machine.
In the method for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, which is described in the embodiment, the metal lithium sheet is used as a negative electrode, the pp film is used as a diaphragm, and a commercial lithium-sulfur electrolyte is selected and added dropwise to two sides of the diaphragm by using a liquid-transferring gun (30 μ L is added to each battery). The assembly of the entire cell was completed in a glove box.
The method for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery according to the embodiment is used for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, and the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery is manufactured into a circular interlayer with the diameter of 16 mm.
Fig. 11 shows the charge and discharge curves of the amorphous vanadium oxide/carbon fiber material for lithium-sulfur batteries at 1 st, 100 th, 300 th, 500 th and 700 th times, and it can be seen from fig. 11 that the initial discharge capacity of the battery can reach 1200mAh g under the activation of a small current density of 0.1C-1The above. After the high-current density charging and discharging of 1C, the 100 th, 300 th, 500 th and 700 th discharge capacities of the battery can still reach 700mAh g-1The above high capacity without significant capacity degradation.
The method for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery according to the embodiment is used for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, fig. 12 is a rate performance curve of the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, and as can be seen from fig. 12, the battery can contribute more than 1000mAh g at a small charge-discharge current density of 0.1C-1The specific capacity of (A). When the current density is increased to a large current density of 1C and 2C, the battery can still maintain 850mAh g-1And 700 mAh. g-1The capacity of the battery shows very excellent rate capability.
The method for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery according to the embodiment is used for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, fig. 13 is a cycle performance curve of the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery for the first 700 times under the condition that the charge-discharge current density is 1C, and as can be seen from fig. 13, the battery can still maintain 900mAh g at the high current density of 1C-1The high specific capacity of the interlayer is about high, and the capacity does not quickly fade after 700 times of long cycles, which shows that the interlayer can greatly improve the cycling stability of the battery when being used in the lithium-sulfur battery.
The third concrete implementation mode:
a method for preparing amorphous vanadium oxide/carbon fiber material for lithium-sulfur battery, comprising the following steps:
step 3, performing electrostatic spinning on the precursor solution prepared in the step 2 to obtain polymer fibers for later use;
step 4, putting the polymer fiber prepared in the step 3 into a tube furnace for heat treatment at 5 ℃ for min-1The temperature is raised to the range of 250-300 ℃ and kept for 1-2h, and then the temperature is raised for 5-10 ℃ min under the protection of argon gas-1Is raised to the range of 650-900 ℃ and kept for 1-2h, and then is heated for 5-10 ℃ min-1The speed is reduced to 300 ℃, and finally, the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery is prepared by annealing to normal temperature.
In the method for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, in step 2, 4-4 diaminodiphenyl ether and pyromellitic dianhydride are subjected to a condensation polymerization reaction to form soluble high molecular weight polyamic acid (PAA), and the mass ratio of the two is 1: 1, the molecular weight of the obtained polyamic acid is maximum, but a slight amount of water is removed during the reaction, so that the content of pyromellitic anhydride is slightly increased, and finally the maximum viscosity is reached.
In the method for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, the nanofiber prepared by the electrospinning technology in the step 3 not only has a high specific surface area and good electrochemical performance, but also has excellent mechanical properties, and the nanofiber serving as an addition layer between the lithium-sulfur battery diaphragm and the sulfur positive electrode can well inhibit the dissolution of polysulfide, so that the high performance of the lithium-sulfur battery can be realized.
In the method for preparing an amorphous vanadium oxide/carbon fiber material for a lithium-sulfur battery in this embodiment, in step 4, the polyamic acid polymer fiber is converted into a light yellow Polyimide (PI) fiber through a gradual imidization reaction in a heating process within a range of 250-300 ℃.
According to the preparation method of the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, vanadyl acetylacetonate and polyamic acid are used as electrostatic spinning precursors, and are converted into a nanofiber mesh containing amorphous vanadium oxide through steps of high-temperature carbonization and the like and are used as an addition layer of the lithium-sulfur battery. The fiber interlayer plays a good limiting role on an intermediate product (polysulfide) of the lithium-sulfur battery and provides good conductivity, a binder and a conductive agent are not required to be added when the interlayer is prepared, and subsequent battery performance tests prove that the interlayer greatly improves the performance of the lithium-sulfur battery.
