KR101841278B1 - Lithium sulfur battery - Google Patents

Abstract

The present invention relates to a lithium sulfur battery, which comprises a negative electrode comprising a positive electrode lithium metal negative electrode active material containing a sulfur-carbon composite positive electrode active material, and a solid electrolyte including a lithium salt, a polymer, a filler and Li ₂ S.

Description

Lithium Sulfur Battery {LITHIUM SULFUR BATTERY}

The present disclosure relates to a lithium sulfur battery.

Recently, with the development of advanced electronic industry, it has become possible to reduce the size and weight of electronic equipment, and the use of portable electronic devices is increasing. The need for a battery having a high energy density as a power source for such portable electronic devices has been increased, and research on lithium secondary batteries has been actively conducted.

Examples of such lithium secondary batteries include a lithium ion battery, a lithium-sulfur battery, and a lithium-air battery. There is a continuing need for research to improve the energy density and safety of such lithium secondary batteries. For example, in transition-insertion chemistry, an innovative conversion system is being studied, one of which is the lithium sulfur system. The lithium sulfur system is a system for reacting 16Li + S ₈ → 8Li ₂ S, which is a system capable of obtaining much higher energy (2,500Whkg ^-1 ) than a conventional lithium ion battery (500Whkg ^-1 ).

However, the lithium sulfur battery has a problem that the cycle life is limited due to the sulfur dissociation at the anode, the safety is poor due to the reactivity of the lithium metal anode active material, the electric conductivity of the cathode active material is poor, It is not applicable.

One embodiment of the present invention is to provide a lithium sulfur battery having excellent battery performance.

According to an embodiment of the present invention, there is provided a lithium sulfur battery including a negative electrode including a positive electrode active material including a positive electrode active material, and a solid electrolyte including a lithium salt, a polymer, a filler, and Li ₂ S.

In the solid electrolyte, the content of Li ₂ S may be 1 to 10 moles with respect to 100 moles of the polymer.

The solid electrolyte is a lithium salt, polymer, filler, and Li ₂ S hot-may be manufactured by a press. The hot-press process is a process in which the primary press is performed at a temperature of 80 to 90 DEG C at a pressure of 0.2 to 1 ton for 15 to 20 minutes and then at 80 to 90 DEG C for 60 to 60 ton at a pressure of 4 to 5 tons. Min to 90 min.

In the solid electrolyte, a filler and Li ₂ S are dispersed in a complex of the polymer and the lithium salt.

The polymer may be selected from the group consisting of polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyvinylidene fluoride, and combinations thereof. In addition, the filler may be selected from the group consisting of ZrO ₂ , Al ₂ O ₃ , SiO ₂ , and combinations thereof.

The average size of the filler may be 10 nm to 20 nm.

The lithium salt _{LiCF 3 SO 3, LiPF 6,} LiClO 4, LiBF 4, LiB (C 2 O 4), LiN (SO 2 F) 2, LiN (SO 2 CF 3) 2, LiN (SO 2 C 2 F ₃ ) ₂ , LiCF ₆ SO _3, and combinations thereof.

Other details of the embodiments of the present invention are included in the following detailed description.

The lithium sulfur battery of the present invention is excellent in reliability and safety.

FIG. 1A is a graph showing ion conductivity of a solid polymer electrolyte prepared according to Example 1 under cooling and heating conditions. FIG.
FIG. 1B is a graph showing the results of measuring the impedance of the solid polymer electrolyte prepared according to Example 1 at a temperature of 60.degree. C. or more while changing the temperature. FIG.
1C is a graph showing the results of measuring the impedance of the solid polymer electrolyte prepared according to Example 1 at a temperature lower than 60 DEG C while changing the temperature.
FIG. 2 is a graph showing the charge / discharge characteristics of a battery obtained by charging / discharging the lithium sulfur battery prepared in Example 1 at 70 ° C. and 90 ° C. FIG.
FIG. 3A is a graph showing the results of charging / discharging characteristics obtained by fully charging a lithium sulfur battery manufactured according to Example 1, charging / discharging at 70 DEG C while changing the amount of current, and FIG.
FIG. 3B is a graph showing the results of charging and discharging the lithium sulfur battery prepared in Example 1 while varying the amount of current at 70 ° C, and measuring the specific capacity change according to the cycle. FIG.
4 is a graph showing the charging / discharging characteristics of a lithium sulfur battery manufactured according to Comparative Example 1. Fig.
5 is a SEM photograph of a cathode active material obtained by thoroughly charging a lithium sulfur battery produced according to Example 1 and decomposing.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

