CN109755446B - Lithium-sulfur battery diaphragm and preparation method thereof - Google Patents
Lithium-sulfur battery diaphragm and preparation method thereof Download PDFInfo
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- CN109755446B CN109755446B CN201811501892.8A CN201811501892A CN109755446B CN 109755446 B CN109755446 B CN 109755446B CN 201811501892 A CN201811501892 A CN 201811501892A CN 109755446 B CN109755446 B CN 109755446B
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- 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
Abstract
The invention provides a lithium-sulfur battery diaphragm and a preparation method thereof, wherein a novel lithium-sulfur battery diaphragm is prepared by compounding carrageenan gel and a conventional diaphragm through an electrostatic spinning method, has the advantages of good electrolyte wettability, high temperature resistance and flame retardance, and can effectively inhibit shuttle effect and lithium dendrite growth, and the cycle stability and the safety of a lithium-sulfur battery are improved; meanwhile, the lithium-sulfur battery composite diaphragm has excellent thermal stability and high temperature resistance, can keep a normal working state in a high-temperature environment, and can further greatly improve the working temperature and safety of the battery. The method has the advantages of low cost of raw materials, simple process and easy large-scale production.
Description
Technical Field
The invention relates to a lithium battery and a preparation method thereof, in particular to a lithium-sulfur battery diaphragm and a preparation method thereof.
Background
The lithium-sulfur battery has higher energy density and can be applied to the fields of individual power supplies, unmanned planes and passenger vehicles. The lithium-sulfur battery takes metal lithium as a negative electrode, and has potential safety hazard when in use. Because of the non-uniformity of the lithium metal surface, lithium dendrite is easy to generate in the cycle process, so that the short circuit occurs in the battery, and the battery is ignited and burnt. The energy density of the lithium-sulfur battery is 3-5 times of that of a common battery, the lithium-sulfur battery generates heat seriously in the charging and discharging process, and the battery is easy to cause thermal runaway due to overheating, so that fire and even explosion are caused. The functional diaphragm can inhibit the occurrence of internal short circuit and thermal runaway of the battery, improve the safety performance of the lithium-sulfur battery and weaken the shuttle flying effect in the cycle process to a certain extent.
Compared with the traditional lithium ion battery, the characteristic of high capacity of the electrode material is formed by the intrinsic characteristic of multi-electron reaction of sulfur molecules, but the lithium sulfur battery system is more complex, and the following problems mainly exist: (1) the safety problem. The surface of the metal lithium negative electrode is uneven and uneven, so that lithium ions are accumulated on the surface of the negative electrode to generate dendritic crystals, the dendritic crystals can pierce through the diaphragm to cause short circuit of the positive electrode and the negative electrode of the battery, and the battery is burnt and exploded; (2) sulfide dissolution problem. The sulfur electrode generates soluble polysulfide in the charging and discharging processes, so that on one hand, high-order polysulfide is diffused across a diaphragm and directly reacts with a lithium metal cathode to generate low-order polysulfide, side reaction circulation, namely shuttle effect, in the lithium-sulfur battery is brought, and the coulomb efficiency of the lithium-sulfur battery is reduced; on the other hand, the sulfur-containing component in the battery is lost, so that the performance of the battery is rapidly attenuated.
The problems are the key reasons for poor safety performance of the lithium-sulfur battery, and the problems can be effectively relieved or even eliminated by modifying the diaphragm of the lithium-sulfur battery, so that the overall performance, particularly the safety performance and the cycle performance of the lithium-sulfur battery are improved.
Disclosure of Invention
The invention aims to provide a lithium-sulfur battery diaphragm and a preparation method thereof, which can effectively solve the problems of lithium dendrite and shuttle effect in a lithium-sulfur battery and can improve the high temperature resistance of the diaphragm.
The purpose of the invention is realized by the following technical scheme:
a lithium-sulfur battery diaphragm is characterized in that flame-retardant carrageenan gel coatings are coated on the two side surfaces of conventional diaphragms with different thicknesses, and a composite lithium-sulfur battery diaphragm with a three-layer structure is prepared by utilizing an electrostatic spinning and sol-gel combination method.
Wherein, the preferred scheme is as follows: the thickness of the carrageenan gel coating with flame retardance is between 1 and 20 mu m.
Wherein, the preferred scheme is as follows: the gel coating of the carrageenan has the porosity of 70-99.9 percent, the size of the pores is 10-50nm, and the specific surface area is 400-1200m2/g。
Wherein, the preferred scheme is as follows: the carrageenan gel coating is formed by combining one or more of K-type carrageenan, I-type carrageenan and L-type carrageenan.
