TWI304803B - Additives for non-aqueous electrolytes and electrochemical device using the same - Google Patents

Description

[Technical Field] The present invention relates to an electrolyte for use in a battery, which comprises an additive for a water-insoluble electrolyte, which can improve cycle characteristics and high temperature characteristics of the battery. Meanwhile, the present invention relates to an electrode having improved heat safety and an electrochemical device, preferably a non-aqueous electrolyte secondary battery including the additive.

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[Prior Art] In recent years, there has been a boom in energy storage technology. The use of batteries has been expanded to include mobile phones, camcorders, notebook computers, personal computers: and t + _ media storage energy. So research on batteries IX:: The exhibition has gradually become more concrete. In the observation, the field of electrochemical devices has been favored by the large Zhuang En, which has received more attention as the development of rechargeable/discharge secondary batteries. Recently, the development of such batteries has been actively studied in the design: a new type of electrode for improving the capacitance density and specific energy, and the primary battery used in the electric battery. The piece 'because of the high driving voltage and the energy density is much larger than the advantages of the battery, such as Ni-MH, Ni_Cd and sulfuric acid/wrong battery, makes it the focus of attention. However, such lithium secondary batteries have a problem of degraded quality during repeated repetition of the ::: ring. The above problem becomes more serious when the temperature of the battery and the temperature of the battery rises. Therefore, the high temperature life characteristics of a non-aqueous/composite electrolyte lithium secondary battery 20 1304803 method has become an uninterrupted demand. Korean Laid-Open Patent No. 0450199 and U.S. Patent No. 2002-0197537' disclose the use of a compound acid salt compound represented by the following formula 2 as an electrolyte additive, thereby providing an improvement in battery characteristics and south temperature characteristics. a way. [Molecular Formula 2]

4 o=s: %, where Ri and R2 each represent π must be 万 万 丞 丞 曰 曰 早期 早期 早期 早期 早期 早期 早期 早期 早期 早期 早期 早期 早期 早期 早期 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 Semi-sexuality and storage characteristics. [Molecular Formula 3] Q %