According to the preparation method of the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, the obtained amorphous vanadium oxide interlayer and a pure sulfur electrode are assembled into the button-type lithium-sulfur battery, and an electrochemical performance test is performed. The rate performance measured indicates: the first-coil discharge capacity of the battery under the current density of 0.1C is up to 1236mA h.g-1And the capacity is maintained at 700mA h.g under the large current density of 2C-1The above; the amorphous vanadium oxide carbon fiber interlayer provided by the invention has a good inhibition effect on the shuttle effect of the lithium-sulfur battery, and the battery has excellent rate performance. Meanwhile, the service life of the button lithium-sulfur battery obtained by the invention is tested, and the result shows that after the battery is charged and discharged for 700 times under the high current density of 1C,the capacity can still be kept at 769mA h g-1(1C 1675 mA/g). The amorphous vanadium oxide carbon fiber interlayer provided by the invention has higher research value on improving the electrochemical performance of the lithium-sulfur battery.
The fourth concrete implementation mode:
according to the third specific embodiment, in the step 1, the material-to-liquid ratio of vanadyl acetylacetonate, dimethylformamide, 4-4 diaminodiphenyl ether and pyromellitic anhydride is 1.0-1.2g, 10-15ml, 1.0-1.2g, and 1.08-1.2 g.
The fifth concrete implementation mode:
according to the third specific embodiment, in the step 2, the magnetic stirring time of adding the dimethylformamide into the vanadyl acetylacetonate is 10-20min, the ultrasonic time is 15-20min, and the mechanical stirring time is 20-30 min.
The sixth specific implementation mode:
according to the third specific embodiment, in the step 3, the electrostatic spinning condition is 35 ℃, the applied voltage is 17kV, and the flow rate is 0.4 ml.h-1The humidity was 40% and the distance between the metal nozzle and the aluminum foil collector was 14 cm.
The seventh embodiment:
according to the third embodiment of the preparation method of the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, the heat treatment process in the step 4 is performed at 5 ℃ for min-1The temperature is raised to be within the range of 300 ℃ and kept for 1h, and then the temperature is raised for 10 min under the protection of argon gas-1Is raised to a temperature in the range of 900 ℃ for 2h and subsequently at 5 ℃ for min-1The rate of the annealing is reduced to 300 ℃, and finally the annealing is carried out to normal temperature.
The specific implementation mode is eight:
according to the method for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, which is described in the third to seventh embodiments, the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery is manufactured into a circular interlayer and is arranged between the diaphragm and the positive electrode of the lithium-sulfur battery.
The specific implementation method nine:
according to the preparation method of the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, the use method of the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery is characterized in that sublimed sulfur powder is used as a positive electrode active substance, Super-P is a conductive agent, PVDF is a binder, after the materials are manually ground in a mortar for 20 minutes, a 5% NMP solution is added, the materials are magnetically stirred for 6 hours until black uniform pasty slurry is formed, then the black uniform pasty slurry is uniformly coated on an aluminum sheet with the diameter of 12mm by using a glass rod, and the aluminum sheet is dried in a vacuum oven at the temperature of 60 ℃ for 24 hours to prepare the positive electrode.
The detailed implementation mode is ten:
according to the method for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, which is described in the embodiment nine, the mass ratio of the sublimed sulfur powder to the Super-P, PVDF is 7:2: 1.
The concrete implementation mode eleven:
according to the method for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, which is described in the embodiment ninth, the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery is prepared, and the separator is a pp film.
The specific implementation mode twelve:
according to the method for preparing the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery, which is described in the embodiment ninth, the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery is prepared by using a small punching machine to be cut into 16mm black round sheets.
