CN110707264B - High-conductivity coating diaphragm for lithium-sulfur battery and preparation method and application thereof - Google Patents
High-conductivity coating diaphragm for lithium-sulfur battery and preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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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
Abstract
The invention discloses a high-conductivity coating diaphragm for a lithium-sulfur battery, and a preparation method and application thereof, wherein the preparation method comprises the following steps: soaking a polyolefin film into the first slurry, and coating the second slurry on the positive electrode side of the polyolefin film to obtain the high-conductivity coating diaphragm for the lithium-sulfur battery, wherein the preparation method of the first slurry comprises the following steps: uniformly dispersing a polymer in deionized water to obtain a first slurry, wherein the preparation method of the second slurry comprises the following steps: and adding the dispersing agent into the solvent, uniformly stirring to obtain a mixed solution, uniformly mixing the tannic acid and the carbon conductor, adding the mixed solution, uniformly stirring, and sanding to obtain a second slurry. According to the invention, the functional layer is introduced to the surface of the polyolefin diaphragm, so that on one hand, the generation of polysulfide is prevented, and the shuttle effect is avoided; on the other hand, the introduction of the functional layer can improve the polarity of the surface of the diaphragm, so that the improvement of the electrolyte wettability of the diaphragm is beneficial to the uniform transmission of lithium ions in the diaphragm, and the ionic conductivity and the lithium ion transference number of the battery are improved.
Description
Technical Field
The invention belongs to the technical field of battery diaphragms, and particularly relates to a high-conductivity coating diaphragm for a lithium-sulfur battery, and a preparation method and application thereof.
Background
Lithium ion batteries are secondary energy sources with the best comprehensive performance at present due to the characteristics of high energy density, long service life, no self-discharge and the like, and are widely applied to portable electronic equipment such as notebooks, mobile phones and the like. With the application of the lithium ion battery in the fields of electric vehicles, energy storage systems and the like, higher requirements are put forward on the performance of the lithium ion battery. Lithium-sulfur batteries, i.e., batteries composed of a positive electrode (cathode) containing sulfur and a negative electrode (anode) containing lithium metal, have been developed in lithium ion batteries due to their high specific energy. The sulfur of the positive electrode becomes a polysulfide compound dissolved in the electrolyte during discharge, and the polysulfide compound passes through the separator to the negative electrode of lithium, reacts with lithium and returns to the positive electrode side, and the process is called shuttle effect. Shuttling effects currently represent the greatest obstacle to cycling stability of lithium-sulfur batteries.
The diaphragm is one of the key components of the lithium ion battery, not only influences the cycle life and the rate capability of the battery, but also plays a decisive role in the safety performance of the battery. The polyolefin diaphragm has the characteristics of good chemical stability, high mechanical strength, low price, high-temperature closed pore and the like, and occupies a dominant position in commercial lithium ion batteries, but the characteristics of low surface energy, low melting point and the like of the material limit the performance of the diaphragm.
In the circulation process of the lithium ion battery, on one hand, the electrolyte participates in electrochemical reaction or is decomposed, so that the electrolyte is consumed; on the other hand, as time increases, the battery sealing substance ages and falls off, so that the sealing performance of the battery is deteriorated, the electrolyte can volatilize and leak, the total amount of the electrolyte is continuously reduced, and the capacity attenuation and the service life reduction of the battery are caused. The polyolefin diaphragm has low surface energy, poor compatibility with electrolyte containing polar components, low liquid absorption rate and poor electrolyte retention rate; in addition, the continuous consumption of the electrolyte will result in insufficient electrolyte in the battery. The uneven distribution causes an electrolyte starvation area on the interface of an electrode and a diaphragm, so that the interface impedance is increased, the polarization is serious, the current distribution is uneven, and the increase of the internal resistance of the battery is shown when the current distribution is reflected on the battery, so that the performance of the battery is sharply reduced.
The method for improving the defect is to improve the affinity of the diaphragm and the electrolyte and increase the liquid storage and retention capacity of the diaphragm, thereby slowing down the loss of the electrolyte, ensuring the good contact between the diaphragm and the electrode and improving the cycling stability of the battery. In addition, sufficient electrolyte also provides a rapid and continuous lithium ion migration channel for the diaphragm to charge and discharge at high rate, so that the battery has better high-current charge and discharge performance.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a preparation method of a high-conductivity coating diaphragm for a lithium-sulfur battery.
