WO2014116082A1 - 겔 폴리머 전해질용 조성물 및 이를 포함하는 리튬 이차 전지 - Google Patents
겔 폴리머 전해질용 조성물 및 이를 포함하는 리튬 이차 전지 Download PDFInfo
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- WO2014116082A1 WO2014116082A1 PCT/KR2014/000793 KR2014000793W WO2014116082A1 WO 2014116082 A1 WO2014116082 A1 WO 2014116082A1 KR 2014000793 W KR2014000793 W KR 2014000793W WO 2014116082 A1 WO2014116082 A1 WO 2014116082A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/18—Homopolymers or copolymers of nitriles
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a gel polymer electrolyte composition and a lithium secondary battery comprising the same, and more particularly, to a gel polymer electrolyte composition comprising a monomer having a functional group capable of bonding with a metal ion eluted from the positive electrode, and the same It relates to a lithium secondary battery.
- battery safety is known to be improved in the order of liquid electrolyte ⁇ gel polymer electrolyte ⁇ solid polymer electrolyte, whereas battery performance is known to decrease.
- electrolytes for electrochemical devices such as batteries and electric double layer capacitors using an electrochemical reaction
- an electrolyte in a liquid state particularly an ion conductive organic liquid electrolyte in which salts are dissolved in a non-aqueous organic solvent
- the use of the electrolyte in the liquid state is not only highly likely to deteriorate the electrode material and volatilize the organic solvent, but also has problems in safety such as combustion due to an increase in the ambient temperature and the temperature of the battery itself.
- Solid polymer electrolytes have not been commercialized yet due to inferior cell performance.
- the gel polymer electrolyte is excellent in electrochemical safety to maintain a constant thickness of the battery, and due to the inherent adhesive strength of the gel phase has an advantage of excellent contact between the electrode and the electrolyte to manufacture a thin film battery. Accordingly, development of various gel polymer electrolytes is expanding.
- lithium ions are small in size, and thus, are not only relatively easy to move directly, but also easily move to a hopping phenomenon in the electrolyte as shown in FIG. 1.
- a lithium secondary battery including the gel polymer electrolyte generally uses a lithium transition metal oxide such as LiCoO 2 as a cathode active material, but when used at high voltage, metal ions are eluted. When the metal ions are eluted, they are reduced to the metal state at the cathode to block the reaction site of the cathode, and when new metal is deposited on the surface of the cathode, the electrolyte forms a new SEI layer on the surface of the metal, consuming the electrolyte continuously. do. In addition, there is a problem in that the SEI layer of the cathode is continuously thickened to increase the resistance and deteriorate the life characteristics.
- a lithium transition metal oxide such as LiCoO 2
- the problem to be solved by the present invention is to prevent the metal ions eluted from the positive electrode to move to the negative electrode or to reduce the moving speed to reduce the precipitation of metal at the negative electrode, thereby improving the life of the battery, as well as general voltage And to provide a composition for a gel polymer electrolyte that can improve the capacity characteristics of the battery in both high voltage region and a lithium secondary battery comprising the same.
- the present invention in accordance with one embodiment, i) electrolyte solvent, ii) ionizable lithium salt, iii) polymerization initiator; And iv) a monomer having a functional group capable of bonding with a metal ion.
- the present invention cathode; Separator; And a lithium secondary battery comprising a gel polymer electrolyte, wherein the gel polymer electrolyte provides a lithium secondary battery formed by polymerizing the composition for the gel polymer electrolyte.
- the composition for a gel polymer electrolyte of the present invention includes a monomer having a functional group capable of bonding with a metal ion, and thus, when applied to a lithium secondary battery, prevents metal ions eluted from the positive electrode from moving to the negative electrode or decreases the moving speed. By reducing the precipitation of the metal at the negative electrode, the battery life can be improved and the capacity characteristics of the battery can be improved in both the normal voltage and the high voltage region.
- 1 is a diagram showing a principle of movement of lithium ions in the case of using a composition for gel polymer electrolyte.