Wherein, the preferred scheme is as follows: the conventional diaphragm with different thicknesses is any one of a polyethylene diaphragm with the thickness of 5-30 micrometers, a polypropylene diaphragm with the thickness of 5-30 micrometers, a polyvinylidene fluoride diaphragm with the thickness of 5-30 micrometers, a nylon film with the thickness of 5-35 micrometers or a non-woven fabric diaphragm.
Wherein, the preferred scheme is as follows: the method comprises the following steps:
the method comprises the following steps: soaking 20-40 parts by weight of carrageenan powder in 50-300 parts by weight of NaOH solution with the concentration of 3-6mol/L, magnetically stirring (250-320 rpm) in a water bath kettle at 50-70 ℃ for 30-50 minutes to obtain clear and transparent solution, centrifuging the obtained solution at 3500rpm for 5 minutes, taking supernate, adding absolute ethyl alcohol to adjust the concentration to 10-12%, and preparing to obtain the electrostatic spinning solution.
Step two: and (3) loading the electrostatic spinning solution obtained in the step one into a spinning nozzle, winding the conventional diaphragm on a receiving roller, spinning at the speed of 0.002-0.005mm/s under the environment of 15-20kV electrostatic voltage output by a high-voltage direct-current power supply, the temperature of 30-40 ℃ and the humidity of 20-25% and at the rotating speed of 400-18 rpm of the receiving roller, wherein the rotating speed of the receiving roller is 600-18 cm, and the single-side coated carrageenan gel coating diaphragm is prepared.
Step three: and (3) winding the diaphragm coated with the carrageenan gel coating on the single surface obtained in the step (II) on a receiving roller, wherein the rotating speed of the receiving roller is 400-600rpm, the distance from a spinning nozzle to the receiving roller is 12-18cm, spinning is carried out under the environment of 15-20kV electrostatic voltage output by a high-voltage direct-current power supply, the temperature is 30-40 ℃, the humidity is 20-25%, the propelling speed is 0.002-0.005mm/s, the diaphragm coated with the carrageenan gel coating on the double surfaces is obtained, and the diaphragm is placed in a drying oven at the temperature of 50-60 ℃ for drying for 20-24h, so that the diaphragm of the lithium-sulfur battery is obtained.
The invention has the advantages and effects that:
according to the invention, the composite carrageenan lithium-sulfur battery diaphragm is prepared by compounding the carrageenan gel with the conventional diaphragm through electrostatic spinning, and compared with the conventional diaphragm material, the composite carrageenan lithium-sulfur battery diaphragm has the advantages of good electrolyte wettability, high temperature resistance, flame retardance, and more effective inhibition of shuttle effect and lithium dendritic crystal growth, and the cycle stability and safety of the lithium-sulfur battery are improved; meanwhile, the method has the characteristics of low raw material cost and simple process, provides a new scheme for preparing the lithium-sulfur battery diaphragm, and is suitable for industrial application. Specifically, the present invention has the following advantages: (1) the carrageenan has wide sources and low price, is beneficial to improving the utilization rate of resources, and after electrostatic spinning, the carrageenan gel forms a three-dimensional network structure with uniform pores, which is beneficial to uniform passing of lithium ions, thereby delaying the growth of lithium dendrites; (2) the carrageenan has abundant sulfate ions on the surface, and the structure can prevent polysulfide generated in the charging and discharging process of the sulfur electrode from passing through the diaphragm, inhibit the shuttle effect and improve the cycle efficiency of the battery; (3) the carrageenan has the advantage of high temperature resistance, and the lithium-sulfur battery composite diaphragm has excellent thermal stability and high temperature resistance, can keep a normal working state in a high-temperature environment, and can further greatly improve the working temperature and the safety of the battery.
Drawings
Fig. 1 is a graph comparing the operation mechanism of a conventional separator and a separator for a lithium sulfur battery according to the present invention.
Detailed Description
The present invention will be described in detail with reference to examples.
The first embodiment is as follows:
the method comprises the following steps: soaking 20g of K-carrageenan powder in 50g of NaOH solution with the concentration of 3mol/L, magnetically stirring (250 rpm) in a water bath kettle at 50 ℃ for 30 minutes to obtain a clear and transparent solution, centrifuging the obtained solution at 3500rpm for 5 minutes, taking supernate, adding absolute ethyl alcohol to adjust the concentration to 10%, and preparing to obtain the electrostatic spinning solution.
