[1]This application claims the benefit of priority based on the February 3 Korea Patent Application No. 10-2016-0013248 and No. 117 dated Korea Patent Application No. 10-2017-0008309 March 2017 and 2016, of the Korea Patent Application It includes all contents disclosed in the literature as part of the specification.
[2]
The present invention is a lithium-sulfur battery relates to a lithium-containing electrolyte, and this sulfur battery.
BACKGROUND
[3]
Recently, the need for high capacity batteries is emerging as portable electronic devices, electric vehicles, and large-capacity power storage system and the like are developed. Lithium-sulfur batteries is a SS bond (Sulfur-sulfur bond) using a sulfur-based material having a positive electrode active material, and a secondary battery using lithium metal as an anode active material, and the main material of the positive electrode active material, the sulfur resource is very rich, toxicity no, it is advantageous to have a low weight per atom.
[4]
In addition, the lithium-sulfur battery of the theoretical discharge capacity was 1672mAh / g-sulfur, and the theoretical energy density as 2,600Wh / kg, theoretical energy density of the other battery systems that are currently studies (Ni-MH cells: 450Wh / kg, Li- FeS cell: 480Wh / kg, Li-MnO 2 has been noted as a battery having a very high because of high energy density properties as compared to 800Wh / kg): cell: 1,000Wh / kg, Na-S cells.
[5]
However, the lithium-sulfur battery has not yet been commercialized due to a point that does not have sufficient capacity is as much as the theoretical capacity of sulfur utilization decreases, the battery short-circuit due to dendrite formation problem of the lithium metal electrode or the like. Thus, development and the like of the electrolytic solution which can increase the positive-electrode material, a sulfur utilization increased the sulfur impregnation amount is made to overcome the above problems.
[6]
Current lithium-sulfur batteries with liquid electrolyte solvents are the most widely used a mixed solvent of 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME). The electrolyte used and the solvent exhibits excellent characteristics in terms of sulfur utilization. However, the swelling phenomenon was observed rising battery is swollen by the gas generated inside the battery during operation of the experimental results of applying the electrolyte solution of the present inventors. This swelling phenomenon is accompanied by the problem of depletion of the electrolyte solution and also cause deformation of the battery as well, causing the desorption of active material from the electrode and lowering the battery performance.
[7]
It was swelling caused by gas generation inside the battery as described above has not disclosed yet the generation mechanism and its cause, and therefore countermeasures are also circumstances nonexistent.
[8]
[9]
[Prior art document]
[10]
U.S. Patent No. 6,218,054 No., Dioxolane and dimethoxyethane electrolyte solvent system
Detailed Description of the Invention
SUMMARY
[11]
The present inventors have found that lithium in order to solve the above problem - were studied in the electrolyte solvent, the composition of the sulfur battery, and completed the present invention as a result.
[12]
Accordingly, it is an object of this invention to significantly reduce the generation amount of the lithium battery-powered - to provide a sulfur battery electrolyte.
[13]
Further, another object of the invention is a lithium containing the electrolyte solution - to provide a sulfur battery.
Problem solving means
[14]
To achieve the above object, the present invention is
[15]
In the sulfur battery electrolyte, lithium-containing lithium salt and a non-aqueous solvent
[16]
The non-aqueous solvents
[17]
Cyclic ethers containing one of oxygen in the molecular structure; And
[18]
Provides a sulfur battery electrolyte - to lithium, it characterized in that it comprises a linear ether of the formula 1:
[19]
Formula 1
[20]
R-O-(CH2CH2O)x-CH2CH3
[21]
(As defined in Formula 1, R and x are as described in the specification.)
[22]
In this case, the cyclic ether solvent is a C1 to alkyl or alkoxy of C4 can be a substituted or unsubstituted 5- to 7-membered cyclic ether, and, preferably a substituted or unsubstituted alkyl or alkoxy group of C1 to C4 in the ring-tetrahydronaphthalene It may be a furan or tetrahydropyran.