- FIG 2 is a view comparing the degree of the metal precipitated from the negative electrode according to the use of the composition for the gel polymer electrolyte according to an embodiment of the present invention and the general electrolyte.
- FIG. 3 is a graph showing capacity characteristics of the lithium secondary batteries prepared in Examples 1 to 4 and Comparative Examples 1 to 3.
- FIG. 1 is a graph showing capacity characteristics of the lithium secondary batteries prepared in Examples 1 to 4 and Comparative Examples 1 to 3.
- FIG. 4 is a graph showing capacity characteristics of the lithium secondary batteries prepared in Examples 5 and 6 and Comparative Examples 4 and 5.
- FIG. 4 is a graph showing capacity characteristics of the lithium secondary batteries prepared in Examples 5 and 6 and Comparative Examples 4 and 5.
- FIG. 5 is a graph showing capacity characteristics at 4.3V high voltage of the lithium secondary batteries prepared in Examples 7 to 10 and Comparative Examples 6 to 8.
- FIG. 5 is a graph showing capacity characteristics at 4.3V high voltage of the lithium secondary batteries prepared in Examples 7 to 10 and Comparative Examples 6 to 8.
- composition for a gel polymer electrolyte may include a monomer having a functional group capable of bonding with an electrolyte solvent, an ionizable lithium salt, a polymerization initiator, and a metal ion.
- the monomer having a functional group is an acrylonitrile or acrylate-based monomer, preferably substituted or unsubstituted with alkyl or halogen having a functional group of C 1 to C 5 And It may include any one selected from the group consisting of or a mixture of two or more thereof.
- the monomer having a functional group may include a functional group in the monomer, such that the functional group is stably present on the gel structure in the gel polymer electrolyte.
- the cyano group and the acrylate are each added in a gel polymer electrolyte composition (gel electrolyte) to polymerize to form a complex
- the complex itself may move in the gel polymer electrolyte composition to cause reduction at the negative electrode.
- Metal may precipitate.
- 2-cyanoethyl acrylate as a monomer having a functional group, as in one embodiment of the present invention, since the cyano group is contained in the monomer having the functional group, it moves itself within the gel structure. It can become impossible.
- the general electrolyte solution in which the metal ions eluted from the positive electrode precipitates at the negative electrode Unlike the use case, it is possible to reduce the precipitation of the metal in the cathode by combining with the metal ions eluted from the anode. As a result, the charge and discharge efficiency of the lithium secondary battery can be improved and good cycle characteristics can be exhibited.
- capacity characteristics may be improved in both a normal voltage and a high voltage region.
- the term “general voltage” refers to a case where the charging voltage of the lithium secondary battery is in the range of 3.0 V to less than 4.3 V, and the term “high voltage” refers to a region in which the charging voltage is 4.3 V to 5.0 V. Means if.
- the monomer having the functional group may be 0.1 wt% to 10 wt%, preferably 0.5 wt% to 5 wt%, based on the total weight of the composition for gel polymer electrolyte. If it is less than 0.1% by weight it is difficult to gel the gel polymer electrolyte properties, and if it exceeds 10% by weight may increase the resistance due to the excessive content of the monomer may decrease the battery performance.
- the gel polymer electrolyte composition may further include a monomer having 2 to 6 acrylate groups, which may be a branched monomer.
- the branched monomer may be, for example, any one selected from the group consisting of ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate, or a mixture of two or more thereof. .
- the branched monomer may be included in an amount of 0.1 wt% to 10 wt%, preferably 0.5 wt% to 5 wt%, based on the total weight of the composition for gel polymer electrolyte.
- the electrolyte composition when the electrolyte composition further comprises a branched monomer, the monomer having a functional group and the branched monomer is mixed for 2 minutes to 12 hours in the temperature range of 30 °C to 100 °C
- the reaction can produce a polymerizable monomer.
- the content ratio of the monomer having a functional group and the branched monomer may be, for example, 1: 0.1 to 10 by weight, but is not limited thereto.