Claims (10)
1. A preparation method of amorphous vanadium oxide/carbon fiber material for lithium-sulfur batteries is characterized by comprising the following steps: the method comprises the following steps:
step 1, respectively weighing a certain mass of vanadyl acetylacetonate, dimethylformamide, 4-4 diaminodiphenyl ether and pyromellitic dianhydride according to a certain feed-liquid ratio for later use;
step 2, adding the dimethylformamide into the vanadyl acetylacetonate weighed in the step 1, magnetically stirring for a certain time, fully dissolving, adding the 4-4 diaminodiphenyl ether, ultrasonically treating for a certain time, adding the pyromellitic dianhydride in portions under the condition of mechanical stirring, and stirring for a certain time to obtain a precursor solution for later use;
step 3, performing electrostatic spinning on the precursor solution prepared in the step 2 to obtain polymer fibers for later use;
step 4, putting the polymer fiber prepared in the step 3 into a tube furnace for heat treatment at 5 ℃ for min-1The temperature is raised to the range of 250-300 ℃ and kept for 1-2h, and then the temperature is raised for 5-10 ℃ min under the protection of argon gas-1Is raised to the range of 650-900 ℃ and kept for 1-2h, and then is heated for 5-10 ℃ min-1The speed is reduced to 300 ℃, and finally, the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery is prepared by annealing to normal temperature.
2. The method of claim 1 for preparing an amorphous vanadium oxide/carbon fiber material for a lithium sulfur battery, wherein: in the step 1, the material-liquid ratio of the vanadyl acetylacetonate, the dimethylformamide, the 4-4 diaminodiphenyl ether and the pyromellitic dianhydride is 1.0-1.2g, 10-15ml, 1.0-1.2g and 1.08-1.2 g.
3. The method of claim 1 for preparing an amorphous vanadium oxide/carbon fiber material for a lithium sulfur battery, wherein: and (3) adding the dimethylformamide into the vanadyl acetylacetonate in the step 2, and performing magnetic stirring for 10-20min, ultrasonic stirring for 15-20min and mechanical stirring for 20-30 min.
4. The method of claim 1 for preparing an amorphous vanadium oxide/carbon fiber material for a lithium sulfur battery, wherein: in the step 3, the electrostatic spinning condition is that under the temperature environment of 35 ℃, the applied voltage is 17kV, and the flow rate is 0.4 ml.h-1The humidity was 40% and the distance between the metal nozzle and the aluminum foil collector was 14 cm.
5. The method of claim 1 for preparing an amorphous vanadium oxide/carbon fiber material for a lithium sulfur battery, wherein: the heat treatment process in step 4 is carried out at 5 deg.C for min-1The temperature is raised to be within the range of 300 ℃ and kept for 1h, and then the temperature is raised for 10 min under the protection of argon gas-1Is raised to a temperature in the range of 900 ℃ for 2h and subsequently at 5 ℃ for min-1The rate of the annealing is reduced to 300 ℃, and finally the annealing is carried out to normal temperature.
6. A method of using the amorphous vanadium oxide/carbon fiber material for lithium sulfur battery prepared by the method of preparing the amorphous vanadium oxide/carbon fiber material for lithium sulfur battery of claims 1 to 5, characterized in that: the amorphous vanadium oxide/carbon fiber material for the lithium-sulfur battery is made into a circular interlayer and is arranged between a diaphragm and a positive electrode of the lithium-sulfur battery.
7. The method for using the amorphous vanadium oxide/carbon fiber material for lithium sulfur battery prepared by the method for preparing the amorphous vanadium oxide/carbon fiber material for lithium sulfur battery according to claim 6, is characterized in that: the preparation method of the anode comprises the steps of taking sublimed sulfur powder as an active substance of the anode, taking Super-P as a conductive agent and PVDF as a binder, manually grinding the materials in a mortar for 20 minutes, adding 5% NMP solution, magnetically stirring the materials for 6 hours until black uniform pasty slurry is obtained, uniformly coating the black uniform pasty slurry on an aluminum sheet with the diameter of 12mm by using a glass rod, and drying the aluminum sheet in a vacuum oven at the temperature of 60 ℃ for 24 hours to obtain the anode.
8. The method of claim 7 for using the amorphous vanadium oxide/carbon fiber material for lithium-sulfur battery prepared by the method for preparing the amorphous vanadium oxide/carbon fiber material for lithium-sulfur battery, wherein: the mass ratio of the sublimed sulfur powder to the Super-P, PVDF is 7:2: 1.
9. The method for using the amorphous vanadium oxide/carbon fiber material for lithium sulfur battery prepared by the method for preparing the amorphous vanadium oxide/carbon fiber material for lithium sulfur battery according to claim 6, is characterized in that: the membrane is a pp membrane.