Step two: and (3) loading the electrostatic spinning solution obtained in the step one into a spinning nozzle, winding a 5-micron polyethylene diaphragm on a receiving roller, spinning the polyethylene diaphragm at the speed of 0.002mm/s under the environment that a high-voltage direct-current power supply outputs 15kV electrostatic voltage, the temperature is 30 ℃, the humidity is 20% and the rotating speed of the receiving roller is 400rpm, and the distance from the spinning nozzle to the receiving roller is 12cm, so that the polyethylene diaphragm with the single-side coated with the carrageenan gel coating is prepared.
Step three: and (3) winding the polyethylene diaphragm coated with the carrageenan gel coating on the single surface obtained in the step (II) on a receiving roller, wherein the rotating speed of the receiving roller is 400rpm, the distance from a spinning nozzle to the receiving roller is 12cm, spinning is carried out under the environment that the output of a high-voltage direct-current power supply is 15kV static voltage, the temperature is 30 ℃, the humidity is 20%, the propelling speed is 0.002mm/s, the polyethylene diaphragm coated with the carrageenan gel on the double surfaces is obtained, and the polyethylene diaphragm is placed in a drying oven at the temperature of 50 ℃ for drying for 20h, so that the lithium-sulfur battery diaphragm is obtained.
Example two:
the method comprises the following steps: soaking 30g of L-carrageenan powder in 200g of NaOH solution with the concentration of 5mol/L, magnetically stirring (280 rpm) for 40 minutes in a water bath kettle at 60 ℃ to obtain a clear and transparent solution, centrifuging the obtained solution for 5 minutes at 3500rpm, taking supernate, adding absolute ethyl alcohol to adjust the concentration to 11%, and preparing to obtain the electrostatic spinning solution.
Step two: and (3) loading the electrostatic spinning solution obtained in the step one into a spinning nozzle, winding a 15-micron polyvinylidene fluoride diaphragm on a receiving roller, spinning the polyvinylidene fluoride diaphragm at the speed of 0.003mm/s under the environment that a high-voltage direct-current power supply outputs 18kV electrostatic voltage, the temperature is 35 ℃, the humidity is 22% and the rotating speed of the receiving roller is 500rpm, and the propelling speed is 0.003mm/s to prepare the polyvinylidene fluoride diaphragm with the single side coated with the carrageenan gel coating.
Step three: and (3) winding the polyvinylidene fluoride membrane coated with the carrageenan gel coating on the single surface obtained in the step (II) on a receiving roller, enabling the rotating speed of the receiving roller to be 500rpm, enabling the distance from a spinning nozzle to the receiving roller to be 15cm, spinning in an environment with the output of a high-voltage direct-current power supply of 18kV static voltage, the temperature of 35 ℃ and the humidity of 22%, enabling the advancing speed to be 0.003mm/s, obtaining the polyvinylidene fluoride membrane coated with the carrageenan gel coating on the double surfaces, and drying in a drying oven at the temperature of 55 ℃ for 20h to obtain the lithium-sulfur battery membrane.
Example three:
the method comprises the following steps: soaking 20g of K-type carrageenan powder and 20g of I-type carrageenan powder in 300g of NaOH solution with the concentration of 6mol/L, magnetically stirring (320 rpm) for 50 minutes in a water bath kettle at 70 ℃ to obtain clear and transparent solution, centrifuging the obtained solution for 5 minutes at 3500rpm, taking supernate, adding absolute ethyl alcohol to adjust the concentration to 12%, and preparing to obtain the electrostatic spinning solution.
Step two: and (3) loading the electrostatic spinning solution obtained in the step one into a spinning nozzle, winding a non-woven fabric diaphragm with the diameter of 20 microns on a receiving roller, spinning at the speed of 0.005mm/s under the environment that a high-voltage direct-current power supply outputs 20kV electrostatic voltage, the temperature is 40 ℃, the humidity is 25%, and the rotation speed of the receiving roller is 600rpm, the distance from the spinning nozzle to the receiving roller is 18cm, and the non-woven fabric diaphragm with the single-side coated with the carrageenan gel coating is prepared.
Step three: and (3) winding the non-woven fabric diaphragm coated with the carrageenan gel coating on the single surface obtained in the step (II) on a receiving roller, wherein the rotating speed of the receiving roller is 600rpm, the distance from a spinning nozzle to the receiving roller is 18cm, spinning is carried out under the environment of 20kV electrostatic voltage output by a high-voltage direct-current power supply, the temperature is 40 ℃, the humidity is 25%, the propelling speed is 0.005mm/s, the non-woven fabric diaphragm coated with the carrageenan gel on the double surfaces is obtained, and the non-woven fabric diaphragm is placed in an oven at the temperature of 60 ℃ for drying for 24h, so that the lithium-sulfur battery diaphragm is obtained.
