[1]This application claims the benefit of priority based on the March 03 date of Korea Patent Application No. 10-2016-0025398 and No. 110 Date of Korea Patent Application No. 10-2017-0003342 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]
Further, a lithium-sulfur battery of the theoretical discharge capacity is 1672mAh / g-sulfur, the theoretical energy density as 2,600Wh / kg, the present study and other cell systems theoretical energy density (Ni-MH battery of which: 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]
The present inventors have found that lithium using conventional electrolytic solution were observed with the gas generated inside of the of the experiment was to produce a sulfur batteries with large capacity, the battery driving the battery swelling phenomenon climb the bulging appear. 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.
[6]
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.
[7]
[8]
[Prior art document]
[9]
Republic of Korea Patent Publication No. 10-2012-0090113 call for a lithium secondary battery electrolyte and a lithium secondary battery comprising the same
Detailed Description of the Invention
SUMMARY
[10]
The present inventors have found that lithium in order to solve the above problem - were studied in the electrolyte composition of the sulfur battery, and completed the present invention as a result.
[11]
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.
[12]
Further, another object of the invention is a lithium containing the electrolyte solution - to provide a sulfur battery.
Problem solving means
[13]
To achieve the above object, the present invention is
[14]
It provides a sulfur battery electrolyte-containing lithium salt and a non-aqueous solvent, lithium further comprising the radical adsorbent.
[15]
In this case, the adsorbent is a radical quinone compound, N- oxyl radical compounds, phenol compounds, amine compounds, yen olgye compounds, thiol-based compounds, azide compounds, cyclopropane derivatives, cyclobutane derivatives, and combinations thereof It may include one member selected from the group consisting of.
[16]
Here, the quinone compound is 1,2-benzoquinone, 1,4-benzoquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, 9,10-anthraquinone, 1,4-anthraquinone, , it may be at least one member selected from the group consisting of acetic naphthoquinone and derivatives thereof.
[17]
In this case, the N- oxyl radical compound is 2,2,6,6-tetramethyl-1-piperidinyl-oxyl, 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyl-oxyl , 4-oxo -2,2,6,6-tetramethyl-1-piperidinyl-oxyl, 4-amino-2,2,6,6-tetramethyl-1-piperidinyl-oxyl, 4-acetamido FIG 2,2,6,6-tetramethyl-1-piperidinyl-oxyl, 4-methoxy-2,2,6,6-tetramethyl-1-piperidinyl-oxyl, and 4-hydroxy-2 , 2,6,6- tetramethyl-1-piperidinyl oxyl - it may be at least one member selected from the group consisting of benzoate.
[18]
At this time, the amine-based compound may be a binary Shima, N1, N4- diphenyl benzene-1,4-diamine, and combinations thereof.
[19]
In this case, the radical adsorbent may be contained in an amount of 0.01 to 5% by weight relative to 100% by weight of electrolyte.
[20]
In this case, the non-aqueous solvent may be at least one member selected from the group consisting of carbonate-based, ester-based, ether-based, ketone-based, alcohol-based, and aprotic solvents.
[21]
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.
[22]
In this case, the lithium salt may be included as 0.2 to 2.0 M concentration.
[23]
The electrolytic solution of the present invention may further include additives having a molecular bond within the NO.
[24]
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.
[25]
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.
[26]
The present invention is a lithium containing the electrolyte solution - provides sulfur battery.
Effects of the Invention
[27]
Li accordance with the present invention-sulfur battery electrolyte is because the generation amount of the battery drivingly is excellent in stability, it is possible to improve the swelling phenomenon of the battery.
Brief Description of the Drawings
[28]
Figure 1 is a graph of gas production compared to Experiment 1.
[29]
Figure 2 is a graph of battery life characteristics compared to Experiment 2.
Best Mode for Carrying Out the Invention
[30]
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.
[31]
[32]
A lithium-sulfur battery electrolyte
[33]
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, comprising a lithium salt and a non-aqueous solvent, lithium further comprising the radical adsorbent - It provides a sulfur battery electrolyte.
[34]
Experimental results by the inventors, the non-aqueous solvent, and when applying the conventional electrolyte composed of lithium salt in large-area pouch-cell and large cell, and a gas such as hydrogen, methane, ethene significant amount generated in one cell driving battery cell is negative the swelling (swelling) development solving have been observed. The phenomenon occurs and causes, but been reported so far, it is judged to be due to the electrolytic solution instability. In particular, sulfur radicals are generated during battery driving is regarded as the electrolyte decomposition and gas generation due to this cause.
