WO2019108031A1 - Composition pour électrolyte polymérique en gel, électrolyte polymérique en gel préparé au moyen de celle-ci, et batterie secondaire au lithium le comprenant - Google Patents

Composition pour électrolyte polymérique en gel, électrolyte polymérique en gel préparé au moyen de celle-ci, et batterie secondaire au lithium le comprenant Download PDF

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WO2019108031A1
WO2019108031A1 PCT/KR2018/015122 KR2018015122W WO2019108031A1 WO 2019108031 A1 WO2019108031 A1 WO 2019108031A1 KR 2018015122 W KR2018015122 W KR 2018015122W WO 2019108031 A1 WO2019108031 A1 WO 2019108031A1
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group
compound
formula
polymer electrolyte
gel polymer
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PCT/KR2018/015122
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English (en)
Korean (ko)
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오정우
안경호
이철행
이정훈
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주식회사 엘지화학
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Priority claimed from KR1020180147637A external-priority patent/KR102287769B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to PL18883233.1T priority Critical patent/PL3660971T3/pl
Priority to US16/638,673 priority patent/US20210194052A1/en
Priority to EP18883233.1A priority patent/EP3660971B1/fr
Priority to CN201880053720.0A priority patent/CN111386624B/zh
Publication of WO2019108031A1 publication Critical patent/WO2019108031A1/fr

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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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • 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 composition for a gel polymer electrolyte, a gel polymer electrolyte prepared therefrom, and a lithium secondary battery comprising the gel polymer electrolyte. More particularly, the present invention relates to a gel polymer electrolyte composition for improving cell safety by suppressing side reactions by lithium salts, And a lithium secondary battery comprising the gel polymer electrolyte.
  • lithium secondary batteries having high energy density and voltage have been commercialized and widely used.
  • Lithium metal oxide is used as the positive electrode active material of the lithium secondary battery, and lithium metal, lithium alloy, crystalline or amorphous carbon or carbon composite material is used as the negative electrode active material.
  • the active material is coated on the current collector with an appropriate thickness and length, or the active material itself is coated in a film form and wound or laminated together with a separator as an insulator to form an electrode assembly.
  • the electrode assembly is then placed in a container such as a can or a pouch. To prepare a secondary battery.
  • the safety of a battery is improved in the order of a liquid electrolyte ⁇ gel polymer electrolyte ⁇ solid polymer electrolyte, while a cell electrolyte Is known to decrease.
  • a cell electrolyte Is known to decrease.
  • the solid polymer electrolyte is not yet commercialized due to inferior battery performance.
  • non-aqueous organic solvents are used in the electrolyte.
  • Propylene carbonate (EC) is conventionally used as a double non-aqueous organic solvent.
  • EC ethylene carbonate
  • it has a problem that it can cause irreversible decomposition reaction with graphite materials.
  • an ethylene / 3-component nonaqueous organic solvent including ethylene carbonate (EC) has been used.
  • ethylene carbonate has a high melting point, the use temperature is limited, and there is a problem that battery performance may be considerably deteriorated at a low temperature.
  • the performance of the battery may be deteriorated.
  • moisture may be contained in the active material during the manufacturing process, or may be contained in a trace amount in the electrolyte.
  • lithium titanium oxide used as an anode active material has a very low structural change during charging and discharging, is excellent in life characteristics due to a zero-strain material, forms a relatively high voltage band, It is known that it has excellent safety and stability and it has the advantage of having a rapid charging electrode characteristic that can be charged within a few minutes.
  • due to the property of absorbing moisture in the air There is a problem in that when the electrode is manufactured using such a material, water contained therein is decomposed to generate a large amount of gas.
  • the moisture present in the electrolyte can react with the electrolyte due to the potential energy provided in the charging process to generate a gas.
  • the cell may be swollen and the reliability of the battery may deteriorate.
  • LiPF 6 one of the lithium salts, reacts with water to form HF, which is a strong acid, which can react spontaneously with an electrode active material exhibiting weak basicity.
  • the electrode active material component is eluted by the above reaction, the battery performance is deteriorated and lithium fluoride (LiF) is formed on the surface of the positive electrode, resulting in electrical resistance in the electrode, and the lifetime of the battery is lowered. Therefore, it is necessary to inhibit the formation of HF in the electrolytic solution and to prevent HF from causing a side reaction.
  • Patent Document 1 Korean Patent Laid-Open No. 10-2009-0030237
  • an object of the present invention is to provide a gel polymer electrolyte having improved safety while suppressing the generation of HF which is an impurity generated from anions of lithium salts during charging, A gel polymer electrolyte prepared using the same, and a lithium secondary battery.
  • the present invention provides an oligomer comprising: an oligomer represented by Formula 1; additive; A polymerization initiator; Lithium salts; And a non-aqueous solvent,
  • the additive comprises at least one compound selected from the group consisting of an imide compound, a compound having a Si-N bond, a nitrile compound, a phosphate compound and a borate compound, and a composition for a gel polymer electrolyte .
  • Each of A and A ' is independently a unit containing a (meth) acrylate group
  • Each of C and C ' is independently a unit containing an oxyalkylene group
  • D is a unit containing a siloxane group
  • k is an integer of 1 to 100;
  • R 10 and R 10 ' are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms and a cycloalkyl group having 3 to 12 carbon atoms.
  • the compound having the Si-N bond may include a compound represented by the following formula (3).
