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    • 专利摘要:
    polymer gel electrolyte and electrochemical device including the same. The present invention provides a polymer electrolyte obtained by gel polymerization and a gelling composition for a polymer gel including an organic solvent, an electrolyte salt and a first polymerizable monomer, wherein the polymer gel electrolyte further comprises a compound represented by the following formula 1 as a first additive; wherein r1 to r3 are independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 5 to 7 carbon atoms, or a fluorine-substituted alkyl group having 1 to 5 carbon atoms, or at least , two substituents selected from r1 to r3 are coupled or bonded together to form a cyclo group having a ring atom composed of 2 to 6 carbon atoms or a heterocyclic group having a ring atom composed of 2 to 8 atoms of carbon and 1 to 3 hetero oxygen atoms.
    公开号:BR112015005331B1
    申请号:R112015005331-9
    申请日:2014-10-31
    公开日:2021-08-10
    发明作者:Doo Kyung Yang；Kyoung Ho Ahn；Jeong Woo Oh；Yi Jin Jung；Min Jung Kim
    申请人:Lg Chem, Ltd.；
    IPC主号:
    专利说明:

    TECHNICAL FIELD
    [001] The present invention relates to a polymer gel electrolyte including an additive capable of imparting effects of formation of the polymer gel electrolyte in an air atmosphere and the function of enhancing flame retardancy, and an electrochemical device including polymer gel electrolyte. TECHNICAL BACKGROUND
    [002] As a field of application of the energy storage technique is extended to a cell phone, a camcorder, a laptop PC and an electric vehicle, efforts in the study and development of batteries have been increasingly incorporated.
    [003] Taking this aspect into account, an electrochemical device receives the greatest attention. Particularly, in line with the trend towards electrical appliances with small size and light weight, efforts to develop a secondary lithium battery having small size, light weight and capable of charging and discharging at high capacity have been continued.
    [004] The secondary lithium battery is composed of a cathode and an anode, which include an active electrode material, which can interleave and deinterleave lithium ions, a separator disposed between them and an electrolyte as a means of delivery of the ions of lithium.
    [005] As an electrolyte, a liquid-state electrolyte, in particular an ion-conducting organic liquid electrolyte obtained by dissolving a salt in a non-aqueous organic solvent, has been widely used. However, with liquid electrolyte, leakage can be generated, and ignition or explosion can be induced due to the high flammability of the non-aqueous organic solvent used. In addition, with the liquid electrolyte, an organic carbonate solvent can be decomposed during charging and discharging a secondary lithium battery, or a secondary reaction with an electrode can be carried out to generate a gas in a battery. The side reaction can be accelerated during storage at elevated temperature to increase the amount of gas generated. The gas that is consistently generated can induce an increase in the battery's internal pressure, which leads to battery alteration, including expansion of battery thickness. In addition, local adhesive difference may be generated on the battery electrode surface, and electrode reaction may not be carried out uniformly over the entire electrode surface.
    [006] Recently, a method of using a polymer gel electrolyte without causing concern for leakage, etc., has been suggested to overcome the problem of safety of an electrolyte having a liquid state. Polymer gel electrolyte is manufactured by impregnating a polymer matrix formed by the polymerization reaction of a polymerizable monomer and a polymer initiator with an electrolyte including an electrolyte salt and a non-aqueous organic solvent, and then gelling.
    [007] However, since the polymer gel electrolyte also includes the non-aqueous organic solvent, defects concerning thermal safety are still mentioned. Furthermore, since inferior battery performance is attainable when compared to a battery using a liquid electrolyte, there are limits to commercialization. DISCLOSURE OF THE INVENTION TECHNICAL PROBLEM
    [008] In order to improve the thermal safety of a polymer gel electrolyte including a non-aqueous organic solvent, a polymer gel electrolyte including a polymerizable monomer containing a flame retardant functional group and a flame retardant additive having effects of forming polymer gel electrolyte and imparting flame retardant performance in an air atmosphere, is provided in the present invention.
    [009] Furthermore, an electrochemical device including the polymer gel electrolyte is provided in the present invention. TECHNICAL SOLUTION
    [010] According to one aspect of the present invention, there is provided a polymer gel electrolyte obtained by polymerizing and gelling a composition for a gel polymer including a non-aqueous organic solvent, an electrolyte salt and a first polymerizable monomer; wherein the polymer gel electrolyte further includes (a) a compound represented by the following Formula 1 as a first additive:
    wherein R1 to R3 are independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 5 to 7 carbon atoms, or a fluorine-substituted alkyl group having 1 to 5 carbon atoms, or at least , two substituents selected from R1 to R3 are coupled or connected to each other to form a cyclic group having a ring atom composed of 2 to 6 carbon atoms or a heterocyclic group having a ring atom composed of 2 to 8 carbon atoms and 1 to 3 hetero oxygen atoms.