- the ionizable lithium salts included in the electrolyte composition according to an embodiment of the present invention may be, for example, LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 , CF 3 SO 3 Li, LiC (CF 3 SO 2 ) 3 And LiC 4 BO 8 It may be any one selected from the group consisting of or a mixture of two or more thereof. It is not.
- electrolyte solvent used according to an embodiment of the present invention those conventionally used in the electrolyte for lithium secondary batteries may be used without limitation, and for example, ether, ester, amide, linear carbonate, or cyclic carbonate may be used alone. Or two or more kinds thereof can be mixed.
- carbonate compounds which are typically cyclic carbonates, linear carbonates or mixtures thereof may be included.
- cyclic carbonate compound include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene Carbonate, vinylene carbonate, and halides thereof, any one selected from the group consisting of or mixtures of two or more thereof.
- linear carbonate compounds include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethylmethyl carbonate (EMC), methylpropyl carbonate (MPC) and ethylpropyl carbonate (EPC). Any one selected from the group consisting of, or a mixture of two or more thereof may be representatively used, but is not limited thereto.
- propylene carbonate and ethylene carbonate which are cyclic carbonates in the carbonate electrolyte solvent, may be preferably used because they have high dielectric constants and dissociate lithium salts in the electrolyte well, such as ethylmethyl carbonate and diethyl carbonate.
- a low viscosity, low dielectric constant linear carbonate such as dimethyl carbonate is mixed and used in an appropriate ratio, an electrolyte having high electrical conductivity can be made, and thus it can be used more preferably.
- ester in the electrolyte solvent is methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -valerolactone And ⁇ -caprolactone, but any one selected from the group consisting of, or a mixture of two or more thereof may be used, but is not limited thereto.
- a polymerization initiator may be used a conventional polymerization initiator known in the art.
- Non-limiting examples of the polymerization initiator are benzoyl peroxide, acetyl peroxide, dilauryl peroxide, di-tert-butyl peroxide, organic peroxides and hydros such as t-butyl peroxy-2-ethyl-hexanoate, cumyl hydroperoxide, and hydrogen peroxide Peroxides with 2,2'-azobis (2-cyanobutane), 2,2'-azobis (methylbutyronitrile), AIBN (2,2'-Azobis (iso-butyronitrile)) and AMVN (2 And azo compounds such as 2'-Azobisdimethyl-Valeronitrile), but are not limited thereto.
- the polymerization initiator is decomposed by heat, non-limiting examples of heat in the cell at 30 ° C. to 100 ° C. or at room temperature (5 ° C. to 30 ° C.) to form radicals, and react with the polymerizable monomer by free radical polymerization. Gel polymer electrolytes can be formed.
- the polymerization initiator may be used in an amount of 0.01% by weight to 2% by weight based on the total weight of the composition for gel polymer electrolyte. If the polymerization initiator is more than 2 parts by weight, gelation may occur too quickly or the unreacted initiator remains after the gel polymer electrolyte composition is injected into the battery, which adversely affects the battery performance. Conversely, if the polymerization initiator is less than 0.01 part by weight. There is a problem that gelation does not work well.
- the gel polymer electrolyte composition according to an embodiment of the present invention may optionally contain other additives known in the art, in addition to the components described above.
- a gel polymer electrolyte according to an embodiment of the present invention is provided. Is formed by polymerizing the composition for gel polymer electrolyte according to conventional methods known in the art. For example, the gel polymer electrolyte may be formed by in-situ polymerization of the composition for gel polymer electrolyte in the secondary battery.
- Injecting the composition for the gel polymer electrolyte according to the polymerization may include the step of forming a gel polymer electrolyte.
- the in-situ polymerization reaction in the lithium secondary battery may proceed through thermal polymerization.
- the polymerization time takes about 2 minutes to 12 hours
- the thermal polymerization temperature may be 30 to 100 °C.