One embodiment of the present invention provides a lithium sulfur battery including a negative electrode including a positive electrode active material including a positive electrode active material, and a solid electrolyte including a lithium salt, a polymer, a filler, and Li ₂ S

In the solid electrolyte according to an embodiment of the present invention, the content of Li ₂ S may be 1 to 10 moles per 100 moles of the polymer. When the content of Li ₂ S is included in this range, not only the lithium ion conductivity of the solid electrolyte can be improved but also it is possible to suppress the dissolution of the sulfide-based compound in the electrolyte during charging and discharging.

The solid electrolyte has a filler and Li ₂ S dispersed in a composite of the polymer and the lithium salt. These solid electrolytes are prepared by hot-pressing lithium salts, polymers, fillers and Li ₂ S.

The hot-press process is a process in which the primary press is performed at a temperature of 80 to 90 DEG C at a pressure of 0.2 to 1 ton for 15 to 20 minutes and then at 80 to 90 DEG C for 60 to 60 ton at a pressure of 4 to 5 tons. Min to 90 min.

When the hot-pressing process is carried out under the above temperature range and pressure, the polymer and the lithium salt, Li ₂ S, can be uniformly mixed, and there is an advantage of producing a solid electrolyte of high strength.

The mixing ratio of the lithium salt, polymer, and Li ₂ S may be 1: 20: 0.2 to 1: 20: 2. Further, the content of the filler is, a lithium salt, a polymer, may be used to adjust the ratio of the mixture by weight of Li ₂ S, a mixing ratio (the content of the lithium salt, polymer, and Li ₂ S) the mixing weight: filler 95: 5% by weight to 90: 10% by weight.

The polymer may be selected from the group consisting of polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyvinylidene fluoride, and combinations thereof.

The filler can improve the ionic conductivity, improve the number of lithium transfer, improve the transfer characteristics of the polymer battery, and can also serve as a stabilizer for the lithium metal electrode and electrolyte interface. Specific examples of such fillers include ZrO ₂ , Al ₂ O ₃ , SiO ₂ , or a combination thereof. The filler may have a micrometer size or smaller, but the use of a filler having a nano size size is advantageous in that the conductivity and the mechanical strength are more excellent. The nano-sized filler may have an average size of 10 nm to 20 nm.

The lithium salt _{LiCF 3 SO 3, LiPF 6,} LiClO 4, LiBF 4, LiB (C 2 O 4), LiN (SO 2 F) 2, LiN (SO 2 CF 3) 2, LiN (SO 2 C 2 F ₃ ) ₂ , LiCF ₆ SO _3, and combinations thereof.

The solid polymer electrolyte may have a thickness of 100 탆 to 500 탆. When the thickness of the solid polymer electrolyte is within the above range, it is possible to obtain a mechanical strength suitable for a battery manufacturing process thereafter and to reduce an increase in resistance due to a thick thickness.

As described above, the solid polymer electrolyte according to one embodiment of the present invention can improve the safety of the lithium sulfur battery because it is a completely solid electrolyte containing no liquid phase. In addition, the composite of the polymer and the lithium salt enables lithium ion transmission, Li ₂ S improves the conductivity, can inhibit sulfide dissociation from the anode, and can improve the performance of the lithium sulfur battery.

In a lithium sulfur battery according to an embodiment of the present invention, the anode includes a cathode active material layer including a cathode active material.

The positive electrode active material is a sulfur-carbon composite, elemental sulfur, sulfur-based compound _{(Li 2 S n (n ≥1} ), dissolved in the cache solrayiteu _{(catholyte) Li 2 S n (} n ≥1), organic sulfur compounds and carbon- (C ₂ S _x ) _n : x = 2.5 to 50, n ≧ 2), and a mixture thereof. Among them, a sulfur-carbon composite can be suitably used.