    [011] In addition, the polymer gel electrolyte may further include a (meth)acrylic acid ester compound as a second additive.
    [012] The polymer gel electrolyte of the present invention may further include a compound represented by the following formula 2, as a third additive:
    where R4 is hydrogen or an alkyl group having 1 to 5 carbon atoms, R5 to R7 are independently hydrogen, fluorine or -O-CO-CH=CH2, and n is an integer from 1 to 5.
    [013] According to another aspect of the present invention, an electrochemical device is provided including a cathode, an anode, a separator disposed between the cathode and the anode, and the polymer gel electrolyte. ADVANTAGEOUS EFFECTS
    [014] According to the present invention, a polymerizable monomer including a flame retardant functional group and a flame retardant additive decreasing the effects of oxygen are further added during preparation of a polymer gel electrolyte, thus improving the effects of forming the polymer gel electrolyte in an atmosphere of air and ensuring the thermal safety of an electrochemical device including the same. BRIEF DESCRIPTION OF THE DRAWINGS
    [015] Preferred embodiments of the invention will be illustrated with reference to the accompanying drawings. The drawings are illustrated for a better understanding of the technical spirit of the present invention and the content of the invention described above, and the present invention is not to be construed as limited to the disclosure in the drawings.
    [016] Figure 1 is a photographic image that illustrates the reaction experiments of formation of a polymer gel electrolyte according to Experimental Example 1 of the present invention.
    [017] Figure 2 is a graph illustrating life properties of cells according to Experimental Example 2 of the present invention. BEST WAY TO CARRY OUT THE INVENTION
    [018] Hereinafter, the present invention will be described in more detail to aid understanding of the present invention. It should be understood that the terms or words used in the specification and claims are not to be interpreted as having a meaning that is commonly used or defined in dictionaries, but should be interpreted as having a meaning that is consistent with their meaning in the context of the present. invention based on the principle that the concept that the terms can be properly defined by the inventors for the best explanation of the invention.
    [019] A non-aqueous organic solvent used for the preparation of a polymer gel electrolyte is decomposed and burns during generation of highly active radicals such as OH-, H+, when the temperature of an electrochemical device increases. In this case, since the radical generation reaction is an exothermic reaction, the combustion reaction of the organic solvent can be a chain reaction, and explosion and ignition of a device can be induced. However, in the case that the polymer gel electrolyte is prepared in the presence of air or oxygen, the reactivity of the polymerizable monomers may decrease, and unreacted monomers may be present. Thus, the effects of polymer gel electrolyte formation may be deteriorated, and battery performance may be diminished.
    [020] In one embodiment of the present invention, there is provided a polymer gel electrolyte obtained by polymerizing and gelling a composition for a gel polymer including a non-aqueous organic solvent, an electrolyte salt and a first polymerizable monomer, wherein the gel polymer electrolyte further includes a compound represented by the following Formula 1 as a first additive:
    wherein R1 to R3 are independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 5 to 7 carbon atoms, or a fluorine-substituted alkyl group having 1 to 5 carbon atoms, or at least , two substituents selected from R1 to R3 are coupled or connected to each other to form a cyclic group having a ring atom composed of 2 to 6 carbon atoms or a heterocyclic group having a ring atom composed of 2 to 8 carbon atoms. carbon and 1 to 3 hetero oxygen atoms.
    [021] On the other hand, when the radical reaction necessary during the preparation of the polymer gel electrolyte is carried out in the presence of oxygen, a peroxide group can be stabilized through oxygen extinction, and the efficiency of the chain reaction is known to decrease.
    [022] In the present invention, the compound represented by Formula 1 as the first additive is a flame retardant additive component and decreases the effect of oxygen in an air atmosphere, for example, performs a reaction with an active oxygen atom of In order to form a phosphate, it consumes oxygen to increase the conversion rate during the reaction (the reactivity of polymerizable monomers), and enhances flame retardancy at the same time.
    [023] In this case, a typical example of the compound represented by Formula 1 as the first additive may be at least one selected from the group consisting of trimethyl phosphite, triethyl phosphite, tributyl phosphate (TBP), triphenyl phosphite , ethyl ethylene phosphate (EEP) and tris (2,2,2-trifluoroethyl) phosphite (TTFEP).