- a gel polymer electrolyte is formed. Specifically, a gel polymer in which a polymerizable monomer is crosslinked with each other by a polymerization reaction is formed, and a liquid electrolyte in which an electrolyte salt is dissociated in an electrolyte solvent can be uniformly impregnated in the formed gel polymer.
- the lithium secondary battery according to an embodiment of the present invention has a charge voltage of 3.0V to 5.0V, and excellent capacity characteristics of the lithium secondary battery in both a normal voltage and a high voltage region.
- the electrode of the lithium secondary battery may be manufactured by a conventional method known in the art.
- a slurry may be prepared by mixing and stirring a solvent, a binder, a conducting agent, and a dispersant in an electrode active material, and then applying (coating) to a current collector of a metal material, compressing, and drying the electrode to prepare an electrode.
- the positive electrode active material in the positive electrode may be applied to a general voltage or a high voltage, and may be used without limitation as long as it is a compound capable of reversibly intercalating / deintercalating lithium.
- the positive electrode active material that can be applied to a high voltage is a lithium transition metal oxide of spinel having a thin-walled layered rock salt structure having a high capacity characteristic, an olivine structure, a cubic structure,
- it may include any one or two or more complex oxides selected from the group consisting of V 2 O 5 , TiS, MoS. More specifically, it may include any one selected from the group consisting of oxides of the following Chemical Formulas 1 to 3 or a mixture of two or more thereof:
- the cathode active material is preferably 0.4 ⁇ c ⁇ 0.7, 0.2 ⁇ a + b ⁇ 0.5 in Formula 1, and any one selected from the group consisting of LiNi 0.5 Mn 1.5 O 4 , LiCoPO 4, and LiFePO 4 or two of them It may contain a mixture of the above.
- a carbon material lithium metal, silicon or tin, etc. which can normally occlude and release lithium ions may be used.
- a carbon material may be used, and as the carbon material, both low crystalline carbon and high crystalline carbon may be used.
- Soft crystalline carbon and hard carbon are typical low crystalline carbon, and high crystalline carbon is natural graphite, Kish graphite, pyrolytic carbon, liquid crystal pitch carbon fiber.
- High temperature calcined carbon such as (mesophase pitch based carbon fiber), meso-carbon microbeads, Mesophase pitches and petroleum or coal tar pitch derived cokes.
- the positive electrode and / or the negative electrode may be prepared by mixing and stirring a binder, a solvent, a conductive agent and a dispersant, which may be commonly used as needed, to prepare a slurry, and then applying the same to a current collector and compressing the negative electrode.
- the binder may be polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HEP), polyvinylidene fluoride (polyvinylidenefluoride), polyacrylonitrile, polymethylmethacrylate, Polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM), Various kinds of binder polymers such as sulfonated EPDM, styrene butyrene rubber (SBR), fluorine rubber, various copolymers and the like may be used.
- PVDF-co-HEP polyvinylidene fluoride-hexafluoropropylene copolymer
- SBR styrene butyrene rubber
- the separator may be a conventional porous polymer film conventionally used as a separator, for example, polyolefin such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer
- the porous polymer film made of the polymer may be used alone or by laminating them, or a conventional porous nonwoven fabric, for example, a non-woven fabric made of high melting point glass fiber, polyethylene terephthalate fiber, or the like may be used. It is not.
- the external shape of the lithium secondary battery according to an embodiment of the present invention is not particularly limited, but may be cylindrical, rectangular, pouch type, or coin type using a can.
- EC ethylene carbonate
- EMC ethyl methyl carbonate
- 5 parts by weight of the polymerizable monomer 2.5 parts by weight of 2-cyanoethyl acrylate and 2.5 parts by weight of ditrimethylolpropane tetraacrylate are used in combination
- 100 parts by weight of the electrolyte, and t-butyl peroxy-2 as a polymerization initiator 0.25 parts by weight of ethylhexanoate was added to prepare a composition for a gel polymer electrolyte.