The sulfur-carbon composite refers to Li ₂ S or S and a carbon composite. The sulfur-carbon composite may be prepared by mixing Li ₂ S or S and a carbonaceous material in a weight ratio of 1: 0.5 to 1: 1.5, and ball milling the mixture. As the carbon-based material, any material used as a conductive material in a lithium secondary battery can be used. For example, a graphite-based material, a carbon-based material, or the like can be used. KS 6 (manufactured by Timcal Co.) may be used as the graphite based material, and Super P (manufactured by MMM), Ketjen black, denca black, acetylene black, carbon Black or the like can be used.

The Li ₂ S or S may be amorphous or crystalline, and the use of the crystalline material may be advantageous in that it is stable in the air and dissolution of the electrolyte is suppressed.

The ball milling process may be performed by low-energy ball milling (LEBM), and may be performed for 1 to 5 hours.

The cathode active material layer may further include a conductive material and a binder depending on the type of the cathode active material.

As the conductive material, a cell conductive conductive material that allows electrons to move smoothly in the anode can be used. Such a conductive material is not particularly limited, but a conductive material such as a graphite-based material, a carbon-based material, or a conductive polymer may be used. KS 6 (manufactured by Timcal) is used as the graphite based material, Super P (manufactured by MMM), Ketjen black, denca black, acetylene black, carbon black, etc. are used as the carbon- . Examples of the conductive polymer include polyaniline, polythiophene, polyacetylene, polythiol, and the like. These conductive conductive materials may be used alone or in combination of two or more.

As the binder, a copolymer of poly (ethylene oxide), polyvinyl pyrrolidone, poly (methyl methacrylate), polyvinylidene fluoride, polyhexafluoropropylene and polyvinylidene fluoride (trade name: Kynar), polyethyl acrylate Polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile, polycaprolactam, polyethylene terephthalate, polybutadiene, polyisoprene, polyacrylic acid, derivatives thereof, blends, copolymers and the like can be used.

The content of the conductive material and the binder can be appropriately adjusted, and is not particularly limited.

The positive electrode may be a current collector for supporting the positive electrode active material layer, and may be made of a conductive material such as stainless steel, aluminum, copper, or titanium. However, the present invention is not limited thereto. In particular, a carbon-coated aluminum current collector as the current collector can be suitably used. The use of such a carbon-coated aluminum current collector is advantageous in that it has an excellent adhesion to an active material, has a low contact resistance, and can prevent corrosion caused by aluminum polysulfide, as compared with a carbon-coated aluminum current collector.

The anode having such a structure can be produced by the following process.

The positive electrode may be prepared in the form of a solid without using a solvent, or may be prepared in the form of a slurry using a solvent. Hereinafter, the case where the sulfur-carbon composite is used as the cathode active material will be described for each step.

1) When solvent is not used

The first mixture is prepared by mixing the sulfur-containing material and the carbon-based material in a weight ratio of 1: 0.5 to 1: 1.5. Examples of the material containing sulfur include, but are not limited to, Li ₂ S, S, or a combination thereof. The material containing such sulfur can be used by drying in a vacuum oven at 60 ° C to 100 ° C for at least 12 hours and for a maximum of 24 hours before mixing.

As the carbon-based material, any material used as a conductive material in a lithium secondary battery can be used. For example, a graphite-based material, a carbon-based material, or the like can be used. KS 6 (manufactured by Timcal Co.) may be used as the graphite based material, and Super P (manufactured by MMM), Ketjen black, denca black, acetylene black, carbon Black or the like can be used.

A second mixture of the polymer and the lithium salt is added to the first mixture. As the polymer, any of the above-mentioned binders can be used. As the lithium salt, any of the above-mentioned lithium salts can be used. The mixing ratio of the polymer and the lithium salt may be 40: 1 to 10: 1.

The mixing ratio of the first mixture and the second mixture may be 10 to 40 parts by weight based on 100 parts by weight of the first mixture. When the mixing ratio of the first mixture and the second mixture is within the above range, the adhesion between the active materials or between the active material and the current collector can be improved.

Then, the mixture is ball-milled for 1 to 12 hours, the obtained product is applied to a current collector, and hot-pressed to produce an electrode. The hot-pressing process can be carried out at a temperature of 80 to 120 DEG C at a pressure of 2 to 5 tons for 30 minutes to 2 hours.