Another object of the present invention is to provide a high-conductivity coated separator for a lithium-sulfur battery obtained by the above preparation method.
It is another object of the present invention to provide a battery based on the above-described high-conductivity coated separator for lithium sulfur batteries.
Another object of the present invention is to provide the use of the above-mentioned high-conductivity coated separator for lithium-sulfur batteries in avoiding the shuttle effect and increasing the ionic conductivity and lithium ion transport number.
The purpose of the invention is realized by the following technical scheme.
A preparation method of a high-conductivity coating diaphragm for a lithium-sulfur battery comprises the following steps:
immersing a polyolefin film into the first slurry for 2-8 min, drying at 40-80 ℃ for 10-50 s, coating the second slurry on the positive electrode side of the polyolefin film, drying at 40-80 ℃ for 10-50 s to obtain the high-conductivity coating diaphragm for the lithium-sulfur battery, wherein,
the preparation method of the first slurry comprises the following steps: uniformly dispersing a polymer in deionized water to obtain the first slurry, wherein the ratio of the polymer to the deionized water (0.02-0.2) is as follows in parts by mass: (10-15), wherein the polymer is polyvinylidene fluoride (PVDF), polymethyl methacrylate (PMMA) or polyethylene oxide (PEO);
the preparation method of the second slurry comprises the following steps: adding a dispersing agent into a solvent, uniformly stirring to obtain a mixed solution, uniformly mixing tannic acid and a carbon conductor, adding the mixed solution, uniformly stirring, and sanding to obtain a second slurry, wherein the solvent is a mixture of ethanol and water, and the ratio of the mass fraction of the dispersing agent, the volume fraction of the ethanol, the volume fraction of the water, the mass fraction of the tannic acid and the mass fraction of the carbon conductor in the second slurry is (0.01-0.02): (1-10): (15-30): (0.1-0.6): (0.1-0.7), the dispersing agent is polyacrylic acid ammonium salt, trimethyl ammonium salt or polyethylene glycol, and the carbon conductor is graphene, Super-p or carbon black.
In the above technical scheme, the polyolefin film is a polyethylene film or a polypropylene film.
In the technical scheme, the dispersing agent accounts for 1.5-5 wt% of the carbon conductor.
In the technical scheme, the dispersing agent is added into the solvent, and the mixture is stirred for at least 10min until the mixture is uniform, so that a mixed solution is obtained.
In the technical scheme, the tannic acid and the carbon conductor are mixed and stirred for 10-30 min to be uniform, then added into the mixed solution, stirred uniformly, and subjected to sanding for 20-60 min to obtain the second slurry.
In the above technical solution, the manner of coating the second slurry on the positive electrode side of the polyolefin film is roll coating.
In the technical scheme, the coating thickness of the second slurry is 1-8 micrometers.
In the above technical solution, when the unit of the mass fraction is kg, the unit of the volume fraction is L.
The high-conductivity coating diaphragm for the lithium-sulfur battery obtained by the preparation method.
And a battery based on the high-conductivity coating diaphragm for the lithium-sulfur battery.
In the above technical solution, the positive electrode of the battery is sulfur, and the negative electrode is lithium.
In the technical scheme, the capacity retention rate of the battery after the battery is cycled for 100 circles under the multiplying power of 0.5C is 97-99%, and the average coulombic efficiency of the battery after the battery is cycled for 20 circles is 99.7-99.9%.
The high-conductivity coating diaphragm for the lithium-sulfur battery is applied to avoiding the shuttle effect and improving the ionic conductivity and the lithium ion transport number.
In the technical scheme, the decomposition voltage of the high-conductivity coating diaphragm for the lithium-sulfur battery is 4.7-4.8V, the thermal shrinkage rate of the diaphragm at 130 ℃ for 1 hour is 0.7-1.1%, and the tensile strength of the diaphragm is 1580-1730 Kg/cm2The contact angle of the electrolyte: 6-13 degrees, liquid absorption rate: 280-330%, ionic conductivity: 1.1X 10-3～1.3×10-3s/cm-1The transference number of lithium ions: 0.5 to 0.8.