[23]
In this case, in Formula 1 R may be a methyl, ethyl, propyl, isopropyl, or butyl.
[24]
At this time, the volume ratio of the cyclic ether solvent and a linear ether solvent is 95 to 95: 5 may be one and may, preferably 30:70 to 70:30 by.
[25]
이때, 상기 리튬염은 LiCl, LiBr, LiI, LiClO4, LiBF4, LiB10Cl10, LiPF6, LiCF3SO3, LiCF3CO2, LiC4BO8, LiAsF6, LiSbF6, LiAlCl4, CH3SO3Li, CF3SO3Li, (CF3SO2)2NLi, (C2F5SO2)2NLi, (SO2F)2 NLi, (CF 3 SO 2 ) 3 CLi, can be selected from a full chloroborane lithium, lower aliphatic carboxylic acid lithium, lithium tetraphenyl borate, lithium already the group consisting of DE, and combinations thereof.
[26]
The electrolyte solution of the present invention may further comprise an additive having the NO bond in the molecule.
[27]
In this case, the additive is lithium nitrate, potassium nitrate, cesium nitrate, barium nitrate, ammonium nitrate, nitrite, lithium nitrite, potassium nitrite, cesium nitrite, ammonium, methyl nitrate, dialkyl imidazolium nitrates, guanidine nitrate, already imidazolium nitrate, pyridinium nitrate, ethyl nitrite, propyl nitrite, butyl nitrite, pentyl nitrite, octyl nitrite, nitromethane, nitropropane, nitro butane and nitrobenzene, dinitrobenzene, nitropyridine, dinitrophenyl pyridine, nitrotoluene, dinitrotoluene, it may be at least one selected from pyridine N- oxide, alkyl pyridine-N- oxide, and tetramethyl-piperidinyl group consisting of oxyl.
[28]
In this case, the additives may be included in an amount of 0.01 to 10% by weight based on 100% by weight of electrolyte.
[29]
The present invention is a lithium containing the electrolyte solution - provides sulfur battery.
Effects of the Invention
[30]
Li accordance with the present invention-sulfur battery electrolyte is a gas generation amount of the battery is significantly less driving is excellent in stability. Thus, it is possible to improve the swelling phenomenon of the battery.
Brief Description of the Drawings
[31]
Figure 1 is a graph of gas production in Experimental Example 1.
[32]
Figure 2 is a graph of battery life characteristics compared to Experiment 2.
Best Mode for Carrying Out the Invention
[33]
In the following, the invention and the accompanying drawings for an embodiment of the present invention to facilitate the self having ordinary skill in the art that belong to the reference embodiment will be described in detail. However, the present invention may be embodied in many different forms, not limited to the embodiments set forth herein.
[34]
[35]
A lithium-sulfur battery electrolyte
[36]
In the present invention, a lithium-to improve the swelling (swelling), caused by the hydrogen, such as gases generated during operation of the sulfur battery, an electrolyte solvent represented by the cyclic ether and the following formula (1) containing one of oxygen in the molecule structure, It provides a sulfur battery electrolyte lithium-containing linear ether.
[37]
Formula 1
[38]
R-O-(CH2CH2O)x-CH2CH3
[39]
(In the formula 1,
[40]
R is an aryl group of an alkyl group, or a C6 to C12 of C1 to C6,
[41]
x is 1 or 2)
[42]
Current lithium is the most widely used as an electrolyte solvent for sulfur batteries is a mixture of 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME). When using a solvent mixture of DOL and DME is improved utilization of sulfur show superior results in terms of cell capacity.
[43]
The electrolyte to be used for a mixed solvent is applied to the small cell when the battery capacity decreased inhibition, battery life, but a generally good performance in terms of cell efficiency, when applied to a large-area pouch-cell and large cell, hydrogen in of battery-powered cell, methane , the swelling (swelling) development to solve the battery unit is observed by a gas, such as ethene, a significant amount occurs.