    [024] Furthermore, the amount of the compound represented by Formula 1 as the first additive can be from 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of polymer gel electrolyte. In the case where the amount of compound is less than 0.01 parts by weight, the flame retardancy improving effect may be insufficient, and the mechanical properties of the electrolyte may be deteriorated, and in the case where the amount exceeds 10 parts by weight, the ionic conductivity of the electrolyte may decrease.
    [025] In addition, the polymer gel electrolyte of the present invention may further include a second polymerizable monomer as a second additive, e.g., a (meth)acrylic acid ester compound including at least two acrylate groups in the molecule to form a polymeric matrix more easily, which is a basic skeleton, during preparation of the polymer gel electrolyte.
    [026] Examples of the (meth)acrylic acid ester compound of the second additive may include a monomer represented by the following general formulas 3a to 3c or its oligomers:
    where R8, R9, R10 and R13 are independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, R11 and R12 are independently hydrogen, oxygen or an alkyl group having 1 to 4 carbon atoms, where in the case where R11 and R12 are oxygen, a double bond is formed with a combined carbon, m is an integer from 1 to 20, and o is an integer from 0 or 1 to 3:
    wherein R14 is an alkyl group having 1 to 5 carbon atoms; or
    where R18 is an alkylene group having 1 to 5 carbon atoms, R19 is an alkyl group having 1 to 5 carbon atoms, an alkyl group including a terminal hydroxyl group and having 1 to 5 carbon atoms or -CO-CO-CH =CH2, and R20 and R21 are -R22-O-CO-CH=CH2, wherein R22 is an alkylene group having 1 to 5 carbon atoms, R15 and R16 are an alkylene group having 1 to 10 carbon atoms or one alkylene group including at least one ether group and having from 1 to 10 carbon atoms, R17 is -CO-(R24)yO-CO-CH=CH2 or -(R24)yO-CO-CH=CH2, wherein R24 is an alkylene group having 1 to 5 carbon atoms, y is an integer from 0 to 5, and P is an integer from 0 to 5:
    where R25 is an alkyl group having 1 to 5 carbon atoms, R26 and R27 are -O-(R23)yO-CO-CH=CH2 or -(R26)yO-CO-CH=CH2, wherein R23 and R26 are an alkylene group having 1 to 5 carbon atoms, and y is an integer from 0 to 5.
    [027] Particularly, typical examples of the (meth)acrylic acid ester compound as the second additive may include a single material or a mixture of at least two selected from the group consisting of trimethylalpropane ethoxylated triacrylate (ETPTA), di(trimethylalpropane) ) tetraacrylate, di(ethylene glycol) diacrylate (Di(EG) DA), di(ethylene glycol) dimethacrylate (Di(EG) MS), ethylene glycol dimethacrylate (EGDM), dipropylene glycol diacrylate (Di(PG) DA), dipropylene glycol dimethacrylate (Di (PG) DM), ethylene glycol divinyl ether (EGDVE), diethylene glycol divinyl ether (Di (EG) DVE), triethylene glycol dimethacrylate (Tri (EG) DM), dipentaerythritol pentaacrylate (DPentA), trimethylolpropane triacrylate ( TMPTA), trimethylalpropane trimethacrylate (TMPTM), propoxylated (3) trimethylalpropane triacrylate (PO (3) TMPTA), propoxylated (6) trimethylalpropane triacrylate (PO (6) TMPTA), poly (ethylene glycol) diacrylate (PAI) and polyethylene glycol dimethacrylate. However, the present invention is not limited to them, and a multiacrylate can be mixed with them.
    [028] The amount of the (meth)acrylic acid ester compound of the second additive is not specifically limited, however, it may be from about 0.1 to about 20 parts by weight based on 0 parts by weight of the amount. total polymer gel electrolyte to enhance the effects that form the polymer matrix, which is the basic skeleton of the polymer gel electrolyte.
    [029] In addition, the polymer gel electrolyte of the present invention may further include a compound represented by the following formula 2, as a third additive to further impart improved flame retardancy effects:
    where R4 is hydrogen or an alkyl group having 1 to 5 carbon atoms, R5 to R7 are independently hydrogen, fluorine or -O-CO-CH=CH2, and n is an integer from 1 to 5.