According to the invention, the functional layer is introduced to the surface of the polyolefin diaphragm, so that on one hand, the generation of polysulfide is prevented, and the shuttle effect is avoided; on the other hand, the introduction of the functional layer can improve the polarity of the surface of the diaphragm, so that the improvement of the electrolyte wettability of the diaphragm is beneficial to the uniform transmission of lithium ions in the diaphragm, and the ionic conductivity and the lithium ion transference number of the battery are improved. And the high ionic conductivity and lithium ion transference number can reduce the polarization in the battery, especially under the condition of high-rate charge and discharge, thereby improving the rate capability of the diaphragm.
Detailed Description
In the technical scheme of the invention, the carbon conductor can form a reduction site for sulfur ions to prevent polysulfide from generating; polyvinylidene fluoride (PVDF), polymethyl methacrylate (PMMA) and polyethylene oxide (PEO) can be swelled by the electrolyte to form gel, so that the interface performance is improved, the interface impedance is reduced, and the liquid absorption and retention capacity of the diaphragm is enhanced;
the tannin is a plant polyphenol, has higher molecular polarity and good affinity with electrolyte, and has better adhesion effect on various substrates;
to avoid the effect of the reduction in porosity on the ionic conductivity, the thinner the coating should be, the better. The coating thickness can be effectively controlled by adopting a mode of combining dip coating and roller coating, and the ultrathin coating diaphragm is prepared.
The technical scheme of the invention is further explained by combining specific examples.
The following examples adopt a stirrer for stirring, and the stirrer is a double-planet power mixer with the model: HY-DLH43L, manufacturer: guangzhou Hongshang mechanical science and technology, Inc.;
the sanding adopts the full ceramic nanometer to grind machine, the model: PT-5L, the manufacturer is a Noo mechanical equipment Co., Ltd.
In the following examples, parts by mass are in kg and parts by volume are in L.
The electrolyte adopted in the following embodiment is purchased from Shenzhen New aegiu science and technology Limited, the solute in the electrolyte is lithium hexafluorophosphate, and the concentration of the lithium hexafluorophosphate in the electrolyte is 1.5 mol/L.
Example 1
A preparation method of a high-conductivity coating diaphragm for a lithium-sulfur battery comprises the following steps:
preparing a 9-micrometer-thick polyolefin film, namely a polyethylene film, immersing the polyolefin film into the first slurry for 5min, drying at 60 ℃ for 0.5min, then rolling the second slurry on the positive electrode side of the polyolefin film, and drying at 60 ℃ for 0.5min to obtain the high-conductivity coating diaphragm for the lithium-sulfur battery, wherein the coating thickness of the second slurry is 2 micrometers.
The preparation method of the first slurry comprises the following steps: uniformly dispersing (dissolving) a polymer in deionized water to obtain a first slurry, wherein the ratio of the polymer to the deionized water is 0.05: 10, the polymer is polyethylene oxide (PEO);
the preparation method of the second slurry comprises the following steps: adding a dispersing agent into a solvent, stirring for 10min to obtain a uniform mixed solution, mixing and stirring tannic acid and a carbon conductor for 10min to obtain a uniform mixed solution, adding the uniform mixed solution into the mixed solution, stirring for 30min to obtain a uniform mixed solution, sanding for 20min to obtain a second slurry, wherein the solvent is a mixture of ethanol and water, and in the second slurry, the mass parts of the dispersing agent, the volume parts of the ethanol, the volume parts of the water, the mass parts of the tannic acid and the mass part ratio of the carbon conductor are 0.01: 10: 30: 0.2: 0.2, the dispersant is polyacrylic ammonium salt, and the carbon conductor is graphene.
The decomposition voltage of the high-conductivity coating diaphragm for the lithium-sulfur battery obtained in example 1 was 4.7V, the thermal shrinkage at 130 ℃ for 1 hour was 0.7%, and the tensile strength was 1650Kg/cm2The contact angle of the electrolyte: 9 ± 2.2, liquid uptake: 330%, ionic conductivity: 1.3X 10-3s/cm-1The transference number of lithium ions: 0.8. the sulfur positive electrode and the lithium negative electrode are adopted to assemble the battery, the capacity retention rate is 98% after the battery is cycled for 100 circles under the multiplying power of 0.5C, and the average coulombic efficiency is 99.84% after the battery is cycled for 20 circles.