  • R 11 is hydrogen or a silyl group in which the alkyl group having 1 to 5 carbon atoms is substituted or unsubstituted
  • R 12 and R 13 are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms
  • the hetero atom is selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms and a substituted or unsubstituted silyl group having an alkyl group having 1 to 5 carbon atoms
  • the hetero atom is selected from the group consisting of oxygen (O), nitrogen (N) (S). ≪ / RTI >
  • the nitrile compound may include at least one compound selected from the group consisting of compounds represented by the following formulas (4-1) and (4-2).
  • R 14 is selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms and a substituted or unsubstituted alkenyl group having 1 to 5 carbon atoms.
  • R 15 is selected from the group consisting of a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms and a substituted or unsubstituted alkenyl group having 1 to 5 carbon atoms.
  • the phosphate-based compound may include at least one compound selected from the group consisting of tris (trimethylsilyl) phosphate and tris (trimethyl) phosphate.
  • the borate compound may include at least one compound selected from the group consisting of lithium tetrafluoroborate and tris (trimethylsilyl) borate.
  • the oligomer of the present invention may include at least one compound selected from the group consisting of compounds represented by 1-1 to 1-5.
  • n, o and p are each independently an integer of 1 to 30, and q is an integer of 1 to 100.
  • the present invention provides a gel polymer electrolyte prepared using the composition for gel polymer electrolyte, and a lithium secondary battery comprising the gel polymer electrolyte.
  • composition for a gel polymer electrolyte By using the composition for a gel polymer electrolyte according to the present invention, formation of HF, which is an impurity generated during formation of an electrolyte, is inhibited and the cathode active material is prevented from being eluted, so that the capacity of the battery can be maintained at a certain level or more.
  • composition for a gel polymer electrolyte according to the present invention comprises an oligomer; additive; A polymerization initiator; Lithium salts; And non-aqueous solvents.
  • the oligomer may be three-dimensionally coupled through a polymerization reaction to form a polymer network, and includes a (meth) acrylate group, an amide group, an oxyalkylene group, and a siloxane group.
  • the lithium secondary battery can be divided into a lithium ion battery using a liquid electrolyte and a lithium polymer battery using a polymer electrolyte depending on the type of electrolyte used.
  • a lithium ion battery using a liquid electrolyte and a lithium polymer battery using a polymer electrolyte depending on the type of electrolyte used.
  • an ion conductive liquid electrolyte in which a lithium salt or the like is dissolved in a liquid electrolyte, particularly, a non-aqueous organic solvent has been mainly used.
  • the safety of a battery is improved in the order of liquid electrolyte ⁇ gel polymer electrolyte ⁇ solid polymer electrolyte, while battery performance is rather reduced.
  • the gel polymer electrolyte is disadvantageous in that the conductivity of the lithium ion is lower than that of the liquid electrolyte composed of the electrolyte solution.
  • the present invention aims to solve these problems by using a gel polymer electrolyte including a polymer network formed by three-dimensionally bonding the oligomer.
  • the degree of freedom of lithium ion is increased by the anion immobilization and stabilization, and the electric resistance is reduced to realize high lithium ion conductivity.
  • the polymer network formed of the oligomer has high heat resistance and high temperature durability, and has low volatility even at a high temperature, resulting in high electrochemical stability. Therefore, even when the lithium secondary battery is used in a high temperature environment or when the temperature inside the battery rises during driving of the battery, it is possible to control the amount of heat generation and suppress the occurrence of ignition, thereby improving the high temperature safety of the battery.
  • the oligomer may be represented by the following general formula (1).
  • D is a unit containing a siloxane group
  • k is an integer of 1 to 100.
  • k is preferably an integer of 1 to 50, more preferably an integer of 1 to 30.
  • the oligomer represented by Formula 1 has an appropriate weight average molecular weight (Mw).
  • the weight average molecular weight in the present specification may mean a value converted to standard polystyrene measured by GPC (Gel Permeation Chromatograph), and unless otherwise specified, the molecular weight may mean a weight average molecular weight.
  • the weight average molecular weight can be measured by Gel Permeation Chromatography (GPC). For example, after a sample of a certain concentration is prepared, the GPC measurement system alliance 4 apparatus is stabilized.
  • the weight average molecular weight (Mw) of the oligomer represented by Formula 1 may be controlled by the number of repeating units, and may be about 1,000 to 20,000, specifically 1,000 to 15,000, more specifically 1,000 to 10,000. When the weight average molecular weight of the oligomer is within the above range, it is possible to effectively improve the mechanical strength of the battery and to improve the processability (moldability) and the cell stability.
  • the units A and A ' are units containing a (meth) acrylate group so that oligomers are combined in a three-dimensional structure to form a polymer network.
  • the units A and A ' may be derived from monomers comprising at least one monofunctional or multifunctional (meth) acrylate or (meth) acrylic acid in the molecular structure.
  • the units A and A ' may each independently include at least one or more units represented by the following formulas (A-1) to (A-5).
  • each of R 1 's may independently be selected from the group consisting of hydrogen and a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms.
  • the ion transfer characteristic is controlled, and the function of controlling mechanical properties and adhesion is given .
  • the performance of the gel polymer electrolyte formed of an oligomer can be improved by stabilizing the anion generated by the side reaction of HF and suppressing the generation of HF.
  • the units B and B ' may each independently include a unit represented by the following formula (B-1).
  • R 2 represents a linear or non-linear alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, a substituted or unsubstituted bicycloalkylene group having 6 to 20 carbon atoms, At least one selected from the group consisting of an unsubstituted aryl group, a unit represented by the following formula: R 2 -1, and a unit represented by the following formula: R 2 -2.