[35]
An electrolyte according to the present invention includes a radical adsorbent further so as to reduce the side reaction by radicals. Electrolytic solution of the present invention is a lithium-represents an improved stability without sacrificing the life, efficiency, such as the battery characteristics of the battery when applied to sulfur battery, whereby the battery driving the electrolyte decomposition and gas generation of the problem is improved desorption active material from the electrolyte loss, the electrode according to the battery performance and cell transformation by it can overcome the degradation problems.
[36]
Radical adsorbent of the present invention is a lithium-If material with a radical substance occurring incidentally during operation of the sulfur battery can act as the first reaction prior to the reaction with the electrolytic solution to prevent the decomposition of the electrolytic solution is not specifically restricted, feed of the electronic easy conjugated compound, a stable radical compound, include compounds such as having an unsaturated bond.
[37]
The radical adsorbent may be a quinone compound. Quinone compounds can be an electron acceptor role have a conjugated structure, specifically, the quinone compound is 1,2-benzoquinone, 1,4-benzoquinone, 1,2-naphthoquinone, 1,4 - it may be at least one member selected from the group consisting of naphthoquinone, 9,10-anthraquinone, 1,4-anthraquinone, acetoxy naphthoquinone and derivatives thereof.
[38]
Further, the adsorbent may be a radical N- oxyl radical compound. N- oxyl radical compound having a stable radical structures, can be used as an oxidation catalyst. Specifically, the N- oxyl radical compound is 2,2,6,6-tetramethyl-1-piperidinyl-oxyl (2,2,6,6-tetramethyl-1-piperidinyloxyl), 4- hydroxy-2, 2,6,6- tetramethyl-1-piperidinyl-oxyl (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxyl), 4- oxo -2,2,6,6-tetramethyl 1-piperidinyl-oxyl (4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy), 4- amino-2,2,6,6-tetramethyl-1-piperidinyl-oxyl (4 -amino-2,2,6,6-tetramethyl-1-piperidinyloxy), 4- acetamido-2,2,6,6-tetramethyl-1-piperidinyl-oxyl (4-acetamido-2,2, 6,6-tetramethyl-1-piperidinyloxy), 4- methoxy-2,2,6,6-tetramethyl-1-piperidinyl-oxyl (4-methoxy-2,2,6,6-tetramethyl-1- a benzoate (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxyl benzoate) - piperidinyloxy), and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyl-oxyl It may be at least one member selected from the group consisting of.
[39]
Other non-limiting examples of such radicals as 2,6-adsorbent-tert-butyl-4-methylphenol (2,6-di-tert-butyl-4-methylphenol, BHT), thiodiethylene-bis [2- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (thiodiethylene bis [2- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]), octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), tetrakis [methylene-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane) phenol compounds, Shima binary (simazine, 6-Chloro-N, N'-diethyl-1,3,5-triazine-2,4-diamine), N1, N4- diphenyl benzene-1,4-diamine (N1, N4-diphenylbenzene-1,4-diamine) such as amine-based compounds, yen olgye compounds, thiol-based compounds, azide compounds, and the like cyclopropane derivatives, cyclobutane derivative, these radicals adsorption It may be used alone or in combination.
[40]
The amount of the radical adsorbent is preferably from 0.01 to 5% by weight relative to 100% by weight of electrolyte. If the amount of the adsorbent is less than the above range radicals insignificant electrolyte decomposition and the gas generation preventing effect when battery powered, and if it exceeds the above range, it may cause undesired side reaction is suitably adjusted within the above range. Further, it is when the content of the radical-adsorbent from 0.5 to 2% by weight, so improving the life characteristics of the battery with a protection gas-generating effect effect can be obtained, the amount of the radical adsorbent is more preferably 0.5 to 2% by weight.
[41]
The solvent of the electrolytic solution according to the invention, if the non-aqueous solvent to the medium serves to move to the ions involved in the electrochemical reaction of the battery is not particularly limited, specifically, a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based or non-positive can be used a magnetic solvents.
[42]
In the carbonate-based solvent include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), ethylene carbonate ( such as EC), propylene carbonate (PC), or butylene carbonate (BC) can be used, but is not limited thereto.