Example 2
A preparation method of a high-conductivity coating diaphragm for a lithium-sulfur battery comprises the following steps:
preparing a 9-micrometer-thick polyolefin film, namely a polyethylene film, immersing the polyolefin film into the first slurry for 5min, drying at 60 ℃ for 0.5min, then rolling the second slurry on the positive electrode side of the polyolefin film, and drying at 60 ℃ for 0.5min to obtain the high-conductivity coating diaphragm for the lithium-sulfur battery, wherein the coating thickness of the second slurry is 1.5 micrometers.
The preparation method of the first slurry comprises the following steps: uniformly dispersing (dissolving) a polymer in deionized water to obtain a first slurry, wherein the ratio of the polymer to the deionized water is 0.02: 15, the polymer is polyvinylidene fluoride (PVDF);
the preparation method of the second slurry comprises the following steps: adding a dispersing agent into a solvent, stirring for 10min till uniformity to obtain a mixed solution, mixing and stirring tannic acid and a carbon conductor for 15min till uniformity, then adding the mixed solution, stirring for 30min till uniformity, sanding for 30min to obtain a second slurry, wherein the solvent is a mixture of ethanol and water, and in the second slurry, the mass parts of the dispersing agent, the ethanol, the water, the tannic acid and the carbon conductor are 0.015: 3: 30: 0.6: 0.3, the dispersant is trimethyl ammonium hydrochloride, and the carbon conductor is Super-p.
The decomposition voltage of the high-conductivity coating diaphragm for the lithium-sulfur battery obtained in example 2 is 4.8V, the thermal shrinkage rate at 130 ℃ for 1 hour is 0.9 percent, and the tensile strength is 1730Kg/cm2The contact angle of the electrolyte: 11 ± 1.2, liquid uptake: 280%, ionic conductivity: 1.1X 10-3s/cm-1The transference number of lithium ions: 0.5. the sulfur positive electrode and the lithium negative electrode are adopted to assemble the battery, the capacity retention rate is 97.2% after the battery is cycled for 100 circles under the multiplying power of 0.5C, and the average coulombic efficiency is 99.71% after the battery is cycled for 20 circles.
Example 3
A preparation method of a high-conductivity coating diaphragm for a lithium-sulfur battery comprises the following steps:
preparing a 9-micrometer-thick polyolefin film, namely a polyethylene film, immersing the polyolefin film into the first slurry for 5min, drying at 60 ℃ for 0.5min, then rolling the second slurry on the positive electrode side of the polyolefin film, and drying at 60 ℃ for 0.5min to obtain the high-conductivity coating diaphragm for the lithium-sulfur battery, wherein the coating thickness of the second slurry is 5 micrometers.
The preparation method of the first slurry comprises the following steps: uniformly dispersing (dissolving) a polymer in deionized water to obtain a first slurry, wherein the ratio of the polymer to the deionized water is 0.17: 10, the polymer is polymethyl methacrylate (PMMA);
the preparation method of the second slurry comprises the following steps: adding a dispersing agent into a solvent, stirring for 10min to obtain a uniform mixed solution, mixing and stirring tannic acid and a carbon conductor for 10min to obtain a uniform mixed solution, adding the uniform mixed solution into the mixed solution, stirring for 40min to obtain a uniform mixed solution, sanding for 40min to obtain a second slurry, wherein the solvent is a mixture of ethanol and water, and in the second slurry, the mass parts of the dispersing agent, the volume parts of the ethanol, the volume parts of the water, the mass parts of the tannic acid and the mass part ratio of the carbon conductor are 0.01: 1: 15: 0.16: 0.64, the dispersant is polyethylene glycol, and the carbon conductor is carbon black.
The decomposition voltage of the high-conductivity coating diaphragm for the lithium-sulfur battery obtained in example 3 is 4.8V, the thermal shrinkage at 130 ℃ for 1 hour is 1.1%, and the tensile strength is 1580Kg/cm2The contact angle of the electrolyte: 10 ± 2.2, liquid uptake: 298%, ionic conductivity: 1.1X 10-3s/cm-1The transference number of lithium ions: 0.7. the sulfur positive electrode and the lithium negative electrode are adopted to assemble the battery, the capacity retention rate is 99% after the battery is cycled for 100 circles under the multiplying power of 0.5C, and the average coulombic efficiency is 99.74% after the battery is cycled for 20 circles.