[44]
The present invention has been made in view of solving the above problems, an electrolytic solution of the present invention exhibit an improved stability, including the cyclic ether and a linear ether solvent ratio of specific content, a lithium-when applied to sulfur battery during battery driving hydrogen such as the gas generation amount is significantly reduced. To, as shown in Test Example, the electrolytic solution of the present invention is a lithium-sulfur batteries have when applied to the battery after driving value of the generation amount inside the measurement cell than 100 μL to 300 μL or less preferred. At this time, and the more the value is small means that the low gas production, reduction of such a gas generation amount is a value that does not occur even when little battery swelling phenomenon solve the unit occurs not significantly affect the cell stability. In other words, had the conventional case using other electrolyte solution as compared to about 500 μL level of gas production (see Comparative Example 1) The gas generation significantly lower when using the electrolytic solution proposed in this invention, it is possible to increase the battery stability, and thus, it is possible to overcome the problem of degradation in battery performance and battery deformation due to the swelling phenomenon.
[45]
An alkyl group of C1 to C6, which is referred to herein contains a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or the isomers thereof, for example. Isomers referred to herein is that the combination of the same number of carbon atoms of the carbon being relationship includes both stereoisomers of differences in the geometric position of the other structural isomers, and coupling.
[46]
Also it can be a pattern of a C6 to C12 aryl groups mentioned in the specification, for example, substituted or non-substituted with an alkyl group of C1 to C6 unsubstituted phenyl group, or naphthyl.
[47]
Cyclic ethers containing one of oxygen in the molecular structure is a cyclic ether or more substituted or unsubstituted 5- to an alkyl group, preferably C1 to alkyl or alkoxy groups substituted or unsubstituted 5 to 7-membered ring ring of C4 and ether type, is more preferably a substituted or unsubstituted tetrahydrofuran or tetrahydropyran alkyl or alkoxy group of C1 to C4. As non-limiting examples, tetrahydrofuran, 2-methyl tetrahydrofuran, 3-methyl tetrahydrofuran, 2,3-dimethyl tetrahydrofuran, 2,4-dimethyl tetrahydrofuran, 2,5-dimethyl-tetrahydrofuran , 2-methoxy-tetrahydrofuran, 3-methoxy tetrahydrofuran, 2-ethoxy-tetrahydro-furan-3-ethoxymethyl tetrahydrofuran, tetrahydropyran, 2-methyl-tetrahydropyran, 3-methyl-tetrahydropyran there may be mentioned 4-methyl tetrahydropyran. The cyclic ether is a good ionic mobility, low viscosity, and high oxidation-reduction stability, because of the show high stability for long-term operation of the cell.
[48]
In addition, the linear ether is an ethylene glycol derivative, ethylene glycol or diethylene glycol as a basic skeleton and an ethyl group at a side end has a structure attached to the ether bond. Wherein R to preferably is methyl, ethyl, propyl, isopropyl, or butyl. Wherein the linear ether is by having at least one ethoxy group appears to contribute to the stability of the electrolytic solution battery driving.
[49]
The volume ratio of the cyclic ether and a linear ether is 95 to 95: 5 and, preferably from 30:70 to 70:30. When outside the aforementioned range, the suppression of the cell driving gas generating effect can not be mimihayeo achieve the desired effect, it is appropriately adjusted within the above range.
[50]
Electrolyte of the present invention comprises a lithium salt is added to the electrolyte to increase the ionic conductivity. The lithium salt may be used without no particular limitation in the present invention, as long as possible generally used in a lithium secondary battery limits. Specifically, the lithium salt is LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiC 4 BO 8 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2 ) 2 NLi, (C 2F 5 SO 2 ) 2 NLi, (SO 2 F) 2 NLi, (CF 3 SO 2 ) 3 CLi, chlorocarbonate borane lithium, lower aliphatic acid lithium, lithium tetraphenyl borate, lithium group have already been made to the DE, and combinations thereof and selected from one member can be, preferably to (CF 3 SO 2 ) 2 is NLi.