Q wherein R represents a burning group. 15 As described above, it is well known that when a sulfonate (S03) compound is used as an additive for an electrolyte, the quality of the battery can be improved. SUMMARY OF THE INVENTION In order to improve the quality of a battery, the inventors of the present invention have conducted many studies using a continuous acid salt 20 = 〇3). Finally, the inventors of the present invention have found that sulfonate compounds substituted with a specific substituent are used in the field (Example 1304803 - eg, at least one substituent is selected from the group consisting of a cyano group, an isocyanate group, a thiocyanate group a base and an isothiocyanate group, a monosulfonate compound as an additive for an electrolyte, which is capable of significantly improving a lithium battery as compared with a conventional sulfonate compound having no such substituent. The life characteristics of the pool and the stability of the high temperature 5 . Accordingly, it is a primary object of the present invention to provide an electrolyte for use in a battery comprising a monosulfonate compound having at least one of the above-mentioned substituents, an electrode comprising the above compound on the electrode active material, An electrochemical device comprising the electrolyte and/or electrode. 1 . According to one aspect of the invention, there is provided an electrolyte for use in a battery, comprising: (a) an electrolyte salt; (b) an electrolyte solvent; and (c) a sulfonate compound, It comprises at least one pull electron selected from the group consisting of monocyano bN), monoisocyanato (-NCO), monothiocyanate (_SCN), and isothiocyanate (-NCS). Base (EWG). At the same time, an electrochemical device, preferably a lithium secondary battery including the electrolyte, is provided. According to another aspect of the present invention, there is provided an electrode comprising a monosulfonate compound or a chemical reaction product thereof, partially or wholly formed on a surface thereof, wherein the sulfonate compound comprises At least one electron withdrawing group (EWG) of a group consisting of free-cyano (_CN), mono-isocyanate (-NCO), monothiocyanate (_SCN), and isothiocyanate (_Ncs) 20 ). Also provided is an electrochemical device, preferably a lithium secondary battery comprising the electrode. Hereinafter, the present invention will be described in detail. The present invention is based on the inclusion of a monosulfonate compound, one of which is substituted with a special substituent, for example, at least one substituent is selected from the group consisting of a cyano group, a 1304803 to provide an electrolysis difference, an acid group, a sulfur bud. Brewed,,,,,,,,,,,,,,,,,,,,,,,,,, Due to the above characteristics, when compared with a battery, the electrolyte used does not have the above-mentioned substituent - the conventional non-substituted sodium salt compound, according to the clock secondary battery of the invention, a good life can be achieved. Characteristics and south temperature characteristics. From this, it can be considered that a sulfonate compound substituted with at least one electron-withdrawing group (ewg) in comparison with other similar beryllate compounds can provide a relatively good influence due to the following mechanism. (1) In general, when a compound is electrochemically reacted to reduce or oxidize ruthenium, a compound having an alkenyl group is polymerized, resulting in formation of a polymer film. In fact, a conventional sulfonate compound having a conventional Wei group (s〇3), an alkenyl group or the like (Korean Patent 0450199 and US Patent 2002-0197537, Formula 2) is charged for the first time. Immediately after the cycle, a polymer film was formed on the surfaces of the anode and the cathode. The polymer film can be provided as a passivation layer, so that the additive and the electrolyte will not be decomposed, thereby inhibiting the co-injection of an electrolyte solvent into the electrode active material, resulting in an electrode active material and an electrolyte solvent. The side reaction between, as well as the collapse of an electrode structure. At the same time, the polymer film can serve as a channel for lithium ions, thereby minimizing the deterioration of battery quality. According to the present invention, the sulfonate compound having a monosulfonic acid group (S〇3) and a monoalkenyl group may be further substituted with an electron withdrawing group (EWG), for example, a cyano group (-CN), a different Cyanate group (-NCO), monothiocyanate (_SCN) or isothiocyanate (-NCS). A sulfonate compound substituted with at least one electron-donating substituent, which exhibits a reduced reduction potential, compared to a conventional type 1304803 acid salt compound substituted or unsubstituted with an electron-donating group (EDG) In the case of half of the battery - an increased reduction potential - in this way it is easy to decompose at a low initial voltage and exhibit high reactivity with the anode. Therefore, when the sulfonate compound according to the present invention is used in an electrolyte, the sulfonate compound can reach a sufficient degree, possibly improving the overall D quality of a battery. More specifically, after the first charge cycle, the acid salt compound can be immediately decomposed to form a "stable and thick film" on the surface of the anode, thereby reducing the irreversible capacity of the cell. Finally, it is possible to improve the overall quality of the battery, including the amount of grain and life characteristics. It follows that the reduced properties of a compound may be primarily affected by the electronic effects within the compound. In other words, the compound has an increased electron density when it is in a substituent-containing compound having an electron-donating ability. Since 15 20 of this 'ready-electron-donating group is introduced into an additive, thereby increasing the reduction potential of the additive (reducing the reduction potential in the case of a half cell), the execution of the adverse reduction reaction is unavoidable, as described herein, When a pull-electron group (e-only) is introduced into the compound of the acid salt additive, it is confirmed that the acid salt compound has a reduced reduction potential (in the case of a half-cell, the reduction potential is increased), which is advantageous for the anode. Perform a reduction reaction. (7) In addition, according to the invention, the substituent is introduced into a diacid salt of a dicyano group (-CN), an iso-acid group (-NC.), a thiocyanate group (-) or an isothiocyanate. The acid group (_NCS) is a pull-electron substituent having a high dipole moment which can be formed into a strong bond with a transition metal, a transition metal oxide or a stor-containing material exposed on the surface of an electrode active material.

9 1304803 - In particular, the substituents can be formed at a high temperature of 45t: or higher, and the surface of the (four) material is formed - stronger bonding, thereby forming a protective layer similar to the composite. From then on, after the first charge cycle of the battery, and the above-mentioned substituent-based acid salt compound is immediately adsorbed by the surface of an electrode, 5 = (10) film. Based on this result, it is easier to form a stable and thicker film than the "n-substituted acid salt" according to the present invention. At the same time, the synthesized purified film is strongly bonded to the surface of the electric (4) (four) material, such as the secretification _ can hold its stability and structural integrity in the repeated charge / release shield ring, and thus can maintain the quality of the battery. The acid salt compounds according to the present invention can significantly improve the cycle characteristics of the battery, especially at high temperatures or higher temperatures. * According to the present invention, one of the essential components for forming an electrolyte for a battery is a - a hydrochloride compound. The compound is not particularly limited as long as it is a monobasic acid compound having a selected from the group consisting of a monocyano group (-CN), an isocyanate group 15 (-NC〇), a thiocyanate group (-SCN), and an isosulfur At least one electron withdrawing group (EWG) of the group of groups I of cyanate groups (-NCS). In particular, it is preferred to use a sulfonate compound and further contain an alkenyl group, and when the compound is electrochemically reacted to be reduced or oxidized, a polymerization reaction can be produced. The hydrochloride compound can be represented by the following formula 1: 2 〇 [Formula 1] '·