Comparative example
A method of making a separator, comprising:
preparing a polyolefin film with the thickness of 9 microns, wherein the polyolefin film is a polyethylene film, immersing the polyolefin film into the first slurry for 5min, drying at 60 ℃ for 0.5min, rolling the third slurry on the positive electrode side of the polyolefin film, and drying at 60 ℃ for 0.5min to obtain the diaphragm, wherein the coating thickness of the third slurry is 2 microns.
The preparation method of the first slurry comprises the following steps: uniformly dispersing (dissolving) a polymer in deionized water to obtain a first slurry, wherein the ratio of the polymer to the deionized water is 0.05: 10, the polymer is polyethylene oxide (PEO);
the preparation method of the third slurry comprises the following steps: adding a dispersing agent into a solvent, stirring for 10min to be uniform, adding a carbon conductor, stirring for 30min to be uniform, sanding for 20min to obtain a third slurry, wherein the solvent is a mixture of ethanol and water, and in the third slurry, the mass parts of the dispersing agent, the ethanol, the water and the carbon conductor are 0.01: 10: 30: 0.2, the dispersant is polyacrylic ammonium salt, and the carbon conductor is graphene.
Comparative example effects:
the decomposition voltage of the separator obtained in the comparative example was 4.7VThe thermal shrinkage rate of 1 hour at 130 ℃ is 1.2 percent, and the tensile strength is 1590Kg/cm2The contact angle of the electrolyte: 29 ± 1.6, liquid uptake: 140%, ionic conductivity: 0.7X 10-3s/cm-1, transference number of lithium ion: 0.28. the sulfur positive electrode and the lithium negative electrode are adopted to assemble the battery, the capacity retention rate is 80% after the battery is cycled for 100 circles under the multiplying power of 0.5C, and the average coulombic efficiency is 80.42% after the battery is cycled for 20 circles.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. A preparation method of a high-conductivity coating diaphragm for a lithium-sulfur battery is characterized by comprising the following steps:
immersing a polyolefin film into the first slurry for 2-8 min, drying at 40-80 ℃ for 10-50 s, coating the second slurry on the positive electrode side of the polyolefin film, drying at 40-80 ℃ for 10-50 s to obtain the high-conductivity coating diaphragm for the lithium-sulfur battery, wherein,
the preparation method of the first slurry comprises the following steps: uniformly dispersing a polymer in deionized water to obtain the first slurry, wherein the ratio of the polymer to the deionized water (0.02-0.2) is as follows in parts by mass: (10-15), wherein the polymer is polyvinylidene fluoride, polymethyl methacrylate or polyethylene oxide;
the preparation method of the second slurry comprises the following steps: adding a dispersing agent into a solvent, uniformly stirring to obtain a mixed solution, uniformly mixing tannic acid and a carbon conductor, adding the mixed solution, uniformly stirring, and sanding to obtain a second slurry, wherein the solvent is a mixture of ethanol and water, and the ratio of the mass fraction of the dispersing agent, the volume fraction of the ethanol, the volume fraction of the water, the mass fraction of the tannic acid and the mass fraction of the carbon conductor in the second slurry is (0.01-0.02): (1-10): (15-30): (0.1-0.6): (0.1-0.7), the dispersing agent is polyacrylic acid ammonium salt, trimethyl ammonium salt or polyethylene glycol, and the carbon conductor is graphene, Super-p or carbon black; the unit of the parts by mass is kg, and the unit of the parts by volume is L.
2. The production method according to claim 1, wherein the polyolefin film is a polyethylene film or a polypropylene film; the dispersant accounts for 1.5-5 wt% of the carbon conductor; adding the dispersing agent into the solvent, and stirring for at least 10min until the mixture is uniform to obtain a mixed solution.
3. The preparation method according to claim 2, wherein the second slurry is obtained by mixing and stirring the tannic acid and the carbon-based conductor for 10 to 30 minutes until uniform, adding the mixture to the mixed solution, uniformly stirring, and sanding for 20 to 60 minutes.