[43]
As the ester-based solvents include methyl acetate, ethyl acetate, n- propyl acetate, 1,1-dimethyl-ethyl acetate, methyl propionate, ethyl propionate, γ- lactone butynyl, big surprise Id (decanolide), ballet lactone, methoxy feet no lactone (mevalonolactone), caprolactone (caprolactone), etc. can be used, but is not limited thereto.
[44]
In the ether solvent is diethyl ether, dipropyl ether, dibutyl ether, dimethoxymethane (DMM), trimethoxy-methane (TMM), dimethoxyethane (DME), diethoxyethane (DEE), diglyme, triglyme, tetra-glyme, tetrahydrofuran, 2-methyl tetrahydrofuran, or glycol dimethyl ether and the like can be used, but is not limited thereto.
[45]
In the ketone-based solvent it can be used, for example, such as cyclohexanone. In addition, amides, 1,3-dioxolane (DOL), such as the alcohol-based solvent include ethyl alcohol, isopropyl this may be used, wherein the aprotic solvent is an alcohol, such as nitriles, such as acetonitrile, dimethylformamide there is a flow-dioxolane, or sulfolane (sulfolane), etc. or the like can be used.
[46]
The non-aqueous organic solvent may be used alone or by mixing more than one, the mixing ratio of which is used by mixing one or more it may be appropriately adjusted according to the desired battery performance. Lithium-sulfur battery, considering the characteristics of the non-aqueous solvent is preferably used in an ether-based solvent described above. In one example, 1, 3-dioxolane (DOL) for 1,2-dimethoxyethane and the volume ratio of (DME) 50: mixed solvent, or tetra 50 as tetrahydrofuran (THF) for 1, 2-dimethoxyethane ( the volume ratio of the DME) 50: can be used in a mixed solvent of 50.
[47]
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.
[48]
The concentration of the lithium salt may be determined in consideration of ion conductivity, preferably from 0.2 to 2.0 M, or 0.5 to 1.6 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.
[49]
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).
[50]
The additives used in the entire electrolyte composition ranges from 0.01 to 10% by weight based on 100% 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.
[51]
Li accordance with the present invention as described above-sulfur battery electrolyte is added a radical absorbent to obtain an electrolyte stability of the battery-driven, during charging and discharging of the battery inhibit cell within the gas generation, and to improve the swelling phenomenon have.
[52]
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.
[53]
[54]
A lithium-sulfur battery
[55]
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.
[56]
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.
[57]
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.
[58]
anode
[59]
A positive electrode according to the present invention includes a positive electrode active material formed on the positive electrode collector.
[60]
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.
[61]
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) . These sulfur material alone is the conductive material and the composite is applied because there is no electrical conductivity.
[62]
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.
[63]
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.
[64]
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.
[65]
cathode
[66]
A negative electrode according to the present invention includes a negative electrode active material formed on the negative electrode collector.
[67]
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.
[68]
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).
[69]
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.
[70]
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 and one member selected from Li and Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, the group consisting of Ra, Al and Sn It may be an alloy of the above metals.
[71]
Membrane
[72]
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.
[73]
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.
[74]
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.
[75]
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.
[76]
[77]
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.
[78]
[79]
EXAMPLES
[80]
Examples 1-5 and Comparative Example 1
[81]
(1) Preparation of electrolytic solution
[82]
1,3-dioxolan the volume ratio of (DOL) and 1,2-dimethoxyethane (DME) 50: LiTFSI in a mixture of 50 ((CF 3 SO 2 ) 2 NLi) 1.0 M, and LiNO 3 1 wt. % was added to prepare a non-aqueous liquid electrolyte of Comparative example 1.
[83]
Example 1-5 A non-aqueous electrolyte solution of the electrolyte solution further comprises a radical absorbent composition of Comparative Example 1 was prepared. To the electrolyte composition it is shown in Examples 1 to 5 and Comparative Example 1 are shown in Table 1.
[84]
TABLE 1
[85]
(2) a lithium-sulfur batteries manufactured in
[86]
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㎛.
[87]
A position so as to face the above-prepared positive and negative electrodes and a separator interposed between the polyethylene was then filled with the electrolyte of one embodiment of Preparation Example 1 or Comparative Example 1.