10. The method for using the amorphous vanadium oxide/carbon fiber material for lithium sulfur battery prepared by the method for preparing the amorphous vanadium oxide/carbon fiber material for lithium sulfur battery according to claim 6, is characterized in that: one method of making a circular sandwich of amorphous vanadium oxide/carbon fiber material for a lithium sulfur battery is to cut it into 16mm black circular sheets using a small punch.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911005717.4A CN110707383B (en) | 2019-10-22 | 2019-10-22 | Preparation method and use method of amorphous vanadium oxide/carbon fiber material for lithium-sulfur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911005717.4A CN110707383B (en) | 2019-10-22 | 2019-10-22 | Preparation method and use method of amorphous vanadium oxide/carbon fiber material for lithium-sulfur battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110707383A true CN110707383A (en) | 2020-01-17 |
| CN110707383B CN110707383B (en) | 2021-01-29 |
Family
ID=69202053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911005717.4A Active CN110707383B (en) | 2019-10-22 | 2019-10-22 | Preparation method and use method of amorphous vanadium oxide/carbon fiber material for lithium-sulfur battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110707383B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113161522A (en) * | 2021-03-12 | 2021-07-23 | 广东工业大学 | Amorphous vanadium oxide/carbon composite material and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006025604A1 (en) * | 2004-09-03 | 2006-03-09 | Avestor Limited Partnership | Process for producing positive electrode material composition for lithium secondary battery |
| JPWO2006025602A1 (en) * | 2004-09-03 | 2008-05-08 | 株式会社日本触媒 | Method for producing positive electrode material composition for lithium secondary battery |
| CN104393349A (en) * | 2014-11-17 | 2015-03-04 | 陕西煤业化工技术研究院有限责任公司 | Protective layer for lithium sulphur battery, preparation method thereof and lithium sulphur battery using protective layer |
| CN104389042A (en) * | 2014-12-16 | 2015-03-04 | 吉林大学 | Electrostatic spinning preparation method of vanadium-oxygen-carbon supercapacitor electrode material |
| CN106498545A (en) * | 2016-06-13 | 2017-03-15 | 杨磊 | A kind of preparation technology of polyamic acid magnetic nano composite fibre |
| CN107591522A (en) * | 2017-08-22 | 2018-01-16 | 中南大学 | A kind of preparation method of the spherical V2O3/C materials of sodium-ion battery negative pole |
| CN109301210A (en) * | 2018-09-28 | 2019-02-01 | 哈尔滨理工大学 | A kind of carbon fiber/boron nitride flexible compound electrode and the preparation method and application thereof |
| CN109888219A (en) * | 2019-02-22 | 2019-06-14 | 东华大学 | A kind of Cu oxide/carbon nano-fiber/sulfur electrode material and its preparation and application |
| CN110112405A (en) * | 2019-05-29 | 2019-08-09 | 哈尔滨理工大学 | A kind of core-shell structure silicon/carbon fiber flexible combination electrode material and the preparation method and application thereof |
| CN110257958A (en) * | 2019-07-10 | 2019-09-20 | 陕西科技大学 | A kind of vanadium nitride/carbon nano-fiber microwave absorption and preparation method thereof |
-
2019
- 2019-10-22 CN CN201911005717.4A patent/CN110707383B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006025604A1 (en) * | 2004-09-03 | 2006-03-09 | Avestor Limited Partnership | Process for producing positive electrode material composition for lithium secondary battery |
| JPWO2006025602A1 (en) * | 2004-09-03 | 2008-05-08 | 株式会社日本触媒 | Method for producing positive electrode material composition for lithium secondary battery |
| CN104393349A (en) * | 2014-11-17 | 2015-03-04 | 陕西煤业化工技术研究院有限责任公司 | Protective layer for lithium sulphur battery, preparation method thereof and lithium sulphur battery using protective layer |
| CN104389042A (en) * | 2014-12-16 | 2015-03-04 | 吉林大学 | Electrostatic spinning preparation method of vanadium-oxygen-carbon supercapacitor electrode material |
| CN106498545A (en) * | 2016-06-13 | 2017-03-15 | 杨磊 | A kind of preparation technology of polyamic acid magnetic nano composite fibre |
| CN107591522A (en) * | 2017-08-22 | 2018-01-16 | 中南大学 | A kind of preparation method of the spherical V2O3/C materials of sodium-ion battery negative pole |