    [030] The compound (oligomer) represented by Formula 2 as the third additive is a flame retardant additive component and can improve flame retardancy and impart battery resistance decreasing effects. Typical examples might include the following general formulas 2a and 2b:


    [031] Generally speaking, a fluorine atom has strong electron withdrawing properties, and a compound that includes the fluorine atom and represented by the above Formula 2 is known to block the combustion reaction during the continuous burning of a solvent by raising the temperature of a device, or blocking the flow of oxygen to the electrolyte, thus restricting burning for longer. That is, the compound represented by Formula 2 can be decomposed when the temperature of an electrochemical device rises to easily form radicals (X-). In this case, the (X-) radicals can capture (OH-, H+) radicals generated from the decomposition of the organic solvent and produce stable and non-combustible HX, thus restricting the continued combustion of the organic solvent. Particularly, since a compound including a C-F bond as in the compound of Formula 2 above, has a very strong bond strength and has very high structural safety, the flame retardancy of the polymer gel electrolyte can be further improved.
    [032] The amount of the compound represented by Formula 2 as the third additive can be 0.5 to 20 parts by weight based on 100 parts by weight of the total amount of polymer gel electrolyte, without limitation. In the case where the amount is less than 0.5 parts by weight, the flame retardant effect may be insufficient, and the mechanical properties of the electrolyte may be deteriorated. In the case where the amount exceeds 20 parts by weight, the ionic conductivity of the electrolyte can be decreased.
    [033] On the other hand, in the polymer gel electrolyte of the present invention the non-aqueous organic solvents used for the preparation of a common electrolyte, can be used without any limitation. Typical examples of the non-aqueous organic solvent may include a cyclic carbonate, a linear carbonate, a lactone, an ether, an ester, an oxide, an acetonitrile solution, a lactam and a ketone.
    [034] Cyclic carbonate may include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), fluoroethylene carbonate (FEC), etc., and linear carbonate may include diethyl carbonate (DEC ), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl ethyl carbonate (EMC), propyl methyl carbonate (MPC), etc. The lactone may include gamma butyrolactone (GBL), and the ether may include dibutyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, etc. The ester may include methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl pivalate, etc. In addition, the sulfoxide may include dimethyl sulfoxide, etc., and may include N-methyl-2-pyrrolidone (NMP) lactam, etc. In addition, the ketone may include polymethyl vinyl ketone. Furthermore, a halogenated derivative of the organic solvent can be used. These solvents can be used alone or as a mixture thereof.
    [035] Particularly, the organic solvent in the polymer gel electrolyte of the present invention may further include a fluorine-containing organic solvent to maximize flame retardancy.
    [036] Furthermore, in the polymer gel electrolyte of the present invention, the electrolyte salt may be an electrolyte salt of a common electrochemical device, and may be a combination of (i) at least one cation selected from the group consisting of Li+, Na+ and K+e (ii) at least one anion chosen from the group consisting of PF6 , BF4 , Cl , Br , I , ClO4 , AsF6 , CH3CO2 , CF3SO3 , N(CF3SO2)2- and C(CF2SO2)3-, without limitation. These electrolyte salts can be used alone or as a mixture thereof. The amount of electrolyte salt is not specifically limited. The electrolyte salt may particularly include a lithium salt or a lithium imide salt.
    [037] In addition, in the polymer gel electrolyte of the present invention, the first polymerizable monomer can be any polyfunctional acrylate compounds used for the preparation of a common gel polymer electrolyte, without limitation. In particular, a phosphate compound or a pyrophosphate compound known to be used as a flame retardant agent may be included. phosphate compounds may include a phosphate acrylate monomer represented by the following general formula 4:
    alkyl group having 1 to 3 carbon atoms, eq is an integer from 1 to 3.
    [038] Typical examples of the first polymerizable monomer may include a phosphate acrylate, represented by the following formula 4a:
    polymerizable can be oxidized by burning when the temperature of a device increases to form a crosslinking compound having a three-dimensional network structure. For example, the phosphate compound is thermally decomposed to form a phosphoric acid, and a dehydration reaction is carried out between the phosphoric acid molecules, transformed to form a crosslink bond. In this way, the electrolyte including the phosphate compound can block the flow of oxygen in the electrolyte to stop the burning of the organic solvent.
    [039] Since the first polymerizable monomer of the present invention includes a phosphate moiety, which is a flame retardant functional group and an acrylate group, a polymer matrix, which is a basic backbone of polymer gel electrolyte, can be formed through a polymerization reaction. Thus, the flow properties are not illustrated in the electrolyte, and the polymer gel electrolyte of the present invention can realize electrochemical safety and thermal safety, particularly by improving flame retardancy effects.