- a positive electrode mixture slurry was prepared by adding 94% by weight of LiCoO 2 as a positive electrode active material, 3% by weight of carbon black as a conductive agent, and 3% by weight of PVdF as a binder to N-methyl-2-pyrrolidone (NMP) as a solvent. It was.
- the positive electrode mixture slurry was applied to a thin film of aluminum (Al), which is a positive electrode current collector having a thickness of about 20 ⁇ m, dried to prepare a positive electrode, and then subjected to roll press to prepare a positive electrode.
- Al aluminum
- a negative electrode mixture slurry was prepared by adding carbon powder as a negative electrode active material, PVdF as a binder, and carbon black as a conductive agent at 96 wt%, 3 wt%, and 1 wt%, respectively, to NMP as a solvent.
- the negative electrode mixture slurry was applied to a copper (Cu) thin film, which is a negative electrode current collector having a thickness of 10 ⁇ m, dried to prepare a negative electrode, and then roll-rolled to prepare a negative electrode.
- Cu copper
- the battery was assembled using a separator composed of the positive electrode, the negative electrode, and three layers of polypropylene / polyethylene / polypropylene (PP / PE / PP). After injecting the prepared gel polymer electrolyte composition into the assembled battery, 80 ° C. was used. It was heated for 2 to 30 minutes to prepare a coin-type secondary battery.
- a separator composed of the positive electrode, the negative electrode, and three layers of polypropylene / polyethylene / polypropylene (PP / PE / PP).
- a coin-type secondary battery was prepared in the same manner as in Example 1, except that 2-cyanoethoxyethyl acrylate was used instead of 2-cyanoethyl acrylate in the gel polymer electrolyte composition of Example 1. Prepared.
- Example 1 In preparing the composition for the gel polymer electrolyte of Example 1, a coin-type secondary battery was manufactured in the same manner as in Example 1, except that acrylonitrile was used instead of 2-cyanoethyl acrylate.
- Example 1 In the manufacturing of the coin-type secondary battery of Example 1, except that a mixture of LiMn 2 O 4 and Li (Ni 0.33 Co 0.33 Mn 0.33 ) O 2 3: 7 by weight as a positive electrode active material was used, Example 1 In the same manner as the coin-type secondary battery was prepared.
- Example 1 In preparing the positive electrode of Example 1, a coin-type secondary battery was manufactured in the same manner as in Example 1, except that Li [Li 0.29 Ni 0.14 Co 0.11 Mn 0.46 ] O 2 was used instead of LiCoO 2 as the positive electrode active material.
- ethyl (E) -3- (pyridin-2-yl) -acrylate is used instead of 2-cyanoethyl acrylate.
- a coin-type secondary battery was manufactured in the same manner as in Example 1, except that Li [Li 0.29 Ni 0.14 Co 0.11 Mn 0.46 ] O 2 was used instead of LiCoO 2 .
- a coin-type secondary battery was manufactured in the same manner as in Example 1, except that the polymerizable monomer and the polymerization initiator were not used.
- ditrimethylol instead of using 5 parts by weight of a polymerizable monomer prepared by mixing 2.5 parts by weight of 2-cyanoethyl acrylate and 2.5 parts by weight of ditrimethylolpropane tetraacrylate.
- a coin-type secondary battery was manufactured in the same manner as in Example 1, except that 5 parts by weight of propane tetraacrylate was used alone.
- Example 1 In preparing the gel polymer electrolyte composition of Example 1, dipentaeryte was used instead of using 5 parts by weight of a polymerizable monomer prepared by mixing 2.5 parts by weight of 2-cyanoethyl acrylate and 2.5 parts by weight of ditrimethylolpropane tetraacrylate. A coin-type secondary battery was manufactured in the same manner as in Example 1, except that 5 parts by weight of lithol pentaacrylate was used alone.
- a coin-type secondary battery was manufactured in the same manner as in Example 5, except that the polymerizable monomer and the polymerization initiator were not used.
- ditrimethylol instead of using 5 parts by weight of the polymerizable monomer prepared by mixing 2.5 parts by weight of 2-cyanoethyl acrylate and 2.5 parts by weight of ditrimethylolpropane tetraacrylate.