Wherein R is a C2~C10 alkenyl group; and I is selected from the group consisting of a C1~C10 alkyl group, an alkenyl group, an aryl group, and a substituent containing up to 1304803'. The substituent is selected from the group consisting of -cyano (_CN), isocyanide A monofunctional group consisting of a phenyl group of an acid group (such as an anthracene), a sulfur group, an acid group (.-), and an isothiol group (inclusion 8). The compound represented by the formula 1 has not only an -alkenyl group but also a 5-electron group (EWG) such as a mono-nitro group, an iso-azide group, a monothiol group and an isothiocyanate group. From then on, the compound readily decomposes at a low initial voltage and forms a firm and slightly thicker positive film on the surface of the anode immediately after the first charge cycle. At the same time, the compound is formed into a cathodic protection thin layer (4) which is formed by a bond between the above substituent and the surface of the cathode active material, which is formed simultaneously with the SEI film. In other words, the compound provides an unshared electron pair present in the above substituent, thereby forming a coordination bond, thereby forming a protective film similar to the composite. Therefore, since the protective layer is on the two electrodes, it is possible to improve the life characteristics associated with the anode, the quality of the cycle characteristics, and the high-temperature storage characteristics associated with the cathode. Based on this result, it is possible to improve the overall quality of the battery and at the same time improve the safety of the battery. • Other sulfonate compounds having a substituent different from the above substituents, which can provide a functional mechanism similar to the above mechanism, and thus improve the battery quality, can be considered to be included in the scope of the present invention. 20 Although the amount of the sulfonate compound used can be controlled to improve the overall quality of the battery, it is preferably used in an amount of from 0.1 to 10 parts by weight based on the mass of the electrolyte. If the amount of the compound used is less than 〇.丨 by weight, the life characteristics and high temperature characteristics of the battery may not be effectively improved. On the other hand, if the amount of the compound used is more than 10 parts by weight, the increase in the amount of irreversible electricity 11 1304803 may result in a decrease in the overall quality of the battery. The electrolyte used in the battery, the compound to be added may include conventional compounds well known in the art, for example, an electrolyte salt and an organic solvent. 5 The electrolyte salts which can be used in the present invention include a salt represented by the formula A+B-, wherein A+ represents an alkali metal cation selected from the group consisting of Li+, Na+, K+ and combinations thereof. And B_ represents a group selected from the group consisting of PF6, BF4, ci, Br, r, C104, AsF6, CH3C (V, N(CF3S02)2-, C(CF2S〇2)3, and a compound thereof An anion. A lithium 10 salt is particularly suitable. The lithium salt is not particularly limited as an example and may include: LiC1〇4,