    [040] The amount of the first polymerizable monomer can be from 0.5 to 20 parts by weight based on 100 parts by weight of the total amount of polymer gel electrolyte, without limitation. In the case where the amount is less than 0.5 parts by weight, the effects as a crosslinking agent are insufficient, the gelling of the polymer may be difficult, and the mechanical properties of the electrolyte may deteriorate. In case the amount exceeds electrolyte, and battery performance, for example, ionic conductivity may decrease.
    [041] In addition, the polymer gel electrolyte of the present invention may further include a polymerization initiator.
    [042] The polymerization initiator can be included in a volume ratio of 0.01 to 5 parts by weight based on 100 parts by weight of the total amount of polymerizable monomer. Examples of the non-limiting polymerization initiator may include an organic peroxide or hydroperoxide such as benzoyl peroxide, acetyl peroxide, dilauryl peroxide, di-tert-butyl peroxide, methyl t-butyl peroxy-2-ethylhexanoate, cumyl hydroperoxide, hydrogen peroxide, etc., and an azo compound, such as 2,2-azobis (2-cyanobutane), 2,2-azobis(methylbutyronitrile), azobis (isobutyronitrile) (AIBN), azobisdimethyl-valeronitrile (AMVN), etc. . The polymerization initiator described above can be thermally decomposed to form radicals and can react with the polymerizable monomer by a free radical polymerization to form a polymer gel electrolyte.
    [043] Furthermore, the gelatinization process of the polymer gel electrolyte of the present invention is not specifically limited, and can be performed according to common methods known in this field.
    [044] Particularly, a type of gel can be formed by i) adding a first polymerizable monomer and a first additive, and selectively at least one additive of second and third additives in an electrochemical device and performing a polymerization reaction in the presence of a polymerization initiator to form a polymer matrix and then gelling by impregnating the polymer matrix with an electrolyte including an electrolyte salt and an organic solvent; or (ii) preparing a precursor solution of a polymer gel electrolyte including a first additive, selectively at least one additive of second and third additives, a polymerizable monomer, a polymerization initiator, an electrolyte salt and a solvent organic, and the execution of a polymerization reaction.
    [045] In this case, the polymerization reaction can be carried out through a heating, electronic beam, gamma radiation and aging by the process of high temperature / room temperature. In the case where the polymerization reaction is a thermal polymerization, about 1 to 8 hours can be consumed, and the reaction temperature can be in the range of 50 to 100°C.
    [046] On the other hand, a common polymerization reaction is inconvenient because it is necessary to be carried out in inert conditions, so as to basically block the reaction of the radical with oxygen which is a radical scavenger in air.
    [047] However, by providing a polymer gel electrolyte including a polymerizable monomer including a flame retardant functional group and a flame retardant additive imparting flame retardant boosting performance in the present invention, the retarding boosting effects Polymer gel electrolyte flame arresters can be conferred and, in addition, a polymerization reaction for preparing a polymer gel electrolyte in the presence of air or oxygen can be carried out. That is, the additive can decrease the influence of oxygen during carrying out the polymerization reaction and the reactivity of the polymerizable monomers can be improved. Furthermore, the extent of the reaction can be increased so that unreacted monomers are little present. As a result, defects such as charge and discharge performance deterioration induced by the remaining unreacted monomers in the battery can be ameliorated.
    [048] Furthermore, in an embodiment of the present invention, an electrochemical device including a cathode, an anode, a separator disposed between the cathode and the anode and the polymer gel electrolyte of the present invention is provided.
    [049] In this case, the electrochemical device includes all devices in which an electrochemical reaction is performed. In particular, all types of primary batteries, secondary batteries, fuel cells, solar cells, capacitors, etc. can be included. The secondary battery can be a lithium secondary battery, and examples of the non-limiting lithium secondary battery may include a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium secondary battery. lithium ion polymer.
    [050] The electrochemical device of the present invention can be manufactured by a common method known in this field. According to a preferred embodiment, the electrochemical device may be manufactured by a method that includes (a) insertion of an electrode assembly formed by winding a cathode, an anode and a spacer disposed between the cathode and the anode in a case of a electrochemical device; and (b) inserting the precursor solution of a polymer-gel electrolyte in the case of polymerization to form a polymer-gel electrolyte.
    [051] Electrochemical device electrode can be manufactured by a common method known in this field. For example, a suspension is prepared by mixing and stirring an active electrode material, a solvent, and a binder, a conductive material and a dispersing agent, as the occasion requires, spreading (coating) the suspension in a current collector of a metal material, compress and dry.
    [052] The active electrode material can utilize either a cathode active material or an anode active material.