4. The production method according to claim 3, wherein the second slurry is applied to the positive electrode side of the polyolefin film by roll coating; the coating thickness of the second slurry is 1-8 microns.
5. The high-conductivity coated separator for a lithium-sulfur battery obtained by the production method according to any one of claims 1 to 4.
6. A battery based on the high-conductivity coated separator for lithium sulfur battery according to claim 5.
7. The battery of claim 6, wherein the positive electrode of the battery is sulfur and the negative electrode is lithium.
8. The battery according to claim 7, wherein the capacity retention rate of the battery after 100 cycles at a rate of 0.5C is 97-99%, and the average coulombic efficiency of the battery after 20 cycles is 99.7-99.9%.
9. Use of the high-conductivity coated separator for lithium-sulfur battery according to claim 5 for avoiding shuttling effect and increasing ion conductivity and lithium ion transport number.
10. The use according to claim 9, wherein the decomposition voltage of the high-conductivity coating separator for lithium-sulfur battery is 4.7-4.8V, the thermal shrinkage at 130 ℃ for 1 hour is 0.7-1.1%, and the tensile strength is 1580-1730 Kg/cm2The contact angle of the electrolyte: 6-13 degrees, liquid absorption rate: 280-330%, ionic conductivity: 1.1X 10-3～1.3×10-3s/cm-1The transference number of lithium ions: 0.5 to 0.8.
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| CN113206344A (en) * | 2020-02-03 | 2021-08-03 | 河北金力新能源科技股份有限公司 | Functional diaphragm for lithium-sulfur battery and preparation method and application thereof |
| CN111525073A (en) * | 2020-03-25 | 2020-08-11 | 河北金力新能源科技股份有限公司 | Functional diaphragm for lithium-sulfur battery and preparation method thereof |
| CN113540686A (en) * | 2020-04-20 | 2021-10-22 | 河北金力新能源科技股份有限公司 | Functional diaphragm for lithium-sulfur battery and preparation method thereof |
| CN112952292B (en) * | 2020-12-23 | 2022-12-09 | 重庆大学 | Composite diaphragm capable of being used for metal lithium battery and metal sodium battery, and preparation method and application thereof |
| CN114976482A (en) * | 2022-04-28 | 2022-08-30 | 清华大学山西清洁能源研究院 | Lithium-sulfur battery diaphragm, preparation method thereof and lithium-sulfur battery |
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| KR100976862B1 (en) * | 2007-11-21 | 2010-08-23 | 주식회사 엘지화학 | secondary battery with improved storage characteristics and method for manufacturing the same |
| KR101329550B1 (en) * | 2012-01-31 | 2013-11-15 | 한밭대학교 산학협력단 | A positive electrode for lithium-sulfur battery and lithium-sulfur battery comprising the same |
| KR20150124301A (en) * | 2014-04-28 | 2015-11-05 | 현대자동차주식회사 | A structure of cathode of lithium sulfur battery |
| DE102014218803A1 (en) * | 2014-09-18 | 2016-03-24 | Robert Bosch Gmbh | Separator for a battery cell and battery cell |
| KR102038543B1 (en) * | 2016-01-28 | 2019-10-30 | 주식회사 엘지화학 | A Separator For Lithium-Sulfur Battery Having Composite Coating Layer Containing Polydopamine, Manufacturing Method Thereof, And Lithium-Sulfur Battery Comprising The Same |
| CN105514482B (en) * | 2016-01-29 | 2018-01-09 | 中南大学 | A kind of preparation method of lithium-sulfur cell function barrier film |
| WO2018027652A1 (en) * | 2016-08-10 | 2018-02-15 | 东莞新能源科技有限公司 | Separator, preparation method and electrochemical energy storage device |
| CN108807819B (en) * | 2018-06-15 | 2021-06-29 | 珠海冠宇电池股份有限公司 | Diaphragm, preparation method thereof and lithium-sulfur battery |
| CN109167012B (en) * | 2018-08-15 | 2022-04-12 | 珠海冠宇电池股份有限公司 | Multilayer composite structure diaphragm, preparation method thereof and lithium-sulfur battery |
| CN109671895A (en) * | 2018-12-10 | 2019-04-23 | 青岛大学 | Lithium-sulfur cell diaphragm and lithium-sulfur cell comprising the diaphragm |
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