LiCF3S03, LiPF6, LiBF4, LiAsF6, LiN(CF3S02)2 and mixtures thereof. The organic solvent which can be used in the present invention includes conventional solvents well known in the art, such as cyclic carbonates and/or linear carbonates. Examples of the organic 15 solvent are not particularly limited 'may include: propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), Dimethylsulfonic acid, acetonitrile, dimethoxyethane, diethoxyethane, tetrahydrofuran, N-fluorenyl-2-pyrrolidone (NMP), ethyl cerium carbonate (EMC), γ-butyl Acid lactone (GBL), fluorinated ethylene carbonate (FEC), decyl decanoate, ethyl decanoate, propyl citrate, decyl acetate, ethyl acetate, propyl acetate, amyl acetate, C Methyl ester, ethyl propionate, propyl propionate, butyl acetonate or a mixture thereof. A dentate derivative of the above organic solvent can also be used. Further, the present invention provides an electrode comprising a hydrogenate compound or a chemical reaction product thereof, partially or wholly formed on the surface thereof, wherein the sulfonic acid 12 1304803 class compound comprises a compound selected from the group consisting of and an isothiocyanate. At least one of the substituent electrodes in the group consisting of the bases may be an anode comprising a solid electrolyte interface (SEi) film, partially or wholly formed on the surface thereof by electrochemical reaction of the above sulfonate compound; And the cathode comprises a protective film similar to the composite, via an electrode active material surface and a group selected from the group consisting of a cyano group, an isocyanate group, a thiocyanate group and an isothiocyanate group. Formed by chemical bonding between at least one substituent. If possible, a protective film is preferably formed on the surface of the two electrodes in order to improve the overall quality of the battery. The electrode has a protective film on the surface of the anode and/or the cathode, which can be obtained by charging/discharging the battery through the electrolyte using the electrolyte, such as an EWG substituent of the sulfonate compound in the electrolyte (for example, a cyano group, a 15 20 isocyanate group, -thiocyanate group or monoisothiocyanate group may form a complex with the surface of the electrode active material. In one variation, the contiguous acid compound may be coated on the surface of an electrode active material, or other materials may be used to form the electrode in a composition. Another variation may be applied to the surface of a starting material forming the electrode. The electrode included in the battery, the surface-forming composition, the surface of the second material, the surface of the material is oxidized by a continuous acid carbonaceous material having at least one species, a transition metal or a transition metal. The carbonaceous material, transition metal or transition metal oxide in the electrode can be "discharge cycle, two. in this way" in repeated charge / discharge. In addition, the pre-(four) metal is partially dissolved from the f-active material, although any When external physical impact is applied to the battery, it can be suppressed

13 1304803 5 10 15 20 The exothermic reaction caused by direct contact between the electrode surface and the electrolyte and the collapse of the electrode active material structure. Finally, it is possible to prevent the battery from burning and exploding due to an increase in internal temperature. In particular, the sulfonate compound containing an EWG substituent can protect the surface of the electrode tougher at a temperature of 45 C or more at a temperature than that at room temperature. Therefore, good thermal stability of the electrode can be provided. The electrode according to the present invention can be formed by applying an electrode active material to a current general-purpose current collector by using a method well known in the art. In a specific embodiment of the method, an electrode slurry comprises a cathode active material or an anode active material which is applied to a current common current collector' and then dried. At the same time, a small amount of a conductive agent and/or an adhesive may be added as needed. In particular, the cathode active material may comprise any of the cathode active materials used in the cathode of a conventional electrochemical device. The cathode active material is not particularly limited, and may include: a lithium transition metal composite oxide, including

LiMxOy (where μ is Co, Ni, Mn, C〇aNibMnc), such as a bellocene composite oxide (such as LiMhCU), lithium nickel oxide (such as LiNi〇2), lithium cobalt oxide (such as LiCo〇2)' or Other oxides include a portion of the transition metal substituted with manganese, nickel, and cobalt; chalcogen compounds (e.g., oxidized, titanium dioxide, molybdenum dioxide, etc.); or other similar compounds. Among such examples, LiC〇02, LiNi〇2, LiMn〇2, LiMn2〇4 ^ are particularly suitable.

Li(NiaCobMnc)02 (where 〇<a<1,0<b<a,〇<c<1,

LiNi^yCovO^ LiC〇1.YMnY〇2> LiNi^yMnyO^^.t 0^Y<1) > Li(NiaCobMnc)04 (where 〇<a<2, 〇<b<2, 〇<;c<2, a+b+c==2) 14 1304803 The polar active material may include any of the anode active materials used in the conventional-conventional electrochemical device. The anode is not particularly limited and may include a bell-embedded material such as activated carbon, graphite or other carbonaceous material on the bell metal. The cathode current set, the eighth example is not particularly limited, and may include a metal foil formed of A, nickel or a composition thereof. The anode current collector is not particularly limited as an example, and may include a metal foil formed of copper, gold, nickel, a copper alloy or a combination thereof. It is possible to use the current adhesive. The adhesive: it is not particularly limited and may include: PVDF (polyethylene dioxide) or dilute butadiene rubber. Further, the present invention provides an electrochemical device comprising: a cathode, an anode, and an electrolyte, wherein the electrolyte comprises the above-mentioned ewg 15 group-acid compound; and/or the cathode and the anode are either - or both The above-mentioned EWG substituent or the chemical reaction product thereof is partially or wholly formed on the surface thereof. The electrochemical device includes any device chemical device that can perform an electrochemical reaction internally, and the financial device may include: all kinds of primary electric 20-person batteries, fuel cells, solar cells, capacitors or the like. The device is a secondary battery, more specifically one clock: a pool 'for example, a lithium metal secondary battery, a lithium ion secondary battery, a lithium secondary battery or a lithium ion secondary battery. The electrochemical device according to the invention can be obtained by using a method well known in the art.