    [053] The cathode active material may include a lithium nickel manganese oxide (LNMO) and other materials, for example, a structured layer composite such as lithium cobalt oxide (LiCoO2), lithium nickel oxide (LiNiO2 ), etc.; a lithium transition metal composite oxide substituted with a transition metal such as Li(NiaCobMnc) O2 (0 < a < 1, 0 < b < 1, 0 < c < 1, a + b + c = 1) ; a lithium manganese oxide, such as LiMnO3, LiMn2O4, LiMnO2, etc.; a copper lithium oxide (Li2CuO2); a vanadium oxide such as LiV3O8, V2O5, Cu2V2O7, etc.; LiFe3O4; a lithium phosphate such as LiFePO4, LiCoPO4, LiFexMn1-xPO4, etc.; a lithium nickel oxide of type Ni site represented by a Formula LiNi1-xMxO2 (wherein M = Co, Mn, Al, Cu, Fe, Mg, B or Ga, and x = 0.01 to 0.3); a lithium manganese oxide compound represented by the Formula LiMn2-xMxO2 (where M = Co, Ni, Fe, Cr, Zn or Ta, ex = 0.01 to 0.1) or Li2Mn3MO8 (where M = Fe, Co, Ni, Cu or Zn), etc., without limitations.
    [054] Anode active material may be a common anode active material used in an anode of a common electrochemical device, without specific limitation. Typical examples of the anode active material used may include a lithium titanium oxide (LTO), and other materials, for example, carbon, such as hard carbon, graphite-based carbon, etc.; LixFe2O3 (0<x<1), LixWO2 (0<x<1), a lithium metal; a lithium alloy; an alloy of silicon; a tin alloy; a metal oxide such as SnO, SnO2, PbO, PbO2, Pb2O3, Pb3O4, Sb2O3, Sb2O4, Sb2O5, GeO, GeO2, Bi2O3, Bi2O4 and Bi2O5; a conductive polymer such as polyacetylene, etc.; a Li-Co-Ni based material; titanium oxide, etc.
    [055] In addition, a metal oxide such as TiO2, SnO2, etc, which can interleave and deinterleave lithium and has a potential less than 2V relative to lithium can be used without any limitation. Particularly a carbon material such as graphite, a carbon fiber, active carbon, etc. can be used, = preferably.
    [056] The current collector of a metal material is a metal with high conductivity and a metal to which the active electrode material suspension can easily attach. Any metals can be used only when the metal has no reactivity over a battery's voltage range. Non-limiting examples of a cathode collector may include aluminum, nickel, or a sheet formed by combining them, and non-limiting examples of an anode collector may include copper, gold, nickel, a copper alloy, or a sheet formed by combination of them.
    [057] The separator is not specifically limited, however, a porous separator can preferably be used. Non-limiting examples of the separator may include polypropylene, polyethylene or polyolefin-based porous separator. In addition, methods of applying the separator to a battery may include a common winding method, a laminating (stacking) method or a method of folding a separator and an electrode, etc.
    [058] The appearance of the electrochemical device of the present invention is not limited, and may have a cylindrical type using a can, a prismatic type, a pouch type or a coin type, etc. WAY TO CARRY OUT THE INVENTION
    [059] Hereinafter, the present invention will be described in more detail with reference to modalities and comparative modalities. However, the following embodiments are to illustrate the present invention, and the scope of the present invention is not limited to the embodiments presented herein. EXAMPLES (Example 1)
    [060] In an organic solvent with a weight ratio of EC:PC:EMC = 1:1:1, LiPF6 was dissolved in air so that its concentration was 1M. Then 5 parts by weight of the acrylate of phosphate of Formula 4a above as a polymerizable first monomer, 0.25 parts by weight of AIBN as a polymerization initiator, and 3 parts by weight of a first TTFEP as an additive based on 100 parts by weight of a polymer electrolyte in gel were added to prepare a polymer electrolyte precursor solution in gel. (Example 2)
    [061] In an organic solvent with a weight ratio of EC:PC:EMC = 1:1:1, LiPF6 was dissolved in air so that its concentration was 1 M. Then 3 parts by weight of the acrylate of phosphate of the above Formula 4a as a polymerizable monomer, 0.25 parts by weight of AIBN as a polymerization initiator, three parts by weight of TTFEP as a first additive and 2 parts by weight of ethoxylated trimethylalpropane triacrylate as a second additive based in 100 parts by weight of a polymer gel electrolyte were added thereto to prepare a precursor solution of the polymer gel electrolyte. (Example 3)
    [062] In an organic solvent with a weight ratio of EC:PC:EMC = 1:1:1, LiPF6 was dissolved in air so that its concentration was 1 M. Then 2 parts by weight of the acrylate of phosphate of the above Formula 4a as a polymerizable monomer, 0.25 parts by weight of AIBN as a polymerization initiator, three parts by weight of TTFEP as a first additive, 2 parts by weight of ethoxylated trimethylalpropane triacrylate as a second additive, and 2 parts by weight of a compound of Formula 2a above as a third additive based on 100 parts by weight of a polymer gel electrolyte was added thereto to prepare a polymer gel electrolyte precursor solution. (Comparative Example 1)