[51]
The concentration of the lithium salt may be determined in consideration of ion conductivity, preferably 0.1 to 4.0 M, or 0.5 to 2.0 M. If Li is the salt concentration is difficult to secure ion conductivity suitable for driving the rear surface is lower than the above range, the battery, when it is more than the above range may deteriorate mobility of lithium ions to increase the viscosity of the electrolyte and the cell by the decomposition reaction of the lithium salt itself increases because of this performance can be reduced appropriately adjusted within the above range.
[52]
Li of the present invention sulfur cell non-aqueous liquid electrolyte may further include an additive having a molecular bond within the NO. The additive is effective to form a stable film on the lithium electrode, and significantly improve the charging and discharging efficiency. These additives may be a nitric acid or nitrous acid compounds, nitro compounds. Lithium nitrate In one example, potassium nitrate, cesium nitrate, barium nitrate, ammonium nitrate, nitrite, lithium nitrite, potassium nitrite, cesium nitrite, ammonium, methyl nitrate, dialkyl imidazolium nitrates, guanidine nitrate, imidazolium nitrate , pyridinium nitrate, ethyl nitrite, propyl nitrite, butyl nitrite, pentyl nitrite, octyl nitrite, nitromethane, nitropropane, nitro butane and nitrobenzene, dinitrobenzene, nitropyridine, di-nitropyridine, nitro toluene, dinitrotoluene, pyridine N- oxide, alkyl pyridine-N- oxide, and at least one element selected from the group consisting of tetramethyl-l-oxyl piperidinyl may be used. In accordance with one embodiment of the present invention, lithium nitrate (LiNO 3 may be used).
[53]
The additives used in the entire electrolyte composition in a 100% by weight 0.01 to 10% by weight, preferably from 0.1 to 5% by weight. If the content is not possible to secure the above effect is less than the above range, on the other hand, because the possibility that rather resistance by the film when it exceeds the above range increases, the properly adjusted within this range.
[54]
Li accordance with the present invention as described above-sulfur battery electrolyte, and a mixed solvent of cyclic ether and a linear ether as a solvent to obtain an electrolyte stability, whereby the charging and the battery within the gas generated during discharge without lowering of the cell performance a can be reduced, improving the swelling phenomenon.
[55]
Method for producing the electrolyte according to the present invention is not particularly limited in the present invention can be prepared by conventional methods known in the art.
[56]
[57]
A lithium-sulfur battery
[58]
Li accordance with the present invention-sulfur battery comprises a separator and an electrolyte interposed between the positive electrode and the negative electrode and these, and lithium in accordance with the present invention as an electrolytic solution-sulfur cell uses a non-aqueous liquid electrolyte.
[59]
Li accordance with the present invention - sulfur battery may improve the quality degradation according to a modification of the battery performance and battery, such as a hydrogen gas generation amount is significantly reduced, the active material generated from the electrode during operation is eliminated.
[60]
The lithium-configuration of a positive electrode, a negative electrode and a separator of sulfur batteries is not particularly limited in the present invention, following the known bar in the art.
[61]
anode
[62]
A positive electrode according to the present invention includes a positive electrode active material formed on the positive electrode collector.
[63]
A total of the positive electrode collector may be either as long as they can be used in the technical field and to the current collector, it is preferable to use the aluminum foam, foamed nickel, or the like having an excellent conductivity in detail.
[64]
The positive electrode active material may include elemental sulfur (Elemental sulfur, S8), a sulfur-based compound, or a mixture thereof. The sulfur-based compound is particularly, Li 2 S n (n≥1), an organic sulfur compound or a carbon-sulfur polymer ((C 2 S x ) n : and the like x = 2.5 ~ 50, n≥2) . It may be applied in combination with a conductive material.
[65]
The challenge may be a porous material. Therefore, as long as the conductive material having a porosity and conductivity can be used without limitation, and for example may be a carbonaceous material having a porosity. Such a carbon-based material may be used carbon black, graphite, graphene, carbon, carbon fibers and the like. In addition, a metallic fiber, such as a metal mesh; Copper, silver, metallic powders of nickel, aluminum and the like; Or polyester may also be used organic conductive materials such as polyphenylene derivatives. The conductive materials may be used alone or in combination.