  • the R 2 may include at least one or more units represented by the following general formulas R 2 -3 to R 2 -8.
  • the units C and C ' are each independently an oxyalkylene group-containing unit to increase dissociation of salts in the polymer network and increase affinity with a surface having a high polarity in a battery. More specifically, it is used to control the impregnation ability of the solvent, the electrode affinity and the ion transporting ability.
  • the units C and C ' may each independently include a unit represented by the following formula (C-1).
  • R 3 is a linear or non-linear alkylene group having 1 to 10 carbon atoms substituted or unsubstituted, and 1 is an integer of 1 to 30.
  • R 3 may be -CH 2 CH 2 - or -CHCH 3 CH 2 -.
  • the unit D is a unit containing a siloxane group and is intended to control the mechanical properties and the affinity with the separator. Specifically, a structure for securing flexibility other than the solid structural region due to the amide bond in the polymer network can be formed, and the affinity with the polyolefin separator membrane fabric can be increased by utilizing the low polarity. In particular, when the affinity with the polyolefin-based separator membrane is improved, the effect of reducing the resistance and further improving the ionic conductivity can be realized at the same time. On the other hand, when a siloxane group is contained, stabilization of anions generated by HF and inhibition of the generation of HF can improve the performance of the oligomer-containing gel polymer electrolyte.
  • the unit D may include a unit represented by the formula D-1.
  • R 8 and R 9 are linear or non-linear alkylene groups having 1 to 5 carbon atoms
  • R 4, R 5, R 6 and R 7 are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, An aryl group having 6 to 12 carbon atoms, and m is an integer of 1 to 500.
  • the above-mentioned m may more preferably be an integer of 10 to 500.
  • the polarity of the oligomer can be lowered, so that the wetting of the battery can be improved and the lithium dendrite (Li dendrite) is formed on the electrode by controlling the chemical reaction with the lithium metal So that the safety of the battery can be improved.
  • the unit D represented by the above formula (D-1) may be a unit represented by the following formula (D-2).
  • R 4, R 5, R 6, and R 7 are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
  • the unit D represented by the formula (D-2) may include one of the units represented by the following formulas (D-3) and (D-4).
  • m is an integer of 1 to 500, respectively. And more preferably an integer of 10 to 500.
  • the oligomer may be contained in an amount of 0.5 to 20 parts by weight, preferably 1.0 to 20 parts by weight, more preferably 1.5 to 20 parts by weight based on 100 parts by weight of the composition for a gel polymer electrolyte .
  • the content of the oligomer is less than 0.5 part by weight, a network reaction between oligomers for forming a gel polymer electrolyte is difficult to be formed.
  • the oligomer content exceeds 20 parts by weight, the gel polymer electrolyte has a viscosity exceeding a certain level, Impregnation, wetting degradation and electrochemical stability may be impaired.
  • the additive may include at least one compound selected from the group consisting of an imide compound, a compound having a Si-N bond, a nitrile compound, a phosphate compound and a borate compound.
  • the gel polymer electrolyte composition includes a lithium salt and a non-aqueous solvent in addition to an oligomer.
  • a fluoride-based lithium salt having a high ionic conductivity is widely used as a lithium salt.
  • the anions generated by the chemical reaction of the fluoride-based lithium salts react with a trace amount of water to produce by-products such as HF, and such by-products cause decomposition of the organic solvent and electrode side reactions, have.
  • the high temperature storability of the secondary battery may be deteriorated due to the negative ions and by-products.
  • PF 6 - which is an anion may lose electrons on the cathode side and PF 5 may be generated. At this time, the following chemical reactions can proceed in a cascade.
  • the decomposition of the organic solvent or the side reaction with the electrode may occur due to HF or other by-products generated, and the performance of the battery may be continuously deteriorated.
  • a method of removing water present in the electrolyte a method of suppressing the generation of HF by using an HF scavenger, a method of stabilizing and stabilizing anions generated from a lithium salt, and the like can be used.
  • the imide compound and the compound having the Si-N bond can fix the H 2 O as shown in the following reaction mechanism to remove moisture in the electrode, react with the anion generated from the lithium salt in the electrolyte It is possible to suppress the generation of HF which is an impurity.
  • the oligomer according to the present invention may be used together with an additive to form HF during the formation of the gel polymer electrolyte.
  • the HF may collapse the polymer structure, and the electrolyte may not be properly formed.
  • the gel polymer electrolyte can be easily formed by stabilizing anions generated by HF generation and HF.
  • the imide compound may include a carbodiimide compound represented by the following formula (2).
  • R 10 and R 10 ' are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms and a cycloalkyl group having 3 to 12 carbon atoms.
  • the imide compound is selected from the group consisting of N, N'-dicyclopentylcarbodiimide, N, N'-dicyclohexylcarbodiimide and N, N'-dicycloheptylcarbodiimide But it is not limited thereto.
  • the compound having Si-N bond may include a compound represented by the following general formula (3).
  • R 11 is hydrogen or a substituted or unsubstituted silyl group having 1 to 5 carbon atoms
  • R 12 and R 13 are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms
  • the hetero atom is selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms and a substituted or unsubstituted silyl group having an alkyl group having 1 to 5 carbon atoms
  • the hetero atom is selected from the group consisting of oxygen (O), nitrogen (N) (S). ≪ / RTI >
  • the compound represented by the general formula (3) is preferably selected from the group consisting of 1,1,1,3,3,3-hexamethyldisilazane, heptamethyldisilazane, N, N-diethylaminotrimethylsilane, O-tris (trimethylsilyl) hydroxyamine, and the like.