    [063] A precursor solution of a polymer gel electrolyte was prepared by performing the same procedure as described in Example 2, except for adding 5 parts by weight of trimethylalpropane ethoxylated triacrylate as the second additive, while excluding the first additive. (Experimental Example 1: Experience in the formation of polymer gel electrolyte)
    [064] The polymer gel electrolyte precursor solution of Example 1 (c), the polymer gel electrolyte precursor solution of Example 2 (d), and the polymer gel electrolyte precursor solutions of Comparative Example 1 ( a and b) prepared in a glove box were placed in jars, respectively, in a dry room. Oxygen was introduced into the vial and mixed. Then, a polymerization reaction was carried out in a chamber at 50 to 80°C, and gel formation (the amount of free liquid) was observed with the naked eye. From the results, gel formation was easy in the polymer gel electrolyte precursor solutions of Examples 1 and 2 of the present invention when compared to a polymer gel electrolyte precursor solution of Comparative Example 1 even with oxygen (see Figure 1). (Experimental Example 2: Experiment in the flame retardancy of polymer gel electrolyte)
    [065] After gel formation using a gel polymer electrolyte precursor solution prepared in Examples 1 to 3 and Comparative Example 1, the gel was fired and the time until the gel burns completely (burning time) and self-extinguishment time were measured. The results are illustrated in Table 1 below. [Table 1]

    [066] From the results of the experiments, it would be ensured that the combustion time and the self-extinguishment time of the gels according to Examples 1 to 3 including an additive containing a flame retardant functional group, etc. According to the present invention they were remarkably long compared to those of the gel according to Comparative Example 1. Therefore, the polymer gel electrolyte of the present invention is able to guarantee safety and flame retardancy. (Experimental Example 3: Experience on Life Cycle Properties)
    [067] A set of electrodes was formed by disposing a separator of a polyethylene material between a cathode including an LCO and an anode including graphite according to a common method, and the precursor solutions of the polymer gel electrolytes of Example 3 and Example Comparative 1 and a common liquid electrolyte were injected, respectively. After carrying out the reaction at 70°C for 5 hours, secondary lithium batteries were manufactured. Then charging and discharging were performed at 0.5 C for 50 times to measure the life cycle properties of secondary batteries.
    [068] As shown in Figure 2, the secondary battery using the polymer gel electrolyte of Example 3 of the present invention has improved life cycle properties when compared to a battery with the polymer gel electrolyte of Comparative Example 1 and it has similar cycling properties to a battery using liquid electrolyte.
    [069] Although this invention has been shown and particularly described with reference to preferred embodiments thereof and drawings, it is to be understood by those skilled in the art that various changes in form and detail can be made without departing from the spirit and scope of the invention. as defined by the appended claims.
    权利要求:
    Claims (18)
    [0001]
    1. Polymer gel electrolyte obtained by polymerizing and gelling a composition for a polymer gel comprising an organic solvent, wherein the organic solvents are the only organic solvents in the polymer gel electrolyte, the organic solvents consisting of two or more selected from a cyclic carbonate, a linear carbonate, a lactone, an ether, a sulfoxide, an acetonitrile, a lactam and a ketone; an electrolyte salt; and a first polymerizable monomer represented by the following formula 4; and CHARACTERIZED in that the gel polymer electrolyte further comprises a compound represented by the following Formula 1 as a first additive
    [0002]
    2. Polymer gel electrolyte according to claim 1, characterized by the fact that the first additive comprises at least one selected from the group consisting of trimethyl phosphite, triethyl phosphite, tributyl phosphite, triphenyl phosphite, sodium phosphite ethylene acetate and tris(2,2,2-trifluoroethyl) phosphite.
    [0003]
    3. Polymer gel electrolyte according to claim 1, characterized in that an amount of the first additive is 0.01 to 10 parts by weight based on 100 parts by weight of a total amount of polymer electrolyte in gel.