| CN109301210A (en) * | 2018-09-28 | 2019-02-01 | 哈尔滨理工大学 | A kind of carbon fiber/boron nitride flexible compound electrode and the preparation method and application thereof |
| CN109888219A (en) * | 2019-02-22 | 2019-06-14 | 东华大学 | A kind of Cu oxide/carbon nano-fiber/sulfur electrode material and its preparation and application |
| CN110112405A (en) * | 2019-05-29 | 2019-08-09 | 哈尔滨理工大学 | A kind of core-shell structure silicon/carbon fiber flexible combination electrode material and the preparation method and application thereof |
| CN110257958A (en) * | 2019-07-10 | 2019-09-20 | 陕西科技大学 | A kind of vanadium nitride/carbon nano-fiber microwave absorption and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 吴恩熙: "《氧化钒制取碳化钒的热力学分析》", 《硬质合金》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113161522A (en) * | 2021-03-12 | 2021-07-23 | 广东工业大学 | Amorphous vanadium oxide/carbon composite material and preparation method and application thereof |
| CN113161522B (en) * | 2021-03-12 | 2022-07-19 | 广东工业大学 | Amorphous vanadium oxide/carbon composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110707383B (en) | 2021-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2023024651A1 (en) | Lithium iron manganese phosphate precursor, lithium iron manganese phosphate positive electrode material and preparation method therefor, electrode material, electrode, and lithium-ion battery | |
| CN110010903B (en) | Positive pole piece and battery | |
| CN110556586A (en) | Polymeric organic-inorganic composite solid electrolyte and in-situ assembled all-solid-state battery | |
| CN109119592B (en) | Lithium titanate negative electrode piece, preparation method and lithium titanate battery | |
| CN110350196B (en) | Composite binder, silicon-based negative plate and preparation method thereof | |
| CN110071289B (en) | Silicon-based negative electrode composite binder of lithium ion battery and preparation method and application thereof | |
| CN113764644B (en) | Quick-filling composite graphite material and preparation method thereof | |
| CN110739427A (en) | Battery diaphragm material and preparation method and application thereof | |
| CN107507961B (en) | Preparation method of conductive polymer modified lithium ion battery positive pole piece | |
| CN102723487A (en) | LiFePO4 cathode material of lithium ion battery compositely coated by TiN and C and preparation method thereof | |
| CN112538692B (en) | Co-Mn bimetallic organic framework derived porous carbon fiber and preparation method and application thereof | |
| CN112151755A (en) | Positive plate and battery | |
| KR20230148406A (en) | Preparation method of negative electrode material for lithium ion battery | |
| CN108269992B (en) | High-capacity lithium ion battery composite cathode material and preparation method thereof | |
| CN110534816A (en) | Fibrous flexible rechargeable zinc-manganese battery based on multi-valence manganese oxide | |
| CN110707383B (en) | Preparation method and use method of amorphous vanadium oxide/carbon fiber material for lithium-sulfur battery | |
| CN114583137B (en) | Method for modifying carbon surface by sulfur doped phosphorus and application thereof | |
| CN115207286A (en) | Dry electrode lithium metal solid-state battery positive plate and manufacturing method and application thereof | |
| CN112382749B (en) | Lithium ion battery anode material and preparation method thereof | |
| CN113471542A (en) | Solid-state lithium battery and preparation method thereof | |
| JP2920079B2 (en) | Organic electrolyte battery | |
| JP2013038070A (en) | Negative electrode active material for lithium ion secondary battery, manufacturing method of negative electrode active material for lithium ion secondary battery, electrode for lithium ion secondary battery, and lithium ion secondary battery | |
| CN113321199A (en) | Polybenzoxazine-co-cresol-based polymer-derived hard carbon microspheres, and preparation method and application thereof | |
| CN114613996B (en) | High-capacity molybdenum polysulfide composite positive electrode material for all-solid-state battery, and preparation method and application thereof | |
| CN114388878B (en) | Composite solid electrolyte and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |