CN110459721B - Acrylic fiber-based lithium-sulfur battery interlayer material and preparation method thereof - Google Patents
Acrylic fiber-based lithium-sulfur battery interlayer material and preparation method thereof Download PDFInfo
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Abstract
本发明涉及一种具有准分子紫外灯辐照修饰ZnO的腈纶基锂锂硫电池夹层材料及其制备方法，属于储能体系器件材料技术领域。具有准分子紫外灯辐照修饰ZnO的腈纶基锂锂硫电池夹层材料的制备方法方法包括以下步骤：腈纶纱线溶解在DMF中，充分搅拌，静电纺丝，高温碳化，得到碳纤维膜，再通过在锌盐的水溶液中进行准分子紫外灯辐照，干燥退火后得到修饰有ZnO的碳纳米纤维薄膜。本发明制备材料来源环保，流程短且绿色安全，高效清洁。所制备的修饰有ZnO的碳纳米纤维薄膜做为锂硫电池的夹层，该夹层不仅可以物理阻挡多硫化物且能通过高效有力的化学吸附固定多硫化物，使得活性物质能高效利用，从而提高锂硫电池的电化学性能。The invention relates to an acrylic fiber-based lithium-lithium-sulfur battery interlayer material with ZnO irradiated by an excimer ultraviolet lamp and a preparation method thereof, and belongs to the technical field of device materials for energy storage systems. The preparation method of the acrylic-based lithium lithium-sulfur battery interlayer material with excimer ultraviolet lamp irradiation modified ZnO comprises the following steps: dissolving the acrylic yarn in DMF, fully stirring, electrospinning, carbonizing at high temperature to obtain a carbon fiber film, and then passing through Excimer UV lamp irradiation was carried out in an aqueous solution of zinc salt, and after drying and annealing, a carbon nanofiber film modified with ZnO was obtained. The preparation material of the invention is environmentally friendly, the process is short, green, safe, efficient and clean. The prepared carbon nanofiber film modified with ZnO is used as the interlayer of lithium-sulfur batteries, which can not only physically block polysulfides but also fix polysulfides through efficient and powerful chemical adsorption, so that active materials can be efficiently utilized, thereby improving Electrochemical performance of lithium-sulfur batteries.
Description
Technical Field
The invention relates to an energy storage system device material, in particular to an acrylic fiber-based lithium sulfur battery interlayer material (ZnO-CNF) and a preparation method thereof, belonging to the technical field of energy storage system device materials.
Background
With the increasing demand and demand for new energy and portable electronic devices, more stable and superior rechargeable energy storage systems are being developed. Wherein lithium sulfur (Li-S) cells with higher energy density (2600W h kg)-1) And the cost is lower than that of the current lithium ion battery, so that the lithium ion battery becomes a next generation energy storage device. However, its practical application is limited by the low sulfur utilization because of poor cycle life due to low electronic conductivity of sulfur, and the severe shuttling effect of soluble lithium polysulfides (LiPSs) formed in electrochemical reactions. Previous research has focused primarily on limiting the LiPS shuttle and increasing conductivity. The electrode captures sulfur by combining carbon, conductive polymers and non-carbon chemicals. However, these inactive components occupy a large space and have a large mass, lowering the energy density of the electrode, and it is important to develop a more efficient method for inhibiting the LiPS shuttling.
A sandwich design between the separator and the anode can be used to prevent the LiPS shuttling. Carbon materials, metal compounds, composite materials thereof, and the like are generally used for such interlayers. Carbon materials are desirable lightweight barriers, and such very thin coating interlayers can produce long-lived cells without adding too much weight and volume to the assembled cell as an inactive material. However, the carbon material can only physically block the diffusion of the LipS, and the nonpolar surface of the carbon material has poor affinity for the polar LipS. Thus, metal compounds are introduced as chemical traps, such as metal oxides (e.g., ZnO, TiO)2) And metal nitrides (e.g., TiN), etc. have been studied to some extent in other electrochemical energy storage devices. Generally, TiO having a strong adsorption effect on polysulfides2Have been used/sandwiched in interlayers. However, due to its inherently low electrical conductivity, immobilized LiPS remains on the surface and is difficult to completely participate in the electrochemical reaction. Therefore, it must be complexed with carbon, since polysulfides must diffuse to the conductive carbon surface to effect conversion, which results in slow blocking of the reaction kinetics and inefficiencies. Furthermore, physical adsorption and chemical trapping suffer from a gradual interruption of the trapping diffusion conversion process due to the limited number of adsorption sites, poor performance at high sulfur loads, and lithium sulfide (Li) due to insolubility and insulation2S) accumulates on the carbon surface and the adsorption/capture efficiency is greatly reduced. Some polar conductors, which can provide adsorption sites and high conductivity for redox reactions, have much lower adsorption capacities than ZnO,TiO2and the like, so that the capture and conversion efficiency of the LiPS is poor. Therefore, the carbon material is modified and modified to a certain extent, ZnO, the metal oxide with excellent polysulfide adsorption property, is loaded on the carbon material through irradiation of excimer ultraviolet, and due to the fact that various oxygen-containing functional groups generated by irradiation have good modification effect on the wettability of a nonpolar carbon surface, the ideal interlayer can adsorb/capture and convert LiPS at the same time, and the long-cycle stability with high sulfur loading is facilitated, and the practical application of the Li-S battery is realized.
Disclosure of Invention
The invention provides an acrylic fiber-based lithium-sulfur battery interlayer material with quasi-molecular ultraviolet lamp irradiation modified ZnO.
The invention also provides a preparation method of the acrylic fiber-based lithium-sulfur battery interlayer material with the quasi-molecular ultraviolet lamp irradiation modified ZnO.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of an acrylic fiber-based lithium-sulfur battery interlayer material with ZnO modified by excimer ultraviolet lamp irradiation comprises the following steps:
(1) preparation of spinning solution: dissolving acrylic fiber yarns in N-N Dimethylformamide (DMF) and fully stirring;
(2) the preparation method of the nanofiber membrane comprises the following steps: preparing the spinning solution obtained in the step (1) into a nanofiber film by a centrifugal spinning method, a melt spinning method or an electrostatic spinning method;
(3) preparing carbonized acrylic fibers: pre-oxidizing the nanofiber membrane obtained in the step (2) at the temperature of 100-; then under the protection of inert gas, carbonizing at 600-1000 ℃ for 1-8 hours to obtain carbon nano-fibers;
(4) preparing ZnO modified carbonized acrylic fibers: and (3) performing excimer irradiation treatment on the carbon nanofiber obtained in the step (3), placing the carbon nanofiber in an aqueous solution containing zinc ions, irradiating the carbon nanofiber through an excimer ultraviolet lamp, drying the carbon nanofiber at the drying temperature of 10-40 ℃ for 5-25 hours, completely drying the carbon nanofiber, and annealing the carbon nanofiber in an inert gas atmosphere to obtain the lithium-sulfur battery interlayer material with ZnO modified by excimer ultraviolet lamp irradiation.
According to the invention, an excimer ultraviolet lamp is adopted for irradiation, so that ZnO which is difficult to combine on the carbon nanofiber originally can be combined simply and rapidly, and the process is clean and efficient; the control of the solution adopted during irradiation, the concentration thereof, the irradiation power and the irradiation time is all technical difficulties. It is difficult to bond the metal oxide ZnO to the surface layer of the carbon nanofiber in a short time without excimer ultraviolet irradiation. Excimer ultraviolet lamp for Zn2+The ions provide enough energy, and are combined with oxygen in water, single metal oxide ZnO can be obtained through irradiation of an excimer ultraviolet lamp, ZnO has reactive active sites for increasing polysulfide adsorption, so that a subsequently manufactured interlayer material has a strong adsorption effect and efficient utilization of active substance sulfur, and meanwhile, because of irradiation, a plurality of oxygen-containing functional groups generated on the carbon nanofiber film can be more effectively combined with polysulfide, and the electrochemical properties such as cycle stability and the like of the lithium-sulfur battery are improved. The power and time of irradiation are the most critical, and the carbon nano-fiber is easily irreversibly damaged by excessive power for a long time, including fiber breakage and surface integrity damage. Insufficient irradiation power and time do not have enough kinetic energy to cause Zn2+Ions are detached from the aqueous solution and attached to the surface of the carbon fiber. The zinc salt used for irradiation has too low concentration to enable the surface of the carbon fiber to generate enough ZnO subsequently, and the zinc salt used for irradiation has too high concentration to waste materials and is not environment-friendly enough. It is therefore important to control the appropriate concentration and irradiation time power.
Preferably, the inert gas in steps (3) and (4) is preferably argon.
Preferably, the stirring action in step (1) is carried out in two steps, first with a long stirring time of 10 to 40 hours at room temperature, followed by stirring at a high temperature of 60 to 130 ℃ for 80 to 160 min.
Preferably, when electrostatic spinning is adopted in the step (2), the electrostatic spinning voltage is 10-40 kV, the receiving distance is 15-35 cm, and the air humidity is 13-53%.
Preferably, the aqueous solution containing zinc ions in step (4) is an aqueous solution of zinc salt, and the zinc salt is selected from one or more of zinc nitrate, zinc chloride, zinc sulfate and zinc acetate.
Preferably, the irradiation power of the excimer ultraviolet lamp in the step (4) is 70-100%, and the irradiation time is 10-40 min.
Preferably, the irradiation power of the excimer ultraviolet lamp in the step (4) is 50-90%, and the irradiation time is 5-35 min.
Preferably, the molar concentration of zinc ions in the irradiation of the excimer ultraviolet lamp in the step (4) is 0.5M to 3M.
Preferably, the drying time after irradiation of the excimer ultraviolet lamp in the step (4) is 5 to 25 hours.
Preferably, the annealing in step (4) is carried out at a temperature of 200 ℃ to 500 ℃, a temperature rise rate of 5 ℃/min and a time of 1 to 5 hours.
An acrylic fiber-based lithium-sulfur battery interlayer material with ZnO modified by excimer ultraviolet lamp irradiation is prepared by the preparation method.
The application of the acrylic fiber-based lithium-sulfur battery interlayer material with the quasi-molecular ultraviolet lamp irradiation modified ZnO in the preparation of the lithium-sulfur battery is provided.
The method comprises the steps of firstly dissolving acrylic fibers in N-N Dimethylformamide (DMF) to prepare spinning solution, then obtaining a carbon nanofiber film through electrostatic spinning and high-temperature carbonization, and then placing the carbon nanofiber in a zinc salt aqueous solution to carry out excimer ultraviolet lamp irradiation to obtain the ZnO modified carbon nanofiber film. The material prepared by the method can be applied to the field of energy storage of lithium-sulfur batteries, and has the following characteristics:
(1) the preparation method is simple, the used reaction materials are clean and environment-friendly, and the preparation process is simple and green;
(2) ZnO and oxygen-containing functional groups are modified on the prepared carbon nanofiber film;
(3) the prepared carbon nanofiber film contains a microporous structure;
(4) the obtained carbon nanofiber membrane can be used as an interlayer of a lithium sulfur battery, and has a good adsorption effect on polysulfide so as to improve the electrochemical performance of the lithium sulfur battery.
Drawings
FIG. 1 is SEM scanning electron micrographs of ZnO-CNF prepared in examples 1 and 3.
FIG. 2 is a SEM scanning electron micrograph of the CNF prepared in example 5.
FIG. 3 is SEM micrographs of different zinc salts prepared in examples 7 and 8 and CNF obtained at different irradiation powers, wherein (a), (b), (c) and (d) correspond to zinc salt concentrations of 0.2M, 0.4M, 0.6M and 0.8M, respectively, in example 7; (e) (f) (g) (h) correspond to 20%, 40%, 60%, 80% irradiation power in example 8, respectively.
FIG. 4 is an SEM scanning electron micrograph of a comparative CNF obtained in example 6.
FIG. 5 is an XRD spectrum of ZnO-CNF and CNF obtained in example 1 and example 5.
FIG. 6 is a graph of electrochemical performance of the ZnO-CNF and CNF sandwich lithium-sulfur battery prepared in example 1 and example 5.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.
In the invention, all parts and percentages are weight units, and all equipment, raw materials and the like can be purchased from the market or are commonly used in the industry, if not specified.
Example 1
A preparation method of a lithium-sulfur battery interlayer material with excimer ultraviolet lamp irradiation modified ZnO based on acrylic yarns as a carbon source comprises the following specific steps:
(1) accurately weighing acrylic fibers by an analytical balance, and dissolving the acrylic fibers in N-N Dimethylformamide (DMF), wherein the total solute concentration is 10%. Stirring for 48h at room temperature, then heating to 85 ℃, and stirring for 2h to obtain a uniform and stable electrostatic spinning solution.