  • the compound having the Si-N bond can be 1,1,3,3,3-hexamethyldisilazane, but is not limited thereto.
  • the nitrile compound can stabilize and stabilize the lithium salt anion in the cell through a non-covalent electron pair in the nitrile.
  • the nitrile compound may include at least one compound selected from the group consisting of compounds represented by the following formulas (4-1) and (4-2).
  • R 14 is selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms and a substituted or unsubstituted alkenyl group having 1 to 5 carbon atoms.
  • R 15 is selected from the group consisting of a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms and a substituted or unsubstituted alkenyl group having 1 to 5 carbon atoms.
  • the nitrile compound is at least one compound selected from the group consisting of adiponitrile, succinonitrile, glutaronitrile, pimelonitrile, hept-3-adnitlinyl, And hex-3-enedinitrile.
  • the compounds represented by the above formulas (4-1) and (4-2) may be succinonitrile, but are not limited thereto.
  • the phosphate-based compound and the borate-based compound can inhibit the generation of HF as an HF scavenger. More specifically, an anion or a by-product (for example, PF 6 - or PF 5 ) produced from the lithium salt acts as a Lewis base, and the phosphate compound and the borate compound act as a Lewis acid ). At this time, the anion and the by-product may be stabilized by the Lewis acid-base reaction to inhibit the chain reaction.
  • an anion or a by-product for example, PF 6 - or PF 5
  • the phosphate-based compound may include at least one compound selected from the group consisting of tris (trimethylsilyl) phosphate and tris (trimethyl) phosphate.
  • the borate compound may include at least one compound selected from the group consisting of lithium tetrafluoroborate and tris (trimethylsilyl) borate.
  • the additive may be added in an amount of 0.1 to 30 parts by weight, preferably 0.1 to 10 parts by weight based on 100 parts by weight of the composition for a gel polymer electrolyte.
  • the content of the additive is within the above range, the gel polymer structure can be maintained by stabilizing the anion without deteriorating the battery performance.
  • the polymerization initiator is for polymerizing the oligomer of the present invention to form a polymer network bonded in a three-dimensional structure, and conventional polymerization initiators known in the art can be used without limitation.
  • the polymerization initiator may be a photo polymerization initiator or a thermal polymerization initiator depending on the polymerization method.
  • the photopolymerization initiator is exemplified by 2-hydroxy-2-methylpropiophenone (HMPP), 1-hydroxy-cyclohexylphenyl-ketone, benzophenone, 2- Phenyl-acetic acid, 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester, oxy-phenyl-acetic acid 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] (2,4,6-trimethylbenzoyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2- (Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (eta 5-2,4-cyclopentadien-1-yl), bis [2,6-difluoro- Methylphenyl iodonium, hexafluorophosphate, and
  • thermal polymerization initiator examples include benzoyl peroxide, acetyl peroxide, dilauryl peroxide, di-tert-butyl peroxide, t-butyl peroxy-2-ethyl-hexanoate, cumyl hydroperoxide and hydrogen peroxide, 2,2'-dicyclohexylcarbodiimide, Azobis (isobutyronitrile), azobis (2-cyanobutane), 2,2'-azobis (methylbutyronitrile), 2,2'-azobis And at least one compound selected from the group consisting of 2,2'-azobisdimethyl-valeronitrile (AMVN).
  • AMVN 2,2'-azobisdimethyl-valeronitrile
  • the polymerization initiator is decomposed by heat at 30 to 100 ° C in a battery or decomposed by light such as UV at room temperature (5 to 30 ° C) to form radicals, and crosslinking is effected by free radical polymerization So that the oligomer can be polymerized.
  • the polymerization initiator may be used in an amount of 0.01 to 5 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the oligomer.
  • the content of the polymerization initiator is used within the above range, the amount of the unreacted polymerization initiator which may adversely affect battery performance can be minimized.
  • gelation can be appropriately performed.
  • the lithium salt is used as an electrolyte salt in a lithium secondary battery and is used as an agent for transferring ions.
  • the lithium salt is selected from the group consisting of 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 3 SO 2 ) 3 , LiC 4 BO 8 , LiTFSI, LiFSI, and LiClO 4 , preferably LiPF 6 , but is not limited thereto .
  • the lithium salt may be contained at 0.5 to 5M, preferably 0.5 to 4M.
  • the content of the lithium salt is less than the above range, the lithium ion concentration in the electrolyte is low, so that the charge and discharge of the battery may not be performed properly. If the content exceeds the above range, the viscosity of the gel polymer electrolyte increases and wetting in the battery decreases So that the battery performance can be deteriorated.
  • the non-aqueous solvent is, for example, ether, ester (Acetate, Propionate), amide, linear carbonate or cyclic carbonate, nitrile (acetonitrile, SN etc.) May be used alone or in combination of two or more.
  • a carbonate-based electrolyte solvent containing a carbonate compound which is typically a cyclic carbonate, a linear carbonate, or a mixture thereof, may be used.
  • cyclic carbonate compound examples include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, Carbonate, vinylene carbonate, and halides thereof, or a mixture of at least two or more thereof.