The electrochemical device obtained by the above method is not particularly limited in shape. The electric device can be a cylindrical, prismatic, pouch or coin type device.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The preferred embodiments of the present invention are described in detail below, but the scope of the invention is intended to be limited by the scope of the claims. Example 1 Preparation of Electrolyte 1 LiPFg was dissolved in a mixed solvent of EC:EMC (3:7), and used as an electrolyte, and added in an amount of 2 parts by weight, represented by the formula 4: Molecular formula 4]

1-2. Fabrication of half-cells Artificial graphite was used as the cathode, and lithium metal foil was used as the anode 16 1304803 pole to provide a hard-type half-cell in a conventional manner. The electrolyte obtained as described in Example 注入 was injected into the half cell. 1-3. Manufacture of a full battery A cathode including LiCo02 and an anode including artificial graphite are used to facilitate the supply of a hardband type battery in a conventional manner. The electrolyte obtained as described in Example 注入 was injected into this full battery. Example 2 An electrolyte was obtained in the same manner as in Example 1 except that the compound represented by the formula 5 was used, and 2 parts by weight of the compound was added to the electrolyte, instead of the compound represented by the formula 4. Half battery and one full battery.

[Molecular formula 5J

15 I Comparative Example 1 to 3 Production of Lithium Secondary Battery] Comparative Example 1 In addition to the compound represented by the formula 6, the amount of 2. G parts by weight was added to the electrolyte, and the compound represented by the formula 4 was substituted. In the same manner as described in Example 1, an electrolyte, a half battery, and a full battery were obtained. [Molecular formula 61 17 1304803

Comparative Example 2, "The compound represented by the X-knife type 7, the amount of 2.0 parts by weight added to the electrolyte' was substituted for the compound represented by the formula 4, and the other was obtained in the same manner as described in Example i - electrolysis f ,—half battery and _ [Molecular Formula 7]

10 Comparative Example 3 An electrolyte, a half cell, and an all-electric battery were obtained in the same manner as described in Example 1, except that the conventional electrolysis f without additives was used. 15 Test Example 1: Measurement of reduction potential of sulfonate-based compound Each of the coin-type half-cells obtained by the conventional method was discharged to 5 mV under 〇 ic by using the electrolyte prepared in Example 2 and Comparative Examples 1 to 3. Then, the test results are plotted with a dQ/dV plot. Figure i shows this plot. After the test, compared with the half-cells obtained in Comparative Examples 1 to 3, the half-cell of Example 2 used 18 1304803 «-basic component' as the electrolyte containing the -cyano-based hydrochloride compound as the electrolyte. The high potential (for the full battery - lower potential) shows - the reduction peak. Therefore, it can be seen from the above results that the introduction-electron-based (EWG) causes the reductive electrochemistry of the acid-based compound at the anode. Test Example 2: Measurement of SEI film formed at the anode The following test was carried out to determine a positive film formed on the surface of the anode from the acid compound having a -electron group based on the present invention.