(2) Preparing a nanofiber membrane by adopting electrostatic spinning equipment, wherein the spinning voltage is 10 kV, the receiving distance is 20 cm, the air humidity is 50%, and performing electrostatic spinning on the uniformly stirred spinning solution.
(3) High-temperature carbonization: pre-oxidizing at 190 deg.c for 90 min, carbonizing at 800 deg.c for 3 hr in argon atmosphere to obtain carbon nanometer fiber film with acrylon as carbon source.
(4) And (3) placing the carbon nanofiber thin film obtained in the step (3) in an aqueous solution of zinc chloride for excimer ultraviolet lamp irradiation, wherein the mass concentration of the zinc chloride is 1M, the irradiation power is 80%, and the irradiation time is 10 minutes.
(5) And after irradiation, the carbon nanofiber membrane is washed by deionized water and dried at room temperature, and is completely dried. And annealing at 400 ℃ for 2h in an argon atmosphere to obtain the ZnO-CNF.
Example 2
A preparation method of a lithium-sulfur battery interlayer material with excimer ultraviolet lamp irradiation modified ZnO based on acrylic yarns as a carbon source comprises the following specific steps:
(1) accurately weighing acrylic fibers by an analytical balance, and dissolving the acrylic fibers in N-N Dimethylformamide (DMF), wherein the total solute concentration is 10%. Stirring for 48h at room temperature, then heating to 85 ℃, and stirring for 2h to obtain a uniform and stable electrostatic spinning solution.
(2) The nanofiber membrane is prepared by adopting electrostatic spinning equipment, the spinning voltage is 10 kV, the receiving distance is 20 cm, and the air humidity is 50%.
(3) High-temperature carbonization: pre-oxidizing at 190 deg.c for 90 min, carbonizing at 800 deg.c for 3 hr in argon atmosphere to obtain carbon nanometer fiber film with acrylon as carbon source.
(4) And (3) placing the carbon nanofiber thin film obtained in the step (3) in an aqueous solution of zinc chloride for excimer ultraviolet lamp irradiation, wherein the concentration of zinc chloride is 2M, the irradiation power is 80%, and the irradiation time is 10 minutes.
(5) And after irradiation, the carbon nanofiber membrane is washed by deionized water and dried at room temperature, and is completely dried. And annealing at 400 ℃ for 2h in an argon atmosphere to obtain the ZnO-CNF.
Example 3
A preparation method of a lithium-sulfur battery interlayer material with excimer ultraviolet lamp irradiation modified ZnO based on acrylic yarns as a carbon source comprises the following specific steps:
(1) accurately weighing acrylic fibers by an analytical balance, and dissolving the acrylic fibers in N-N Dimethylformamide (DMF), wherein the total solute concentration is 10%. Stirring for 48h at room temperature, then heating to 85 ℃, and stirring for 2h to obtain a uniform and stable electrostatic spinning solution.
(2) The nanofiber membrane is prepared by adopting electrostatic spinning equipment, the spinning voltage is 10 kV, the receiving distance is 20 cm, and the air humidity is 50%.
(3) High-temperature carbonization: pre-oxidizing at 190 deg.c for 90 min, carbonizing at 800 deg.c for 3 hr in argon atmosphere to obtain carbon nanometer fiber film with acrylon as carbon source.
(4) And (3) placing the carbon nanofiber thin film obtained in the step (3) in an aqueous solution of zinc chloride for excimer ultraviolet lamp irradiation, wherein the mass concentration of the zinc chloride is 1M, the irradiation power is 90%, and the irradiation time is 20 minutes.
(5) And after irradiation, the carbon nanofiber membrane is washed by deionized water and dried at room temperature, and is completely dried. And annealing at 400 ℃ for 2h in an argon atmosphere to obtain the ZnO-CNF.
Example 4
A preparation method of a lithium-sulfur battery interlayer material with excimer ultraviolet lamp irradiation modified ZnO based on acrylic yarns as a carbon source comprises the following specific steps:
(1) accurately weighing acrylic fibers by an analytical balance, and dissolving the acrylic fibers in N-N Dimethylformamide (DMF), wherein the total solute concentration is 10%. Stirring for 48h at room temperature, then heating to 85 ℃, and stirring for 2h to obtain a uniform and stable electrostatic spinning solution.
(2) The nanofiber membrane is prepared by adopting electrostatic spinning equipment, the spinning voltage is 10 kV, the receiving distance is 20 cm, and the air humidity is 50%.