  • linear carbonate compound examples include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC) and ethyl propyl carbonate (EPC) , Or a mixture of at least two of these compounds may be used.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • DPC dipropyl carbonate
  • EMC ethyl methyl carbonate
  • MPC methyl propyl carbonate
  • EPC ethyl propyl carbonate
  • EPC ethyl propyl carbonate
  • EPC e
  • propylene carbonate and ethylene carbonate which are cyclic carbonates in the carbonate electrolyte solution, are highly viscous organic solvents having a high dielectric constant and can dissociate the lithium salt in the electrolytic solution well.
  • cyclic carbonates such as ethylmethyl carbonate, diethyl carbonate Or a low viscosity, low dielectric constant linear carbonate such as dimethyl carbonate in an appropriate ratio can be used to more advantageously use an electrolytic solution having a high electrical conductivity.
  • esters in the electrolyte solvent examples include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate,? -Butyrolactone,? -Valerolactone,? -Caprolactone,? -Valerolactone And? -Caprolactone, or a mixture of at least two of them, but the present invention is not limited thereto.
  • composition for a gel polymer electrolyte according to an embodiment of the present invention may further include other additives capable of realizing such physical properties known in the art in order to increase the efficiency of polymer network formation reaction and reduce resistance of the oligomer, , Inorganic particles, and the like.
  • Examples of the other additives include VC (vinylene carbonate), VEC (vinyl ethylene carbonate), PS (propane sultone), SN (succinonitrile), AdN (adiponitrile), ESa (ethylene sulfate), PRS , TMSPa (3-trimethoxysilanyl-propyl-N-aniline), TMSPi (Tris (trimethylsilyl) Phosphite), LiPO 2 F 2 , LiODFB (Lithium difluorooxalatoborate), LiBOB (Lithium bis- , LiBF 4, and the like.
  • the inorganic particles may be BaTiO 3 , BaTiO 3 , Pb (Zr, Ti) O 3 (PZT), Pb 1 -a La a Zr 1-b Ti b O 3 (PLZT, Pb (Mg 1/3 Nb 2/3 ) O 3 -PbTiO 3 (PMN-PT), hafnia (HfO 2 ), SrTiO 3 , SnO 2 , CeO 2 2 , MgO, NiO, CaO, ZnO, ZrO 2 , Y 2 O 3 , Al 2 O 3 , TiO 2 , SiC and mixtures thereof, or a mixture of at least two or more thereof .
  • inorganic particles having lithium ion transferring ability that is, lithium phosphate (Li 3 PO 4 ), lithium titanium phosphate (Li c Ti d (PO 4 ) 3 , 0 ⁇ d ⁇ 2, 0 ⁇ d ⁇ 3) as phosphate (Li a1 Al b1 Ti c1 ( PO 4) 3, 0 ⁇ a1 ⁇ 2, 0 ⁇ b1 ⁇ 1, 0 ⁇ c1 ⁇ 3), 14Li 2 O-9Al 2 O 3 -38TiO 2 -39P 2 O 5 like (LiAlTiP) a2 O b2 series glass (glass) (0 ⁇ a2 ⁇ 4, 0 ⁇ b2 ⁇ 13), lithium lanthanum titanate (Li a3 La b3 TiO 3, 0 ⁇ a3 ⁇ 2, 0 ⁇ b3 ⁇ 3) (Li a4 Ge b4 P c2 S d , 0 ⁇ a4 ⁇ 4, 0 ⁇ b
  • the gel polymer electrolyte is prepared using the gel polymer electrolyte composition.
  • the gel polymer electrolyte according to the present invention is characterized in that fluorine is a unit A comprising a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, units B and B 'each independently containing an amide group, By forming a polymer network with oligomers comprising units C and C 'comprising an acrylate group, ionic conductivity and mechanical properties can be improved.
  • the gel polymer electrolyte composition of the present invention contains an additive, when the electrolyte is prepared from the gel polymer electrolyte composition, the formation of HF or the reaction of HF with the electrolyte can be inhibited, .
  • the gel polymer electrolyte according to the present invention is formed by polymerizing a composition for a gel polymer electrolyte according to a conventional method known in the art.
  • gel polymer electrolytes can be prepared by in-situ polymerization or coating polymerization.
  • the in-situ polymerization includes the steps of (a) inserting an electrode assembly comprising a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode into a battery case, and (b) And injecting a composition for a gel polymer electrolyte according to the method of the present invention, followed by polymerization, to prepare a gel polymer electrolyte.
  • the in-situ polymerization in the lithium secondary battery can be performed by E-BEAM, gamma ray, room temperature / high temperature aging process, and may be performed through thermal polymerization or photopolymerization according to one embodiment of the present invention.
  • the polymerization time is about 2 minutes to 12 hours
  • the thermal polymerization temperature may be 30 to 100 ° C
  • the light polymerization temperature may be room temperature (5 to 30 ° C).
  • an in-situ polymerization reaction in a lithium secondary battery is performed by injecting the gel polymer electrolyte composition into a battery cell, and then gelating through a polymerization reaction to form a gel polymer electrolyte.
  • the gel polymer electrolyte composition may be coated on one surface of an electrode and a separator, cured (gelled) using heat such as heat or UV, and then the electrode and / The electrode assembly may be manufactured by inserting the electrode assembly into the battery case and reusing the existing liquid electrolyte.
  • a secondary battery according to another embodiment of the present invention includes a cathode, an anode, a separator interposed between the anode and the cathode, and a gel polymer electrolyte.
  • the gel polymer electrolyte is the same as that described above, so a detailed description thereof will be omitted.