- a coin-type secondary battery was manufactured in the same manner as in Example 5, except that 5 parts by weight of propane tetraacrylate was used alone.
- a coin-type secondary battery was manufactured in the same manner as in Example 7, except that the polymerizable monomer and the polymerization initiator were not used.
- ditrimethylol instead of using 5 parts by weight of the polymerizable monomer prepared by mixing 2.5 parts by weight of 2-cyanoethyl acrylate and 2.5 parts by weight of ditrimethylolpropane tetraacrylate.
- a coin-type secondary battery was manufactured in the same manner as in Example 7, except that 5 parts by weight of propane tetraacrylate was used alone.
- Example 7 In preparing the composition for the gel polymer electrolyte of Example 7, dipentaeryte instead of using 5 parts by weight of the polymerizable monomer prepared by mixing 2.5 parts by weight of 2-cyanoethyl acrylate and 2.5 parts by weight of ditrimethylolpropane tetraacrylate. A coin-type secondary battery was manufactured in the same manner as in Example 7, except that 5 parts by weight of lithol pentaacrylate was used alone.
- Examples 1 to 4 and Comparative Examples 1 to 3 were similar at the fifth cycle, but Comparative Examples 1 to 3 were rapidly reduced after about 20 cycles.
- Examples 1-4 had little capacity change until the 20th cycle.
- Examples 1 to 4 exhibited a capacity change of 2 to 3 times or more compared to Comparative Examples 1 to 3 with a moderate change in capacity change even up to the 100th cycle.
- the lithium secondary batteries (2.5mAh battery capacity) prepared in Examples 5 and 6 and Comparative Examples 4 and 5 were charged at 45 ° C. until a constant current of 4.2 V was 0.7 C, and then charged at a constant voltage of 4.2 V to charge current. Charging was terminated when became 0.125 mA. Thereafter, it was left for 10 minutes and then discharged until it reached 3.0V at a constant current of 0.5 C.
- the battery capacity was measured after 100 cycles of charge and discharge, and is shown in FIG. 4.
- the lithium secondary battery (4.3 mAh) prepared in Examples 7 to 10 and Comparative Examples 6 to 8 was charged at 55 ° C. until the constant current was 4.3 V at 0.7 C, followed by charging at a constant voltage of 4.3 V. Charging was terminated when the current became 0.215 mA. Thereafter, it was left for 10 minutes and discharged until it became 3.0V with a constant current of 0.5C. After 40 cycles of the charging and discharging, the battery capacity was measured and shown in FIG. 5.
- Examples 7 to 10 and Comparative Examples 6 to 8 were similar under the fifth cycle, but Comparative Example 6 rapidly decreased after the fifth cycle. 7 sharply decreased after the 30th cycle and Comparative Example 8 rapidly after the 20th cycle.
- Examples 7 to 10 had a gentle change in capacity until the 40th cycle compared to Comparative Examples 6 to 8, and particularly 40 and 40 cycles for Examples 8 and 9 using 2-cyanoethoxyethyl acrylate and acrylonitrile. There was almost no change in capacity even at high voltage, and showed capacity characteristics of 2 to 4 times or more compared to Comparative Examples 6 to 8.
- composition for gel polymer electrolyte of the present invention When the composition for gel polymer electrolyte of the present invention is applied to a lithium secondary battery, it prevents the metal ions eluted from the positive electrode from moving to the negative electrode or lowers the moving speed, thereby reducing the precipitation of metal from the negative electrode, thereby reducing the life of the battery. Not only can it be improved, but also the capacity characteristics of the battery can be improved in both the normal voltage and the high voltage region, and thus can be usefully used in secondary batteries.
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Abstract
Description
Claims (19)
- i) 전해액 용매,ii) 이온화 가능한 리튬염,iii) 중합 개시제; 및iv) 금속이온과 결합할 수 있는 작용기를 갖는 모노머를 포함하는 겔 폴리머 전해질용 조성물.