(3) High-temperature carbonization: pre-oxidizing at 190 deg.c for 90 min, carbonizing at 800 deg.c for 3 hr in argon atmosphere to obtain carbon nanometer fiber film with acrylon as carbon source.
(4) And (3) placing the carbon nanofiber thin film obtained in the step (3) in an aqueous solution of zinc chloride for excimer ultraviolet lamp irradiation, wherein the concentration of zinc chloride is 2M, the irradiation power is 90%, and the irradiation time is 10 minutes.
(5) And after irradiation, the carbon nanofiber membrane is washed by deionized water and dried at room temperature, and is completely dried. And annealing at 400 ℃ for 2h in an argon atmosphere to obtain the ZnO-CNF.
Example 5
A preparation method of a lithium-sulfur battery interlayer material with excimer ultraviolet lamp irradiation modified ZnO based on acrylic yarns as a carbon source comprises the following specific steps:
(1) accurately weighing acrylic fibers by an analytical balance, and dissolving the acrylic fibers in N-N Dimethylformamide (DMF), wherein the total solute concentration is 10%. Stirring for 48h at room temperature, then heating to 85 ℃, and stirring for 2h to obtain a uniform and stable electrostatic spinning solution.
(2) The nanofiber membrane is prepared by adopting electrostatic spinning equipment, the spinning voltage is 10 kV, the receiving distance is 20 cm, and the air humidity is 50%.
(3) High-temperature carbonization: pre-oxidizing at 190 deg.c for 90 min, carbonizing at 800 deg.c for 3 hr in argon atmosphere to obtain carbon nanometer fiber film with acrylon as carbon source.
Example 6
A preparation method of a lithium-sulfur battery interlayer material with excimer ultraviolet lamp irradiation modified ZnO based on acrylic yarns as a carbon source comprises the following specific steps:
(1) accurately weighing acrylic fibers by an analytical balance, and dissolving the acrylic fibers in N-N Dimethylformamide (DMF), wherein the total solute concentration is 10%. Stirring for 48h at room temperature, then heating to 85 ℃, and stirring for 2h to obtain a uniform and stable electrostatic spinning solution.
(2) The nanofiber membrane is prepared by adopting electrostatic spinning equipment, the spinning voltage is 10 kV, the receiving distance is 20 cm, and the air humidity is 50%.
(3) High-temperature carbonization: pre-oxidizing at 190 deg.c for 90 min, carbonizing at 800 deg.c for 3 hr in argon atmosphere to obtain carbon nanometer fiber film with acrylon as carbon source.
(4) And (3) placing the carbon nanofiber thin film obtained in the step (3) in an aqueous solution of zinc chloride, wherein the mass concentration of the zinc chloride is 1M, the irradiation power is 90%, and the time is 20 minutes.
(5) The carbon nanofiber membrane was washed with deionized water and dried at room temperature, and completely dried. Annealing was carried out at 400 ℃ for 2 hours in an argon atmosphere to obtain a control CNF.
Example 7 investigation of Zinc chloride at different Mass concentrations upon irradiation
A preparation method of a lithium-sulfur battery interlayer material with excimer ultraviolet lamp irradiation modified ZnO based on acrylic yarns as a carbon source comprises the following specific steps:
(1) accurately weighing acrylic fibers by an analytical balance, and dissolving the acrylic fibers in N-N Dimethylformamide (DMF), wherein the total solute concentration is 10%. Stirring for 48h at room temperature, then heating to 85 ℃, and stirring for 2h to obtain a uniform and stable electrostatic spinning solution.
(2) The nanofiber membrane is prepared by adopting electrostatic spinning equipment, the spinning voltage is 10 kV, the receiving distance is 20 cm, and the air humidity is 50%.
(3) High-temperature carbonization: pre-oxidizing at 190 deg.c for 90 min, carbonizing at 800 deg.c for 3 hr in argon atmosphere to obtain carbon nanometer fiber film with acrylon as carbon source.
(4) And (3) placing the carbon nanofiber thin film obtained in the step (3) into zinc chloride aqueous solutions with different mass concentrations, wherein the mass concentrations of zinc chloride are 0.2M, 0.4M, 0.6M and 0.8M respectively, the irradiation power is 90%, and the time is 20 minutes.