[66]
The cathode may include a binder in order to further bond for the positive electrode active material and the conductive material in combination with the house. The binder may include a thermoplastic resin or a thermosetting resin. For example, polyethylene, polyethylene oxide, polypropylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), styrene-butadiene rubber, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-chloro-trifluoro ethylene copolymer, an ethylene-ethylene-tetrafluoroethylene copolymer, poly-chlorotrifluoroethylene, fluorinated beanie fluoride-penta to print Luo propylene copolymer, propylene -tetrafluoroethylene copolymer, an ethylene-chlorotrifluoroethylene copolymer, vinylidene fluoride-hexa fluoro propylene-tetrafluoroethylene copolymer, vinylidene fluoride-vinyl ether perfluoro-tetrafluoroethylene air copolymers, ethylene-but it is used alone or a mixture of acrylic acid copolymer and the like, be they It is not limited as long as they can both be used as binders in the art.
[67]
Positive electrode as described above can be prepared according to a conventional method, specifically, the positive electrode active material and conductive material and a binder, the composition for forming a positive electrode active material layer was prepared by mixing in an organic solvent to the coating and drying, and, optionally, on the current collector in order to improve the electrode density may be prepared by compression-molding the current collector. At this time, the organic solvent may be uniformly dispersed in the positive electrode active material, binder and conductive material, it is preferable to use those that easily evaporates. Specifically, there may be mentioned acetonitrile, methanol, ethanol, tetrahydrofuran, water, isopropyl alcohol, and the like.
[68]
cathode
[69]
A negative electrode according to the present invention includes a negative electrode active material formed on the negative electrode collector.
[70]
The anode current collector may be one which is specifically copper, stainless steel, titanium, is selected from palladium, nickel, alloys thereof and combinations thereof. The stainless steel may be treated with carbon, nickel, titanium or silver surface, the alloy is aluminum-cadmium alloys. In addition, there may also be such as sintered carbon, a surface treated with a conductive material, a non-conductive polymer, or a conductive polymer is used.
[71]
The cathode active material is a lithium ion (Li + ) for reversibly storing (Intercalation) or discharge (Deintercalation) materials that can, by reacting with the lithium-ion substance capable of forming a lithium-containing compound by reversibly, lithium metal or a lithium alloy the can be used. The lithium ion (Li + material capable of reversibly storing or discharging a) may be, for example, crystalline carbon, amorphous carbon, or a mixture thereof. The lithium ion (Li + material capable of forming a reversible lithium-containing compound to react with a) may be, for example, tin oxide, titanium nitrate or a silicone. The lithium alloy is, for example, lithium (Li) and sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), Francium (Fr), beryllium (Be), magnesium (Mg), calcium ( Ca), may be a strontium (Sr), barium (Ba), radium (Ra), aluminum (alloy of a metal selected from the group consisting of Al), and tin (Sn).
[72]
The cathode may include a binder to better binding to the negative electrode active material and the conductive material in combination with the house, particularly the binder is the same as described above in the binder of the positive electrode.
[73]
In addition, the anode may be a lithium metal or a lithium alloy. Non-limiting examples, the negative electrode may be a thin film of lithium metal, lithium, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Al and at least one metal selected from Sn group It may be an alloy of.
[74]
Membrane
[75]
Between the anode and the cathode has the conventional separation membrane can be interposed. The separator is a physical separation membrane has a function of separating the electrodes physically, so long as it is used in a conventional membrane can be used without particular limitation, and is especially low in resistance, yet preferably excellent in electrolytic solution humidification ability against ion mobility of the electrolyte solution.
[76]
Further, the separator makes it possible to transport of lithium ions between the positive electrode and the negative electrode, while separated from each other or insulated to the positive electrode and the negative electrode. This membrane is porous and may be made of a non-conductive or insulative material. The membrane may be either an independent member such as a film, or the anode and / or cathode in addition to the coating layer.