- 제 1 항에 있어서,상기 작용기를 갖는 모노머는 아크릴로니트릴 또는 아크릴레이트계 모노머인 것을 특징으로 하는 겔 폴리머 전해질용 조성물.
- 제 1 항에 있어서,상기 작용기를 갖는 모노머는 하기 화합물로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물인 것을 특징으로 하는 겔 폴리머 전해질용 조성물:(1) 2-시아노에틸아크릴레이트;(2) 2-시아노에톡시에틸 아크릴레이트;(3) 아크릴로니트릴;(4) 에틸 (E)-3-(피리딘-2-일)-아크릴레이트;(5) 에틸 (E)-3-(4-피리딘일)-2-프로페논염;(6) 2-프로펜산, 3,3'-[2,2'-바이피리딘]-4,4'-디일비스-, 디메틸 에스테르;(7) 2-프로펜산, 2-[2,2'-바이피리딘]-6-일에틸 에스테르;(8) 2-프로펜산, 2-[2,2'-바이피리딘]-5-일에틸 에스테르;(9) 2-프로펜산, 2-[2,2'-바이피리딘]-4-일에틸 에스테르;(10) 2-프로펜산, 1,1'-[[2,2'-바이피리딘]-4,4'-디일비스(메틸렌)] 에스테르;(11) 2-프로펜산, 1,10-페난트롤린-2,9-디일비스(메틸렌) 에스테르;(12) 2-프로펜산, 3-(1,10-페난트롤린-2-일)-, 페닐메틸 에스테르; 및(13) 2-프로펜산, 2-[[(1-옥소-2-프로페닐)옥시]메틸]-2-[(1,10-페난트롤린-5-일메톡시)메틸]-1,3-프로판디일 에스테르.
- 제 1 항에 있어서,상기 조성물은 2 내지 6개의 아크릴레이트기를 갖는 모노머를 추가로 포함하고, 상기 모노머는 분지형 모노머인 것을 특징으로 하는 겔 폴리머 전해질용 조성물.
- 제 5 항에 있어서,상기 분지형 모노머는 디트리메틸올프로판 테트라아크릴레이트, 디펜타에리트리톨 펜타아크릴레이트 및 디펜타에리트리톨 헥사아크릴레이트로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물인 것을 특징으로 하는 겔 폴리머 전해질용 조성물.
- 제 1 항에 있어서,상기 작용기를 갖는 모노머는 조성물 총 중량에 대해 0.1 중량% 내지 10 중량%의 양으로 포함되는 것을 특징으로 하는 겔 폴리머 전해질용 조성물.
- 제 5 항에 있어서,상기 분지형 모노머는 조성물 총 중량에 대해 0.1 중량% 내지 10 중량%의 양으로 포함되는 것을 특징으로 하는 겔 폴리머 전해질용 조성물.
- 제 5 항에 있어서,상기 작용기를 갖는 모노머와 상기 분지형 모노머의 함량비는 1: 0.1 내지 10 중량비인 것을 특징으로 하는 겔 폴리머 전해질용 조성물.
- 제 1 항에 있어서,상기 리튬염은 LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiN(C2F5SO2)2, LiN(CF3SO2)2, CF3SO3Li, LiC(CF3SO2)3 및 LiC4BO8로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물인 것을 특징으로 하는 겔 폴리머 전해질용 조성물.
- 제 1 항에 있어서,상기 전해액 용매는 선형 카보네이트, 환형 카보네이트 또는 이들의 조합인 것을 특징으로 하는 겔 폴리머 전해질용 조성물.
- 제 11 항에 있어서,상기 선형 카보네이트는 디메틸 카보네이트, 디에틸 카보네이트, 디프로필 카보네이트, 에틸메틸 카보네이트, 메틸프로필 카보네이트 및 에틸프로필 카보네이트로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물을 포함하고, 상기 환형 카보네이트는 에틸렌 카보네이트, 프로필렌 카보네이트, 1,2-부틸렌 카보네이트, 2,3-부틸렌 카보네이트, 1,2-펜틸렌 카보네이트, 2,3-펜틸렌 카보네이트, 비닐렌 카보네이트, 및 이들의 할로겐화물로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물을 포함하는 것을 특징으로 하는 겔 폴리머 전해질용 조성물.