  • the anode may be prepared by coating a cathode mixture slurry containing a cathode active material, a binder, a conductive material, and a solvent on a cathode collector.
  • the positive electrode collector is not particularly limited as long as it has electrical conductivity without causing chemical change in the battery.
  • the positive electrode collector may be formed of a metal such as carbon, stainless steel, aluminum, nickel, titanium, sintered carbon, , Nickel, titanium, silver, or the like may be used.
  • the cathode active material is a compound capable of reversibly intercalating and deintercalating lithium, and may specifically include a lithium composite metal oxide including lithium and at least one metal such as cobalt, manganese, nickel, or aluminum have. More specifically, the lithium composite metal oxide may be at least one selected from the group consisting of lithium-manganese-based oxides (for example, LiMnO 2 and LiMn 2 O 4 ), lithium-cobalt oxides (for example, LiCoO 2 ), lithium- (for example, LiNiO 2 and the like), lithium-nickel-manganese-based oxide (for example, LiNi 1-Y1 Mn Y1 O 2 (here, 0 ⁇ Y1 ⁇ 1), LiMn 2-z1 Ni z1 O 4 ( here, 0 ⁇ Z1 ⁇ 2) and the like), lithium-nickel-cobalt oxide (e.
  • LiMnO 2 and LiMn 2 O 4 lithium-cobalt oxides
  • LiCoO 2 lithium-
  • lithium-manganese-cobalt oxide e. g., LiCo 1-Y3 Mn Y3 O 2 (here, 0 ⁇ Y3 ⁇ 1), LiMn 2-z2 Co z2 O 4 ( here, 0 ⁇ z2 ⁇ 2) and the like
  • the lithium composite metal oxide may be LiCoO 2 , LiMnO 2 , LiNiO 2 , lithium nickel manganese cobalt oxide (for example, Li (Ni 0.6 Mn 0.2 Co 0.2 ) O 2 , Li (Ni 0.5 Mn 0.3 Co 0.2) O 2 or Li (Ni 0.8 Mn 0.1 Co 0.1 ) O 2 ), or lithium nickel cobalt aluminum oxide (e.g., LiNi 0.8 Co 0.15 Al 0.05 O 2 , etc.) or the like Considering the remarkable improvement effect according to the kind and content ratio of constituent elements forming the lithium composite metal oxide, the lithium composite metal oxide is Li (Ni 0.6 Mn 0.2 Co 0.2 ) O 2 , Li (Ni 0.5 Mn 0.3 Co 0.2 ) O 2, Li (Ni 0.7 Mn 0.15 Co 0.15) O 2 or Li (Ni 0.8 Mn 0.1 Co 0.1 ) O 2 and the like, any one or a mixture of two or more may be used of which have.
  • the cathode active material may be contained in the cathode mixture slurry in an amount of 60 to 98% by weight, preferably 70 to 98% by weight, more preferably 80 to 98% by weight, based on the total weight of the solids excluding the solvent have.
  • the binder is a component that assists in bonding of the active material to the conductive material and bonding to the current collector.
  • binders examples include polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene (PE) , Ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers and the like.
  • CMC carboxymethylcellulose
  • EPDM Ethylene-propylene-diene terpolymer
  • EPDM Ethylene-propylene-diene terpolymer
  • EPDM Ethylene-propylene-diene terpolymer
  • sulfonated EPDM styrene-butadiene rubber
  • fluorine rubber various copolymers and the like.
  • the binder is included in the positive electrode material mixture slurry in an amount of 1% by weight to 20% by weight, preferably 1% by weight to 15% by weight, more preferably 1% by weight to 10% by weight, based on the total weight of the solids excluding the solvent .
  • the conductive material is a component for further improving the conductivity of the cathode active material.
  • the conductive material is not particularly limited as long as it has electrical conductivity without causing chemical changes in the battery, for example, graphite; Carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black; Conductive fibers such as carbon fiber and metal fiber; Metal powders such as carbon fluoride, aluminum, and nickel powder; Conductive whiskey such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • Carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black
  • Conductive fibers such as carbon fiber and metal fiber
  • Metal powders such as carbon fluoride, aluminum, and nickel powder
  • Conductive whiskey such as zinc oxide and potassium titanate
  • Conductive metal oxides such as titanium oxide
  • Conductive materials such as polyphenylene derivatives and the like can be used.
  • acetylene black series such as Chevron Chemical Company, Denka Singapore Private Limited, Gulf Oil Company, etc.
  • Ketjenblack EC (Armak Company)
  • Vulcan XC-72 Cabot Company
  • Super P Tucal
  • the conductive material is used in an amount of 1 to 20% by weight, preferably 1 to 15% by weight, more preferably 1 to 10% by weight, based on the total weight of the solid material excluding the solvent, .
  • the solvent may include an organic solvent such as NMP (N-methyl-2-pyrrolidone), and may be used in an amount that makes it desirable to contain the cathode active material, and optionally, a binder and a conductive material .
  • concentration of the solid content including the positive electrode active material, and optionally the binder and the conductive material is 50 wt% to 95 wt%, preferably 70 wt% to 95 wt%, more preferably 70 wt% to 90 wt% %. ≪ / RTI >
  • the negative electrode may be prepared, for example, by coating a negative electrode current collector with a negative electrode mixture slurry containing a negative electrode active material, a binder, a conductive material and a solvent, or a carbon (C) electrode or metal itself as a negative electrode.