(5) The carbon nanofiber membrane was washed with deionized water and dried at room temperature, and completely dried. Annealing was carried out at 400 ℃ for 2 hours in an argon atmosphere to obtain a control CNF.
EXAMPLE 8 investigation of different irradiation powers upon irradiation
A preparation method of a lithium-sulfur battery interlayer material with excimer ultraviolet lamp irradiation modified ZnO based on acrylic yarns as a carbon source comprises the following specific steps:
(1) accurately weighing acrylic fibers by an analytical balance, and dissolving the acrylic fibers in N-N Dimethylformamide (DMF), wherein the total solute concentration is 10%. Stirring for 48h at room temperature, then heating to 85 ℃, and stirring for 2h to obtain a uniform and stable electrostatic spinning solution.
(2) The nanofiber membrane is prepared by adopting electrostatic spinning equipment, the spinning voltage is 10 kV, the receiving distance is 20 cm, and the air humidity is 50%.
(3) High-temperature carbonization: pre-oxidizing at 190 deg.c for 90 min, carbonizing at 800 deg.c for 3 hr in argon atmosphere to obtain carbon nanometer fiber film with acrylon as carbon source.
(4) And (3) placing the carbon nanofiber thin film obtained in the step (3) in a zinc chloride aqueous solution with the mass concentration of 1M, wherein the irradiation power is respectively 20%, 40%, 60% and 80%, and the irradiation time is 20 minutes.
(5) The carbon nanofiber membrane was washed with deionized water and dried at room temperature, and completely dried. Annealing was carried out at 400 ℃ for 2 hours in an argon atmosphere to obtain a control CNF.
FIG. 1 shows ZnO-CNF carbon nanofibers prepared in examples 1 and 3. As can be seen from the SEM scanning electron microscope in fig. 1 (a), the ZnO particles formed on the carbon nanofibers modified by irradiation with zinc chloride at a mass concentration of 1M and an irradiation power of 80% for 10 minutes were not uniformly distributed and were few. As can be seen from the SEM scanning electron microscope in fig. 1 (b), the mass concentration of zinc chloride is 1M, the irradiation power is 90%, and the ZnO particles formed on the modified carbon nanofibers are irradiated and modified by irradiation for 20 minutes. Obtaining the modified carbon nanofiber with the fiber diameter of 330-360nm after irradiation, wherein the surface of the fiber is provided with micropores. FIG. 2 shows the CNF carbon nanofiber prepared in example 5, which has a diameter of 230-260 nm. The carbon nanofiber has smooth surface and uniform fiber thickness. FIG. 4 is a SEM image of a CNF prepared as a comparative example in example 6, in which zinc chloride was used at a mass concentration of 1M and an irradiation power of 90%, and the CNF was immersed in a zinc chloride solution for 20 minutes without irradiation and then subjected to annealing. Fig. 3 (a), (b), (c) and (d) respectively correspond to the CNF after annealing with the zinc chloride concentration of 0.2M, 0.4M, 0.6M and 0.8M and the irradiation power of 90% in example 7, and it can be seen from the figure that, at these concentrations, it is difficult to generate ZnO particles on the surface of the carbon nanofiber by irradiation, and the fiber shows only thickness variation of different degrees, and the variation is very slight and basically maintains the original shape. Fig. 3 (e) (f) (g) (h) respectively correspond to the irradiation power of 20%, 40%, 60%, 80%, the zinc chloride concentration of 1M, the irradiation time of 20 minutes, and the CNF after annealing in example 8, and it can be seen from the figure that, under these several irradiation powers, ZnO particles are difficult to be generated on the surface of the carbon nanofiber, and the fiber only shows thickness variation of different degrees, and the variation is very slight, and the original shape is basically maintained. Through a series of comparative tests, the preferable irradiation conditions of the excimer ultraviolet lamp are as follows: the irradiation power is 90%, the irradiation time is 20min, and the concentration of zinc chloride is 1M. When the irradiation time is increased, the fibers are damaged to different degrees, the structural integrity of the conductive carbon nanofiber cannot be maintained, and when the irradiation power is too low or the concentration of zinc chloride is too low, ZnO particles cannot be formed on the surface of the carbon fiber. Increasing the concentration of zinc chloride is wasteful to some extent, and a good particle distribution is exhibited already at 1M concentration and the subsequent formation of a lithium-sulfur battery interlayer can provide a battery with excellent electrochemical performance.