2) When solvent is used

First, a cathode active material, a binder, and a conductive material are added to a solvent to prepare a slurry-type cathode active material composition. At this time, as the solvent, a cathode active material, a binder, a conductive material and an additive can be uniformly dispersed and easily evaporated. Typical examples thereof include N-methylpyrrolidone, acetonitrile, methanol, ethanol, Butanol, tetrahydrofuran, water, isopropyl alcohol, dimethylpyrrolidone and the like can be used.

The prepared composition is applied to a current collector and dried to form a positive electrode.

The negative electrode includes a negative electrode active material. Examples of such an anode active material include a material capable of reversibly intercalating / deintercalating lithium ions, a material capable of reversibly reacting with lithium ions to form a lithium-containing compound, a lithium metal and a lithium alloy May be used. Of these, lithium metal can be suitably used.

As the material capable of reversibly intercalating / deintercalating lithium ions, a carbon-based active material can be used, and any carbon-based negative electrode active material commonly used in lithium ion secondary batteries can be used. May be crystalline carbon, amorphous carbon or a combination thereof. Typical examples of the material capable of reacting with the lithium ion to form a lithium-containing compound reversibly include tin oxide (SnO ₂ ), titanium nitrate, silicon (Si), and the like, but are not limited thereto. As the lithium alloy, an alloy of lithium and a metal selected from the group consisting of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Al and Sn can be used.

Hereinafter, examples and comparative examples of the present invention will be described. The following embodiments are only examples of the present invention, and the present invention is not limited to the following embodiments.

(Example 1)

(Planetary Fritsch Pulverisett 7) at a ratio of 1: 1 by weight of pure crystalline sulfur (S, Aldrich) and carbon black (Super P, MMM Ltd. Belgium) And milling in air with low energy ball milling (LEBM) for 3 hours to prepare a sulfur-carbon composite cathode active material.

The prepared positive electrode active material was mixed with carbon black (Super P, MMM Company, Belgium) and polyvinylidene fluoride binder (6020, Solvay) in an N-methylpyrrolidone solvent in an 80:10:10 weight ratio to obtain a positive electrode active material Slurry. The cathode active material slurry was coated on an aluminum foil by a doctor blade method and dried to prepare a cathode film.

Polyethylene oxide (weight average molecular weight: 6 x 10 ⁵ ), LiCF ₃ SO ₃ , Li ₂ S and ZrO ₂ (Aldrich, average size 20 nm) were dried, classified and placed in sealed polyethylene bottles in the correct proportions. The mixing ratio of polyethylene oxide, LiCF ₃ SO ₃ , Li ₂ S and ZrO ₂ was 20: 1: 1: 10, ZrO ₂ was the total weight of polyethylene oxide, LiCF ₃ SO ₃ , Li ₂ S and ZrO ₂ To 10% by weight. The bottle was thoroughly mixed with a soft glass ball mill for 24 hours to obtain a uniform powder mixture. All processes were carried out in a controlled, argon atmosphere dry box to prevent air contamination.

The powder mixture was first pressed for 15 minutes at a pressure of 0.5 ton at 90 ° C and then subjected to secondary press molding at 90 ° C and a pressure of 4 tons for 60 minutes to prepare a 150 μm thick uniform and rigid polymer electrolyte.

The positive electrode film, the polymer electrolyte and the lithium metal were laminated in order, and then the laminate was placed between two stainless steel plates, which are current collectors, in a Teflon container to prepare a lithium sulfur battery. This process was carried out in a dry box where all of the regulated, argon filled, moisture and oxygen contents were all less than 10 ppm.

(Example 2)

(Planetary Fritsch Pulveriset 7) was added in a weight ratio of 1: 1, pure crystalline lithium sulfide (Li ₂ S, Aldrich) and carbon black (Super P, 7) was milled in air with low energy ball milling (LEBM) for 3 hours to prepare a sulfur-carbon composite cathode active material.

To the sulfur-carbon composite, a mixture of polyethylene oxide (weight average molecular weight: 6 × 10 ⁵ ) and LiCF ₃ SO ₃ in a molar ratio of 20: 1 was added. At this time, the mixture was adjusted to 30 parts by weight based on 100 parts by weight of the sulfur-containing carbon composite material.