- 양극; 음극; 세퍼레이터; 및 겔 폴리머 전해질을 포함하는 리튬 이차 전지에 있어서,상기 겔 폴리머 전해질은 제 1 항의 겔 폴리머 전해질용 조성물을 중합시켜 이루어지는 것을 특징으로 하는 리튬 이차 전지.
- 제 13 항에 있어서,상기 겔 폴리머 전해질용 조성물은 2 내지 6개의 아크릴레이트기를 갖는 모노머를 추가로 포함하고, 상기 모노머는 분지형 모노머인 것을 특징으로 하는 리튬 이차 전지.
- 제 14 항에 있어서,상기 분지형 모노머는 디트리메틸올프로판 테트라아크릴레이트, 디펜타에리트리톨 펜타아크릴레이트 및 디펜타에리트리톨 헥사아크릴레이트로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물인 것을 특징으로 하는 리튬 이차 전지.
- 제 13 항에 있어서,상기 리튬 이차 전지의 충전 전압은 3.0V 내지 5.0V인 것을 특징으로 하는 리튬 이차 전지.
- 제 16 항에 있어서,상기 리튬 이차 전지의 충전 전압은 4.3V 내지 5.0V인 것을 특징으로 하는 리튬 이차 전지.
- 제 17 항에 있어서,상기 양극용 양극 활물질은 하기 화학식 1 내지 화학식 3의 산화물로 이루어진 군으로부터 선택된 어느 하나 또는 이들 중 2종 이상의 혼합물인 것을 특징으로 하는 리튬 이차 전지:<화학식 1>Li[LixNiaCobMnc]O2 (0 < x ≤ 0.3, 0.3 ≤ c ≤ 0.7, 0 < a+b < 0.5, x+a+b+c=1) ;<화학식 2>LiMn2-xMxO4 (M=Ni, Co, Fe, P, S, Zr, Ti 및 Al로 이루어진 군에서 선택되는 하나 이상의 원소, 0 < x ≤ 2) ;<화학식 3>Li1+aCoxM1-xAX4 (M=Al, Mg, Ni, Co, Mn, Ti, Ga, Cu, V, Nb, Zr, Ce, In, Zn 및 Y 로 이루어진 군에서 선택되는 하나 이상의 원소이고, X는 O, F, 및 N으로 이루어진 군에서 선택되는 하나 이상의 원소이며, A는 P, S 또는 이들의 혼합 원소이고, 0≤a≤0.2, 0.5≤x≤1임).
- 제 16 항에 있어서,상기 양극용 양극 활물질은 LiCoO2, LiNiO2, LiMnO2, LiMn2O4, LiNi1-yCoyO2(O≤y<1), LiCo1-yMnyO2(O≤y<1), LiNi1-yMnyO2 (O≤y<1), 및 Li[NiaCobMnc]O2 (0 < a, b, c ≤ 1, a+b+c=1)로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물인 것을 특징으로 하는 리튬 이차 전지.
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Publication number | Priority date | Publication date | Assignee | Title |
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TWI624990B (zh) * | 2016-06-14 | 2018-05-21 | 財團法人工業技術研究院 | 電解質組成物及包含其之金屬離子電池 |
US10367227B2 (en) | 2016-06-14 | 2019-07-30 | Industrial Technology Research Institute | Electrolyte composition and metal-ion battery employing the same |
Also Published As
Publication number | Publication date |
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EP2790260A4 (en) | 2015-01-07 |
US9882239B2 (en) | 2018-01-30 |
EP2790260A1 (en) | 2014-10-15 |
US20140220427A1 (en) | 2014-08-07 |
EP2790260B1 (en) | 2016-03-23 |
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