From the XRD spectrum analysis of the ZnO-CNF and CNF prepared in example 1 and example 5 in FIG. 5, it can be seen that the solid particles formed are ZnO particles, and the particles are uniform.
FIG. 6 is a graph showing the electrochemical performance of ZnO-CNF and CNF obtained in examples 1 and 5 as interlayers applied to a lithium-sulfur battery, the diameter of the interlayer being 14mm, and it can be seen that the lithium-sulfur battery with the ZnO-CNF interlayer has a first cycle capacity of 1215.5 mAh g under a constant current cycle of 0.2C-1Sulfur utilization was 72.5%, and capacity was 874 mAh g after 100 cycles-1The capacity retention rate is 72%, the capacity attenuation per circle is only 0.28%, and the average coulombic efficiency is as high as 98%. Lithium sulfur battery with CNF interlayer at 0.2CThe first loop capacity under constant current circulation is 992.1 mAh g-1Sulfur utilization was 59.2%, capacity after 100 cycles was 706mAh g-1The capacity retention rate was 70.9%, and the average coulombic efficiency was 92%. The lithium-sulfur battery with the ZnO-CNF interlayer shows more excellent electrochemical performance.
In conclusion, the preparation material provided by the invention is environment-friendly in source, short in process, green, safe, efficient and clean. The prepared ZnO modified carbon nanofiber film is used as an interlayer of the lithium-sulfur battery, the interlayer can physically block polysulfide and can fix the polysulfide through efficient and powerful chemical adsorption, so that active substances can be efficiently utilized, and the electrochemical performance of the lithium-sulfur battery is improved.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (7)
1. A preparation method of an acrylic fiber-based lithium-sulfur battery interlayer material with ZnO modified by excimer ultraviolet lamp irradiation is characterized by comprising the following steps:
(1) preparation of spinning solution: dissolving acrylic fiber yarns in N-N Dimethylformamide (DMF) and fully stirring;
(2) the preparation method of the nanofiber membrane comprises the following steps: preparing the spinning solution obtained in the step (1) into a nanofiber film by a centrifugal spinning method, a melt spinning method or an electrostatic spinning method;
(3) preparing carbonized acrylic fibers: pre-oxidizing the nanofiber membrane obtained in the step (2) at the temperature of 100-; then under the protection of inert gas, carbonizing at 600-1000 ℃ for 1-8 hours to obtain carbon nano-fibers;
(4) preparing ZnO modified carbonized acrylic fibers: performing excimer irradiation treatment on the carbon nanofiber obtained in the step (3), placing the carbon nanofiber in an aqueous solution containing zinc ions, irradiating the carbon nanofiber through an excimer ultraviolet lamp, drying the carbon nanofiber at the drying temperature of 10-40 ℃ for 5-25 hours, completely drying the carbon nanofiber, and annealing the carbon nanofiber in an inert gas atmosphere to obtain the lithium-sulfur battery interlayer material with ZnO modified by excimer ultraviolet lamp irradiation;
the irradiation power of the excimer ultraviolet lamp is 90%, the irradiation time is 20min, and the molar concentration of zinc ions in irradiation is 1M.
2. The method of claim 1, wherein: the stirring action in the step (1) is divided into two steps, firstly stirring for a long time of 10-40 hours at room temperature, and then stirring for 80-160 min at a high temperature of 60-130 ℃.
3. The method of claim 1, wherein: when electrostatic spinning is adopted in the step (2), the electrostatic spinning voltage is 10-40 kV, the receiving distance is 15-35 cm, and the air humidity is 13-53%.
4. The method of claim 1, wherein: the water solution containing zinc ions in the step (4) is a zinc salt water solution, and the zinc salt is selected from one or more of zinc nitrate, zinc chloride, zinc sulfate or zinc acetate.
5. The method of claim 1, wherein: the annealing condition in the step (4) is that the temperature is 200-500 ℃, the heating rate is 5 ℃/min, and the time is 1-5 hours.
6. An acrylic fiber-based lithium-sulfur battery interlayer material with ZnO modified by excimer ultraviolet lamp irradiation, which is prepared by the preparation method of claim 1.
7. An application of the acrylic fiber-based lithium-sulfur battery interlayer material with quasi-molecular ultraviolet lamp irradiation modified ZnO, which is disclosed by claim 6, in the preparation of a lithium-sulfur battery.
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