Comparative example 1
Commercial polypropylene separators were used as a comparison to illustrate the relevant performance parameters of the lithium sulfur battery separators of this patent.
The different membranes of the above examples one, two, three and the comparative example one were subjected to performance tests and characterization, and the results of the data detected are shown in table 1.
TABLE 1
According to the detection result, the lithium-sulfur battery diaphragm prepared by the method provided by the invention has higher porosity, liquid absorption rate and limiting oxygen index value, has very low shrinkage rate, meets the requirement of the lithium battery diaphragm, and can further greatly improve the working temperature and safety of the battery.
The lithium-sulfur battery is formed by adopting metal lithium as a negative electrode, sulfur as a positive electrode and the separator in the first example, the second example, the third example and the first comparative example. The current density of different diaphragms in charging and discharging is 1.0mA cm-2、2.0mA cm-2、3.0mA cm-2The average coulombic efficiency after 120 cycles of the lower cycle is shown in table 2.
TABLE 2
According to the detection result, the lithium-sulfur battery diaphragm disclosed by the invention shows high coulombic efficiency under low current density and high current density, and the fact that the diaphragm disclosed by the invention can effectively inhibit the growth and shuttle effect of lithium dendrites and improve the cycle stability of the lithium-sulfur battery is proved.
Claims (1)
1. A preparation method of a lithium-sulfur battery diaphragm is characterized by comprising the following steps:
the method comprises the following steps: soaking 20-40 parts by weight of carrageenan powder in 50-300 parts by weight of NaOH solution with the concentration of 3-6mol/L, magnetically stirring for 30-50 minutes at 320rpm in a water bath kettle at 50-70 ℃ to obtain clear and transparent solution, centrifuging the obtained solution for 5 minutes at 3500rpm, taking supernate, adding absolute ethyl alcohol to adjust the concentration to 10-12%, and preparing to obtain electrostatic spinning solution;
step two: loading the electrostatic spinning solution obtained in the step one into a spinning nozzle, winding a conventional diaphragm on a receiving roller, spinning at the speed of 0.002-0.005mm/s under the environment that the rotating speed of the receiving roller is 400-18 rpm, the distance from the spinning nozzle to the receiving roller is 12-18cm, the output voltage of a high-voltage direct-current power supply is 15-20kV electrostatic voltage, the temperature is 30-40 ℃, the humidity is 20-25%, and the propelling speed is 0.002-0.005mm/s to prepare the diaphragm with the single side coated with the carrageenan gel coating;
step three: winding the diaphragm coated with the carrageenan gel coating on the single surface obtained in the step two on a receiving roller, wherein the rotating speed of the receiving roller is 400-600rpm, the distance from a spinning nozzle to the receiving roller is 12-18cm, spinning is carried out under the environment that the output of a high-voltage direct-current power supply is 15-20kV electrostatic voltage, the temperature is 30-40 ℃, the humidity is 20-25%, the propelling speed is 0.002-0.005mm/s, the diaphragm coated with the carrageenan gel coating on the double surfaces is obtained, and the diaphragm is placed in a drying oven at the temperature of 50-60 ℃ for drying for 20-24h, so that the diaphragm of the lithium-sulfur battery is prepared;
the lithium-sulfur battery diaphragm is a composite lithium-sulfur battery diaphragm with a three-layer structure, which is prepared by coating flame-retardant carrageenan gel coatings on the surfaces of two sides of conventional diaphragms with different thicknesses and utilizing an electrostatic spinning method; the thickness of the carrageenan gel coating with flame retardance is between 1 and 20 mu m; the gel coating of the carrageenan has the porosity of 70-99.9 percent, the size of the pores is 10-50nm, and the specific surface area is 400-1200m2(ii)/g; the carrageenan gel coating is formed by combining one or more of K-type carrageenan, I-type carrageenan and L-type carrageenan;
the conventional diaphragm with different thicknesses is any one of a polyethylene diaphragm with the thickness of 5-30 micrometers, a polypropylene diaphragm with the thickness of 5-30 micrometers, a polyvinylidene fluoride diaphragm with the thickness of 5-30 micrometers, a nylon film with the thickness of 5-35 micrometers or a non-woven fabric diaphragm.
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