    [0004]
    4. Polymer gel electrolyte according to claim 1, characterized by the fact that it further comprises a (meth)acrylic acid ester compound containing at least two acrylate groups in one molecule as a second additive.
    [0005]
    5. Polymer gel electrolyte according to claim 4, characterized by the fact that the second additive is at least one selected from a group consisting of compounds represented by the following formulas 3a to 3c:
    [0006]
    6. Polymer gel electrolyte according to claim 4, CHARACTERIZED by the fact that the second additive is a single material or a mixture of at least two selected from the group consisting of trimethylalpropane ethoxylated triacrylate, di(trimethylalpropane) tetraacrylate , diethylene glycol diacrylate, diethylene glycol dimethacrylate, ethylene glycol dimethacrylate, dipropylene glycol diacrylate, dipropylene glycol dimethacrylate, ethylene glycol divinyl ether, divinyl ether diethylene glycol, triethylene glycol dimethacrylate, dipentaerythritol pentaacrylate, teimethylolpropane dimethacrylate, trimethylpropanetrioxylate (3) (6) trimethylalpropane triacrylate, polyethylene glycol diacrylate and polyethylene glycol dimethacrylate.
    [0007]
    7. Polymer gel electrolyte according to claim 4, characterized by the fact that the second additive is composed in a volume ratio of 0.1 to 20 parts by weight based on 100 parts by weight of a total amount of polymer gel electrolyte.
    [0008]
    8. Polymer gel electrolyte according to claim 1, characterized by the fact that it further comprises a compound represented by the following formula 2, as a third additive:
    [0009]
    9. Polymer gel electrolyte according to claim 8, CHARACTERIZED by the fact that the third additive is represented by the following general formula 2a or 2b:
    [0010]
    10. Polymer gel electrolyte according to claim 1, characterized by the fact that an amount of the third additive is 0.5 to 20 parts by weight based on 100 parts by weight of a total amount of polymer electrolyte in gel.
    [0011]
    11. Polymer gel electrolyte according to claim 1, characterized by the fact that the electrolyte salt comprises a combination of (i) at least one cation selected from the group consisting of Li+, Na+ and K+e ( ii) at least one anion chosen from the group consisting of PF6-, BF4-, Cl-, Br-, I-, ClO4-, AsF6-, CH3CO2-, CF3SO3-, N(CF3SO2)2- and C(CF2SO2 )3-.
    [0012]
    12. Polymer gel electrolyte according to claim 1, characterized by the fact that the first polymerizable monomer is represented by the following formula 4:
    [0013]
    13. Polymer gel electrolyte according to claim 1, characterized by the fact that the first polymerizable monomer is comprised in a volume ratio of 0.5 to 20 parts by weight based on 100 parts by weight of a total amount of polymer electrolyte in gel.
    [0014]
    14. Polymer gel electrolyte according to claim 1, characterized by the fact that the composition of a polymer gel electrolyte further comprises a polymerization initiator.
    [0015]
    15. Polymer gel electrolyte according to claim 14, characterized by the fact that the polymerization initiator is composed in a volume ratio of 0.01 to 5 parts by weight based on 100 parts by weight of a total amount of a polymerizable monomer.
    [0016]
    16. Polymer gel electrolyte according to claim 14, characterized by the fact that the polymerization initiator is selected from the group consisting of benzoyl peroxide, acetyl peroxide, dilauryl peroxide, di-tert-butyl peroxide, t-butyl peroxy-2-ethyl-hexanoate, cumyl hydroperoxide, hydrogen peroxide, 2,2-azobis (2-cyanobutane), 2,2-azobis (methylbutyronitrile), azobis (isobutyronitrile) and azobisdimethyl-valeronitrile.
    [0017]
    17. Electrochemical device CHARACTERIZED by the fact that it comprises: a cathode, an anode, a separator disposed between the cathode and the anode, and the polymer gel electrolyte as defined in claim 1.
    [0018]
    18. Electrochemical device, according to claim 17, CHARACTERIZED by the fact that the electrochemical device is a secondary lithium battery.
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    法律状态:
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-22| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-07-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-08-10| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 31/10/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    KR20130131474|2013-10-31|
    KR10-2013-0131474|2013-10-31|
    KR1020140150127A|KR101637090B1|2013-10-31|2014-10-31|Gel polymer electrolyte and electrochemical device comprising the same|
    PCT/KR2014/010360|WO2015065101A1|2013-10-31|2014-10-31|Gel polymer electrolyte and electro-chemical device comprising same|
    KR10-2014-0150127|2014-10-31|
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