[88]
[89]
Experimental Example 1: lithium- sulfur battery manufacturer and charge and then discharge gas production analysis
[90]
Examples and Comparative Examples each Li is manufactured by - a fifth charge and discharge the battery after the gas generation amount in the 0.1C rate controlling sulfur battery at 25 ℃ was measured, given in the results in Table 2 and Fig.
[91]
To it it can be seen that represents the Examples 1 to 5 has a reduced gas production, which does not contain a radical absorbent as compared to a gas generation amount of 473 μL, containing the radical adsorbent as shown in Table 2. That is, it was a case of adding a 1,4-benzoquinone of 67 ~ 73%, when the addition of TEMPO The addition of about 33%, Shima binary gas production of about 25% inhibitory effect.
[92]
TABLE 2
[93]
Experimental Example 2: Battery life characteristic evaluation
[94]
While the above Examples and was charged and discharged in the following conditions with respect to the prepared battery in Comparative Example measured a capacity retention rate of the cell, it was also shown in 2 the results.
[95]
Charging: rate determining 0.1C, voltage 2.8V, CC / CV (5% current cut at 0.1C)
[96]
Discharge: rate determining 0.1C, 1.5V voltage, CC
[97]
Also it can be confirmed that 2, all of Examples 1 to 5 further comprising a radical adsorbent cells showing a similar capacity retention rate as in Comparative Example 1. In particular, in the case of Examples 1, 4 and 5 with a radical adsorbent it comprises 1% by weight, exhibited improved life characteristics than. From this, the electrolyte of the present invention is reduced to a standing gas production without affecting the cell performance, it can be seen that can prevent a battery swelling phenomenon and improve reliability.

Claims

[Claim 1]Sulfur electrolyte lithium salt and a non-aqueous solvent, include, lithium, characterized in that it further comprises a radical adsorbent.
[Claim 2]
The method of claim 1 wherein the adsorbent is a radical quinone compound, N- oxyl radical compounds, phenol compounds, amine compounds, yen olgye compounds, thiol-based compounds, azide compounds, cyclopropane derivatives, cyclobutane derivatives, and in that it comprises one member selected from the group consisting of lithium, characterized-sulfur battery electrolyte.
[Claim 3]
3. The method of claim 2, wherein quinone compound is 1,2-benzoquinone, 1,4-benzoquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, 9,10-anthraquinone, 1, 4-anthraquinone, naphthoquinone and acetoxy from the group consisting of a lithium derivative, characterized in that at least one member selected-sulfur battery electrolyte.
[Claim 4]
The method of claim 2, wherein the N- oxyl radical compound is 2,2,6,6-tetramethyl-1-piperidinyl-oxyl, 4-hydroxy-2,2,6,6-tetramethyl-1 piperidinyl-oxyl, 4-oxo -2,2,6,6-tetramethyl-1-piperidinyl-oxyl, 4-amino-2,2,6,6-tetramethyl-1-piperidinyl-oxyl, 4-acetamido-2,2,6,6-tetramethyl-1-piperidinyl-oxyl, 4-methoxy-2,2,6,6-tetramethyl-1-piperidinyl-oxyl, and 4- hydroxy-2,2,6,6-tetramethyl-1-piperidinyl-oxyl-sulfur battery electrolyte - lithium benzoate, characterized in that at least one member selected from the group consisting of.
[Claim 5]
The method of claim 2, wherein the amine compound is binary Shima, N1, N4- diphenyl benzene-1,4-diamine, and Li, characterized in that a combination of - sulfur battery electrolyte.
[Claim 6]
According to claim 1, wherein said adsorbent is a lithium radical, characterized in that contained in an amount of 0.01 to 5% by weight relative to 100% by weight of the electrolyte-sulfur battery electrolyte.
[Claim 7]
The method of claim 1, wherein the non-aqueous solvent is a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based and non-positive lithium, characterized in that at least one member selected from the group consisting of magnetic solvent-sulfur battery electrolyte.
[Claim 8]
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 9]
The method of claim 1, wherein the lithium characterized in that the lithium salt is contained in 0.2 to 2.0 M concentration-sulfur battery electrolyte.
[Claim 10]
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 11]
The method of claim 10 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 12]
Claim 10 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 13]
anode; cathode; A separator interposed between the positive electrode and the negative electrode; And lithium-containing electrolyte-sulfur battery according to the electrolytic solution is lithium claim, characterized in that any one of items 1 to 12, wherein the electrolyte-sulfur battery.