The mixture was ball milled for 12 hours. The product obtained by ball milling was spread evenly on an aluminum foil current collector and hot-pressed at a temperature of 90 DEG C and a pressure of 4 tons for 1 hour to prepare a positive electrode.

The positive electrode, the polymer electrolyte prepared in Example 1, and the lithium metal were laminated in order, and then the laminate was placed between two stainless steel plates as a current collector to produce a lithium sulfur battery . This process was carried out in a dry box where all of the regulated, argon filled, moisture and oxygen contents were all less than 10 ppm.

(Comparative Example 1)

1.0 M LiPF ₆ was dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate (1: 1 by volume) to prepare an electrolyte.

The electrolyte, the positive electrode prepared in Example 1 and the lithium metal were laminated in order, and then the laminate was placed between two stainless steel plates, which are current collectors, in a Teflon container to produce a lithium sulfur battery . This process was carried out in a dry box where all of the regulated, argon filled, moisture and oxygen contents were all less than 10 ppm.

* Ionic conductivity measurement

The electrolyte prepared in Example 1 was made to have a diameter of 8 mm in a Teflon O-ring, and the electrolyte was placed between stainless steel blocking electrodes to prepare a battery. The battery was heated to about 120 ° C and maintained at that temperature for 24 hours to reach thermal equilibrium. Then, the ion conductivity was measured by AC impedance spectroscopy using VersaStat Ametek equipment using this battery. The measurements were carried out in the temperature range of 120-40 < 0 > C for cooling and heating scans.

The measured results are shown in Fig. As shown in FIG. 1A, since lithium ion transfer occurs mainly in an amorphous region of a polyethylene oxide polymer electrolyte which is a polymer stable at a high temperature exceeding 70 ° C, the conductivity is lowered in a low temperature range.

It can also be clearly seen from the results shown in Figs. 1B and 1C that the impedance of the battery was measured at a temperature of 60 DEG C or more and less than 60 DEG C, and the results are shown. This impedance measurement was carried out in the frequency range of 50 kHz to 100 Hz at 60 ° C or higher and in the frequency range of 50 kHz to 1 Hz at temperatures lower than 60 ° C. The impedance results measured at temperatures above 60 ° C of the cell exhibited a linear shape over the entire measured frequency range, which is a fast, uniform, liquid-like conductance-like behavior. At temperatures below 60 ° C, the polyethylene oxide chains begin to crystallize and thus exhibit a broader low frequency semi-circular shape as temperature decreases, which represents inter particle grain boundary resistance. This result is not different from the results shown in FIG. 1A in an actual manner, and shows that an irreversible thermal effect occurs.

From the results shown in Figs. 1A to 1C, it can be seen that the solid polymer electrolyte according to Example 1 has a conductivity of 10 -4 to 10 ^-3 Scm ^-1 at a temperature of about 70 ° C or higher.

* Galvanostatic charge-discharge characteristics measurement

The lithium sulfur battery produced according to Example 1 was subjected to Galvano static charge / discharge at a temperature of 70 ° C and 90 ° C in a voltage range of 1.5 to 3.0 V with C / 20 (1C = 836 mA / g) The characteristics are shown in Fig. The results shown in Fig. 2 show the charging / discharging characteristics of a typical lithium sulfur battery, and at 70 deg. C, the cost was comparatively low, while at 90 deg. C, a capacity close to the theoretical value was obtained. This result means that the charge / discharge Coulomb efficiency reaches almost 100%, which means that the dissociation of lithium sulfide is well controlled.

The fact that the charge / discharge efficiency reaches almost 100% means that the electrode stability can be effectively controlled without loss of the active material, which means that the charge / discharge cost is high as shown in FIG. 2, and the produced electrolyte is lithium Indicating that the ionic conductivity is suitable for driving the sulfur cell. From these results, it can be seen that lithium polysulfide (Li ₂ S _n , 1? N) produced during charging and discharging of the sulfur battery by Li ₂ S contained in the polymer electrolyte suppresses dissociation into the electrolyte, %, And the lifetime characteristics could be improved as well.

