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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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 229940113118 carrageenan Drugs 0.000 claims abstract description 41
- 229920001525 carrageenan Polymers 0.000 claims abstract description 41
- 239000000679 carrageenan Substances 0.000 claims abstract description 41
- 235000010418 carrageenan Nutrition 0.000 claims abstract description 39
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 238000001523 electrospinning Methods 0.000 claims abstract 4
- 238000000576 coating method Methods 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- -1 polyethylene Polymers 0.000 claims description 11
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 229920006284 nylon film Polymers 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 210000001787 dendrite Anatomy 0.000 abstract description 5
- 238000013329 compounding Methods 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000009987 spinning Methods 0.000 description 18
- 238000010041 electrostatic spinning Methods 0.000 description 11
- 238000004804 winding Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000004745 nonwoven fabric Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229920001021 polysulfide Polymers 0.000 description 4
- 239000005077 polysulfide Substances 0.000 description 4
- 150000008117 polysulfides Polymers 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
Images
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- 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
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- Cell Separators (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明提供了一种锂硫电池隔膜及其制备方法，通过静电纺丝的方法将卡拉胶凝胶与常规隔膜复合制备得到了一种新型锂硫电池隔膜，具有电解液浸润性好、耐高温阻燃、更有效抑制穿梭效应和锂枝晶生长的优点，提高了锂硫电池的循环稳定性和安全性；同时本发明的锂硫电池复合隔膜具有优异的热稳定性，可耐高温，在高温环境中能够保持正常工作状态，可以进一步大幅提高电池的工作温度和安全性。该方法原料成本低、工艺简单，易于大规模生产。The invention provides a lithium-sulfur battery separator and a preparation method thereof. A new type of lithium-sulfur battery separator is prepared by compounding carrageenan gel and a conventional separator by an electrospinning method, which has good electrolyte wettability and high temperature resistance. The advantages of flame retardancy, more effective inhibition of the shuttle effect and lithium dendrite growth improve the cycle stability and safety of the lithium-sulfur battery; at the same time, the lithium-sulfur battery composite separator of the present invention has excellent thermal stability, can withstand high temperatures, and is suitable for The normal working state can be maintained in a high temperature environment, which can further greatly improve the working temperature and safety of the battery. The method has low cost of raw materials, simple process and easy mass 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.
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