  • the negative electrode collector when a negative electrode is manufactured by coating a negative electrode mixture slurry on the negative electrode collector, the negative electrode collector generally has a thickness of 3 to 500 ⁇ m.
  • the negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • the negative electrode current collector include copper, stainless steel, aluminum, nickel, titanium, sintered carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver or the like, aluminum-cadmium alloy, or the like can be used.
  • fine unevenness can be formed on the surface to enhance the bonding force of the negative electrode active material, and it can be used in various forms such as films, sheets, foils, nets, porous bodies, foams and nonwoven fabrics.
  • Examples of the negative electrode active material include natural graphite, artificial graphite, carbonaceous material; Lithium-containing titanium composite oxide (LTO), metals (Me) with Si, Sn, Li, Zn, Mg, Cd, Ce, Ni or Fe; An alloy composed of the metal (Me); An oxide of the metal (Me) (MeOx); And a composite of the metal (Me) and the carbon (C).
  • LTO Lithium-containing titanium composite oxide
  • Me metals with Si, Sn, Li, Zn, Mg, Cd, Ce, Ni or Fe
  • An alloy composed of the metal (Me) An oxide of the metal (Me) (MeOx)
  • a composite of the metal (Me) and the carbon (C) a composite of the metal (Me) and the carbon (C).
  • the negative electrode active material may include 80 wt% to 99 wt%, preferably 85 wt% to 99 wt%, and more preferably 90 wt% to 98 wt% based on the total weight of the solid material excluding the solvent in the negative electrode material mixture slurry have.
  • the binder is a component that assists in bonding between the conductive material, the active material, and the current collector.
  • binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • CMC carboxymethylcellulose
  • EPDM ethylene-propylene-diene polymer
  • sulfonated-EPDM styrene-butadiene rubber
  • fluorine rubber various copolymers thereof.
  • the binder is used in an amount of 1 wt% to 20 wt%, preferably 1 wt% to 15 wt%, more preferably 1 wt% to 10 wt% based on the total weight of the solid material excluding the solvent in the negative electrode material mixture slurry .
  • the conductive material is a component for further improving the conductivity of the negative electrode active material.
  • a conductive material is not particularly limited as long as it has electrical conductivity without causing chemical changes in the battery, for example, graphite such as natural graphite or artificial graphite; Carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black; Conductive fibers such as carbon fiber and metal fiber; Metal powders such as carbon fluoride, aluminum, and nickel powder; Conductive whiskey such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • the conductive material may include 1 wt% to 20 wt%, preferably 1 wt% to 15 wt%, and more preferably 1 wt% to 10 wt% based on the total weight of the solid material excluding the solvent in the negative electrode material mixture slurry .
  • the solvent may include water or an organic solvent such as NMP (N-methyl-2-pyrrolidone), and may be used in an amount that is preferred to contain the negative electrode active material, and optionally a binder and a conductive material.
  • concentration of the solid material including the negative electrode active material, and optionally the binder and the conductive material may be 50 wt% to 95 wt%, preferably 70 wt% to 90 wt%.
  • the negative electrode When the metal itself is used as the negative electrode, the negative electrode may be manufactured by a method of physically bonding a metal to the metal thin film itself or the negative electrode collector, followed by rolling or vapor deposition. The deposition may be performed using an electric or chemical vapor deposition method.
  • the metal to be bonded / rolled / deposited on the metal thin film itself or on the negative electrode current collector may include lithium (Li), nickel (Ni), tin (Sn), copper (Cu), and indium Or an alloy of two kinds of metals, and the like.
  • a conventional porous polymer film conventionally used as a separator for example, a polyolefin such as an ethylene homopolymer, a propylene homopolymer, an ethylene / butene copolymer, an ethylene / hexene copolymer, and an ethylene / methacrylate copolymer
  • a porous polymer film made of a high molecular weight polymer may be used alone or in a laminated manner, or a nonwoven fabric made of a conventional porous nonwoven fabric such as a glass fiber having a high melting point, a polyethylene terephthalate fiber or the like may be used. It is not.
  • the external shape of the lithium secondary battery of the present invention is not particularly limited, but may be a cylindrical shape, a square shape, a pouch shape, a coin shape, or the like using a can.
  • a battery module including the lithium secondary battery as a unit cell and a battery pack including the same. Since the battery module and the battery pack include the lithium secondary battery having a high capacity, a high rate-limiting characteristic, and a cycling characteristic, the battery module and the battery pack can be suitably used as a middle- or large- And can be used as a power source of the device.
  • Ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed in a volume ratio of 3: 7, and 0.7 M of LiPF 6 and 0.3 M of LiFSI were added to prepare a mixed solvent. Then, 91.78 g of the mixed solvent 5 g of an oligomer (weight average molecular weight: 5000) of 1 to 5 and 0.2 g of N, N'-dicyclohexylcarbodiimide as an additive, 0.02 g of a polymerization initiator (AIBN), 1.5 g of vinylene carbonate g, 0.5 g of propane sultone (PS) and 1 g of ethylene sulfate (ESa) were added to prepare a gel polymer electrolyte composition.
  • AIBN polymerization initiator
  • PS propane sultone
  • ESa ethylene sulfate
  • a positive electrode active material LiNi 1/3 Co 1/3 Mn 1/3 O 2 ; NCM
  • carbon black 3% by weight
  • PVDF 3% by weight
  • NMP solvent N-methyl -2-pyrrolidone
  • the positive electrode material mixture slurry was applied to an aluminum (Al) thin film as a positive electrode current collector having a thickness of about 20 mu m, dried, and then rolled to produce a positive electrode.