[77]
Specifically, the sole of a porous polymer film, such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymers and ethylene / meta produced by the polyolefin-based polymers such as methacrylate copolymer porous polymer film or to use them to be stacked and, or conventional porous nonwoven, for example, and can be used, but the non-woven fabric of glass fiber, polyethylene terephthalate fiber, such as the melting point, and the like.
[78]
The lithium, wherein the positive electrode, a negative electrode and a separator included in the sulfur battery may be prepared according to the respective conventional ingredients and production process, and the lithium-appearance of sulfur batteries Although there is no particular limitation, cylindrical with cans, prismatic, pouch (Pouch) may be a type or coin (Coin) type.
[79]
[80]
Or less to present one, the preferred embodiment for better understanding of the invention examples are apparent according to intended as the scope and spirit the scope those skilled in the art will that various changes and modifications within the possible according to the present invention illustrating the invention, this it will be obvious that belong to the claims the modifications and the appended.
[81]
[82]
EXAMPLES
[83]
Examples 1-6 and Comparative Example 1
[84]
(1) Preparation of electrolytic solution
[85]
To the non-aqueous liquid electrolyte of Examples 1 to 6 and Comparative Example 1 in the proportion shown in Table 1 was prepared. The solvent used is as follows: (v / v is the volume ratio means).
[86]
THF: 테트라히드로퓨란 (Tetrahydrofuran)
[87]
THP: tetrahydropyran (Tetrahydropyran)
[88]
EGEME: glycol methyl ether (Ethyleneglycol ethyl methyl ether)
[89]
EGDEE: ethylene glycol diethyl ether (diethyl ether Ethyleneglycol)
[90]
DOL: 1,3- dioxolane (1,3-Dioxolane)
[91]
DME: dimethoxyethane, 1,2- (1,2-Dimethoxyethane)
[92]
TABLE 1
[93]
[94]
(2) a lithium-sulfur batteries manufactured in
[95]
By mixing with acetonitrile to 65% by weight of sulfur, 25 wt% carbon black, polyethylene oxide and 10% by weight to prepare a positive electrode active material. The positive electrode active material, the aluminum current collector coated on the whole and to dry it with the size 30 × 50 ㎟, loading amount mAh 5 / cm 2 to prepare a positive electrode of. In addition, the negative electrode was a lithium metal having a thickness of 150㎛.
[96]
A position so as to face the above-prepared positive and negative electrodes and a separator interposed between the polyethylene was then injected into each electrolyte solution of the above (1).
[97]
[98]
Experimental Example 1: lithium-sulfur batteries manufactured and charge and then discharge gas production analysis
[99]
The Examples and Comparative Examples of lithium-sulfur batteries to charge five times with 0.1C rate determining in 25 ℃ · were measured after discharging the battery within a gas production, are shown in the following Table 2. As a result, and FIG.
[100]
You can see that, as shown in Table 2, Examples 1 to 6 For the generation amount is 12.7 ~ 86.5 μL to, compared to the 473 μL of Comparative Example 1 significantly reduced.
[101]
TABLE 2
[102]
[103]
Experimental Example 2: Battery life characteristic evaluation
[104]
Example 1, 4 and 5 and Comparative Examples was to with respect to the battery of the first measurement condition of the battery while charge and discharge capacity maintenance rate, the results were also shown in the second.
[105]
Charging: rate determining 0.1C, voltage 2.8V, CC / CV (5% current cut at 0.1C)
[106]
Discharge: rate determining 0.1C, 1.5V voltage, CC
[107]
Embodiment as shown in FIG. 2, for example, 1, 4, and shows a significantly improved capacity retention rate compared to Comparative Example 1 In 5. It can be seen that to improve the life characteristics of the sulfur battery - from the experiment result, the electrolytic solution of the present invention, gas generation is significantly reduced and can prevent a battery swelling phenomenon and lithium.