The comparative example 10 -/77 谷 个 经 孓 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 电池 在 在 电池 在 在 23 23 23 23 23 The anode was analyzed by DSC (Micro Scanning Calorimeter). The result is shown in Figure 2. It can be seen from the figure that the radio wave peak generated by the thermal collapse of the anode surface t SE! film appears in the range of 70 to l ° ° C. The change in the exothermic reaction caused by the collapse of the anode surface as shown in Fig. 2 is due to the type of the additive for the electrolyte. Further, all of the above test results demonstrate that the electrolyte additive ' participates in the formation of the film at the anode according to the present invention. Test Example 3: Evaluation of high-temperature expansion characteristics of the battery The following operation was performed to evaluate the quality of the secondary battery according to one aspect of the present invention. — As a test sample, a clock secondary battery (whole battery) including Examples 1 and 2 containing a cyano group-containing compound as an electrolyte additive was used. For the purpose of testing, use a comparative example of an electrolyte or a conventional electrolyte comprising a compound containing no cyano group as a 191304803 添加 additive; a battery at a temperature range of 4.2 to 3 ν, The charge/discharge cycle was repeated with a 0.5 C electric/melon. After the 5 15 20 m type, the battery produced by Comparative Example 3 using a conventional electrolyte showed a marked decrease in cycle characteristics. According to the battery of Comparative Example 1, the use of a compound containing no cyano sulphate, and a battery having a cyano group but not containing a gynecological group, showed a significant decrease in the % characteristic. (Please refer to Figure 3). This means that when a conventional hydrogenate compound is used, a purification layer cannot be formed (several to a sufficient extent. Conversely, Examples i and 2 use an organic acid-containing compound as an electrolyte additive, even in After 60 cycles, the cycle characteristics showed only a slight decrease. The batteries of Examples i & 2 showed good cycle characteristics and improved life characteristics at high temperatures (please refer to Figure 3). - As can be seen from the foregoing, according to the present invention The lithium battery described above, which uses a polythene-based electron group as an additive, can provide significantly improved high-temperature lifetime characteristics. ^Electrolysis Although the present invention 6 is currently considered to be the most practical and preferred DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT OF THE INVENTION The present invention is not limited to the specific embodiments and illustrations disclosed herein. Instead, it is intended to cover various modifications that are included in the spirit and scope of the claims. And a change. [Simplified description of the drawings] Fig. 1 shows the electric power obtained by measuring the half-cell including the electrolyte in the second embodiment and the comparative examples 1 to 3 of the present invention. Fig. 2 shows the "collected from the half-cells" after the charge/discharge cycles of the first, second and comparative examples of the first embodiment of the present invention. Fig. 3 shows the results of the measurement of the results of the measurement by the differential scanning calorimeter (DSC). Fig. 3 shows the high temperature of the lithium secondary battery in the embodiment 1, the embodiment 2 and the comparative examples 1 to 3. (6〇.〇Characteristics display diagram. Main component symbol description

twenty one

Claims (1)

X. Application Patent Range: 1. An electrolyte for a battery comprising: (a) an electrolyte salt; (b) an electrolyte solvent; and (c) a monosulfonate compound selected from the group consisting of a cyanide At least one electron-withdrawing group (eWg) of the group consisting of a group (-CN), an isocyanato group (-NCO), a thiocyanate group (-SCN), and an isothiocyanate group (-NCS). 2. The electrolyte according to claim 1, wherein the sulfonate compound has an alkenyl group. 3. The electrolyte according to claim 1, wherein the acid salt compound is a compound which can be represented by the following formula: [Formula 1] Wherein R! is a C2~CIO alkenyl group; and 15 R2 is selected from the group consisting of a C1~c10 alkyl group, an alkenyl group, an aryl group, and at least one substituent selected from the group consisting of a cyano group (-CN), an isocyanate A monofunctional group of the group consisting of phenyl group (_NC〇), thiocyanate group (-SCN) and phenyl group of isothiocyanate group (_NCS). 4. The electrolyte according to the invention of claim 2, wherein the sulfonate compound 20 performs an electrochemical reaction in the battery to form a passivation layer, which exhibits a drop due to introduction of an electron withdrawing group (EWG). Reduction potential. 22 1304803 5. The electrolyte according to claim i, wherein the compound is used in an amount of 1 part by weight of the electrolyte rail HG. 6. The electrode 'includes a rhein compound or a chemical reaction product thereof, which is partially or wholly formed on the surface thereof, wherein the acid salt compound comprises: a monocyano group, an isocyanate group, and a At least one electron withdrawing group (EWG) of the group consisting of a thiocyanate group and an isothiocyanate group. 10. The electrode according to claim 6, wherein the sulfonate compound is a compound which can be represented by the following formula 1. [Formula 1] R2 wherein R! is a C2~CIO alkenyl group; and I is selected from the group consisting of a C1 to C10 alkyl group, an alkenyl group, an aryl group, and a group containing at least a substituent selected from the group consisting of a -cyano group, an isocyanate group, and a sulfur. a functional group in the group consisting of a nitro acid group and a phenyl group of a ruthenium I5 isothiocyanate group. 8. The electrode according to claim 6, wherein a solid electrolyte interface (SEI) film is formed on the surface of the electrode via the electrochemical reaction of the sulfonate compound. 9. The electrode according to claim 6, wherein the electrode comprises a protective layer similar to 20, and the surface of the active material and the sulfonate-containing compound are selected from the group consisting of a cyano group and a sulphuric acid. Formed by a chemical bond between at least one substituent in the group consisting of a rock, a rocky acid group, and an isothiocyanate group. twenty three