Evaluation of charge / discharge characteristics of the battery manufactured according to the example

The battery prepared in Example 2 was thoroughly charged at 70 ° C at 1/20 C and then charged and discharged again at 70 ° C in a voltage range of 1.5 to 3.2 V while varying the amount of current Respectively. Among these results, the charge / discharge characteristics results are shown in Fig. 3A, and the non-capacity change according to the cycle is shown in Fig. 3B. In Fig. 3A, the capacitance value shown on the x-axis takes into consideration the mass of only Li ₂ S used, and the capacitance value on the lower side takes into account the mass of Li ₂ SC. Further, in Figure 3b, the capacitance value of the left side, will only consider a mass of Li ₂ S used, the capacitance shown in the right side is a value taking into account the mass of Li ₂ SC. Also, in FIG. 3A, 120 mA / g, 75 mA / g, 60 mA / g, 40 mA / g and 30 mA /

In Fig. 3A, a specific capacity of about 290 mAh / g accounts for the Li ₂ SC cathode active material mass, and if the mass of Li ₂ S alone is taken into account, the specific capacity can be increased to 580 mAh / g. These high energy densities are very high as compared with general lithium ion batteries. From this result, it can be seen that the lithium sulfur battery of Example 1 can be usefully used.

As shown in FIG. 3 (b), the stability is maintained even if the cycle is repeated, and the capacity decrease rate increases as the cycle increases. However, when the charge / discharge returns to the initial capacity, the capacity is also converted to the original value.

* Evaluation of charge / discharge characteristics of batteries manufactured according to Comparative Example

The battery manufactured according to Comparative Example 1 was charged and discharged 8 times at 0.3 to 4.6 V at 0.05 C, and its charge-discharge characteristics are shown in FIG. As shown in FIG. 4, when the Li ₂ S positive electrode active material is used together with a general electrolyte of a lithium secondary battery, the charge / discharge characteristics are greatly deteriorated.

* SEM pictures

The battery prepared in Example 2 was fully charged with 1 / 20C. When the complete charging is performed in this manner, the cathode active material in the sulfur-carbon state is converted to the Li ₂ S-carbon state. Thus, after complete charging, the battery was disassembled to separate the positive electrode active material from the positive electrode, and the SEM photograph of the separated positive electrode active material was measured. The results are shown in FIG.

5, it can be expected that some Li2S particles remain separated from the active material layer because they remain uncoated, and thus the total capacity is somewhat reduced. However, as can be seen from the foregoing results, the lithium sulfur battery according to Example 1 of the present invention had a high capacity at 70 DEG C, which is a property that can not be obtained using a general polyethylene oxide electrolyte. Therefore, the sulfur- It is thought that battery performance was maintained over a wide temperature range by using an electrolyte having a high ion conductivity.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (9)

A cathode comprising a cathode active material;
A negative electrode comprising a negative electrode active material; And
Lithium salt, a polymer, a lithium sulfur battery comprising a solid electrolyte containing a filler, and Li ₂ S nano-sized. The method according to claim 1,
In the solid electrolyte, the Li ₂ S content is 1 to 10 moles per 100 moles of the polymer. The method according to claim 1,
Wherein the solid electrolyte is produced by hot-pressing the lithium salt, the polymer, the filler, and the Li ₂ S. The method of claim 3,
The hot-press is first press-molded at a temperature of 80 to 90 占 폚 at a pressure of 0.2 to 1 ton for 15 to 20 minutes and then pressurized at 80 to 90 占 폚 at a pressure of 4 to 5 tons for 60 to 90 Wherein the lithium sulfur battery is carried out by a secondary pressing step for a minute. The method according to claim 1,
Wherein the solid electrolyte has the filler and the Li ₂ S dispersed in a composite of the polymer and the lithium salt. The method according to claim 1,
Wherein the polymer is selected from the group consisting of polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyvinylidene fluoride, and combinations thereof. The method according to claim 1,
The filler is _{ZrO 2, Al 2 O 3,} SiO 2, and a lithium sulfur battery is selected from the group consisting of. The method according to claim 1,
Wherein the filler has an average size of 10 nm to 20 nm. The method according to claim 1,
The lithium salt _{LiCF 3 SO 3, LiPF 6,} LiClO 4, LiBF 4, LiB (C 2 O 4), LiN (SO 2 F) 2, LiN (SO 2 CF 3) 2, LiN (SO 2 C 2 F ₃ ) ₂ , LiCF ₆ SO _3, and combinations thereof.

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