Claims

[Claim 1]Li-containing lithium salt and a non-aqueous solvent in the sulfur battery electrolyte, wherein the nonaqueous solvent is a cyclic ether containing one of oxygen in the molecular structure; And to lithium, it characterized in that it comprises a linear ether of the formula 1 - sulfur battery electrolyte [Formula 1] RO- (CH 2 CH 2 O) x -CH 2 CH 3 (in the formula 1, R is C1 to an alkyl group, or C6 to C12 aryl group of C6, x is 1 or 2)
[Claim 2]
The method of claim 1 wherein said cyclic ether solvent is lithium, characterized in that the C1 to C4 alkyl group or alkoxy group substituted or unsubstituted 5- to 7-membered cyclic ether-sulfur battery electrolyte.
[Claim 3]
The method of claim 1 wherein said cyclic ether solvent is a substituted or unsubstituted C1 to C4 alkyl or alkoxy unsubstituted tetrahydrofuran or tetrahydropyran in that lithium which is characterized-sulfur battery electrolyte.
[Claim 4]
2. The method of claim 1, wherein R is Li, characterized in that methyl, ethyl, propyl, isopropyl, or butyl-sulfur battery electrolyte.
[Claim 5]
The method of claim 1, wherein the volume ratio of the cyclic ether solvent and a linear ether solvent is 95 to 95: Li, characterized in that 5-sulfur battery electrolyte.
[Claim 6]
The method, the cyclic ether solvent and the volume ratio of the linear ether solvent is 30:70 to 70:30 on lithium, characterized in that 1-sulfur battery electrolyte.
[Claim 7]
제 1 항 에 있어서, 상기 리튬 염 은 LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 . Cl 10 , LiPF 6 , LiCF 3 the SO 3 , LiCF 3 CO 2 , LiC 4 by BO 8 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH The 3 the SO 3 Li, the CF 3 the SO 3 Li, ( the CF 3 the SO 2 ) 2 NLi, ( the C 2 F 5 the SO 2 ) 2 NLi, ( the SO 2F) 2 NLi, (CF 3 SO 2 ) 3 CLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, lithium tetraphenyl borate, lithium already comprising the one selected from the group consisting of DE, and combinations thereof a lithium-sulfur battery electrolyte.
[Claim 8]
The method of claim 1, wherein the lithium salt is 0.1 to 4.0 lithium, characterized in that contained as M concentration-sulfur battery electrolyte.
[Claim 9]
According to claim 1, wherein said electrolyte is lithium, it characterized in that it further comprises an additive having the NO bond in the molecule-sulfur battery electrolyte.
[Claim 10]
The method of claim 9 wherein the additive is lithium nitrate, potassium nitrate, cesium nitrate, barium nitrate, ammonium nitrate, nitrite, lithium nitrite, potassium nitrite, cesium nitrite, ammonium, methyl nitrate, dialkyl imidazolium nitrates, guanidine knit rate, imidazolium nitrate, pyridinium nitrate, ethyl nitrite, propyl nitrite, butyl nitrite, pentyl nitrite, octyl nitrite, nitromethane, nitropropane, nitro butane and nitrobenzene, dinitrobenzene, a nitro sulfur electrolyte-pyridine, di-nitropyridine, nitrotoluene, dinitrotoluene, pyridine N- oxide, alkyl pyridine-N- oxide, and tetramethyl piperidinyl one kinds of lithium, characterized in that at least selected from the group consisting of oxyl.
[Claim 11]
Claim 9 wherein said additive is lithium, characterized in that contained in an amount of 0.01 to 10% by weight based on 100% by weight of electrolyte in-sulfur battery electrolyte.
[Claim 12]
anode; cathode; A separator interposed between the positive electrode and the negative electrode; And lithium-containing electrolyte-in, the electrolyte is lithium claim, characterized in that 1 to which any one of an electrolytic solution of claim 11 wherein the sulfur battery-sulfur battery.