  • the 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 material to 96 wt%, 3 wt% and 1 wt%, respectively, as a solvent.
  • the negative electrode material mixture slurry was applied to a copper (Cu) thin film as an anode current collector having a thickness of 10 mu m, dried, and then rolled to produce a negative electrode.
  • the electrode assembly was manufactured using the separator composed of the anode, the cathode and the three layers of polypropylene / polyethylene / polypropylene (PP / PE / PP). After the composition for the gel polymer electrolyte was injected into the electrode assembly, Followed by heating at 60 DEG C for 24 hours to prepare a lithium secondary battery containing the gel polymer electrolyte.
  • PP / PE / PP polypropylene / polyethylene / polypropylene
  • Example 1 except that 0.5 g of 1,1,3,3,3-hexamethyldisilazane was used instead of 0.2 g of N, N'-dicyclohexylcarbodiimide as an additive, 1, a lithium secondary battery including a gel polymer electrolyte was prepared .
  • Example 1 0.5 g of 1,1,1,3,3,3-hexamethyldisilazane and 2 g of succinonitrile were used instead of 0.2 g of N, N'-dicyclohexylcarbodiimide as an additive. And adiponitrile (2 g) were added to the lithium secondary battery, a lithium secondary battery including a gel polymer electrolyte was prepared.
  • Example 2 In the same manner as in Example 1 except that 2 g of lithium tetrafluoroborate was used instead of 0.2 g of N, N'-dicyclohexylcarbodiimide as an additive in Example 1, lithium containing a gel polymer electrolyte A secondary battery was manufactured.
  • Ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed at a volume ratio of 3: 7, and LiPF 6 and LiFSI 0.3M were added. Then, 1.5 g of Vinylene Carbonate (VC) , 0.5 g of propane sultone (PS) and 1 g of ethylene sulfate (ESa) were added to prepare an electrolytic solution.
  • VC Vinylene Carbonate
  • PS propane sultone
  • ESa ethylene sulfate
  • a positive electrode active material LiNi 1/3 Co 1/3 Mn 1/3 O 2 ; NCM
  • carbon black 3% by weight
  • PVDF 3% by weight
  • NMP solvent N-methyl -2-pyrrolidone
  • the positive electrode material mixture slurry was applied to an aluminum (Al) thin film as a positive electrode current collector having a thickness of about 20 mu m, dried, and then rolled to produce a positive electrode.
  • the 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 material to 96 wt%, 3 wt% and 1 wt%, respectively, as a solvent.
  • the negative electrode material mixture slurry was applied to a copper (Cu) thin film as an anode current collector having a thickness of 10 mu m, dried, and then rolled to produce a negative electrode.
  • the electrode assembly was manufactured using the separator composed of the anode, the cathode and the three layers of polypropylene / polyethylene / polypropylene (PP / PE / PP), and the prepared electrolyte was injected into the electrode assembly to produce a lithium secondary battery .
  • PP / PE / PP polypropylene / polyethylene / polypropylene
  • Example 2 In the same manner as in Example 1 except that 5 g of an oligomer composed of dipentaerythritol pentaacrylate instead of 5 g of the oligomer of the formula (1-5) was used as the oligomer in Example 1, A lithium secondary battery including a polymer electrolyte was prepared.
  • Example 1 a lithium secondary battery including a gel polymer electrolyte was prepared in the same manner as in Example 1, except that an additive was not used.
  • the lithium secondary batteries prepared according to Examples 1 to 5 and Comparative Examples 1 to 3 were set to have a SOC (state of charge) of 50% at 25 ° C., followed by discharging for 10 seconds at 2.5 C rate discharge pulse , And the resistance value for each lithium secondary battery was confirmed through the voltage drop at that time.
  • SOC state of charge
  • the measured resistance values and voltage drop values are shown in Table 1 below.
  • the lithium secondary batteries prepared according to Examples 1 to 5 and Comparative Examples 1 to 3 were allowed to stand for 1 hour under conditions of SOC 50% and 25 ° C, and were then scanned to 1 KHz-1 mHz.
  • the Rct resistance ) Were measured and are shown in Table 2. At this time, the amplitude of the alternating current was 10 mV, and the DC potential of the battery was 3.68 V.
  • the Rct resistance in the battery manufactured by the comparative examples is larger. This indicates that the Rct resistance (interfacial resistance) is larger due to the side reaction induced from the anion of the salt, as compared with the battery produced by the embodiments.
  • Each of the secondary batteries prepared according to Examples 1 to 5 and Comparative Examples 1 to 3 was stored at a high temperature for 10 weeks (10weeks) under a condition of SOC 100% (4.15 V) at a temperature of 60 ° C. Thereafter, the SOC 50% was set at 25 per foot for each week, and the resistance value was measured by discharging for 10 seconds with a discharge pulse at 5C rate. Then, the resistance was measured based on the resistance value measured at the initial (0 week) The rate of change was measured. The results are shown in Table 3 below.

Abstract

La présente invention concerne une composition pour électrolyte polymérique en gel, un électrolyte polymérique en gel préparé au moyen de celle-ci, et une batterie secondaire au lithium, la composition comprenant : un oligomère représenté par la formule chimique (1); un additif; un initiateur de polymérisation; des sels de lithium; et un solvant non aqueux. L'additif comprend un ou plusieurs composés choisis dans le groupe constitué par un composé à base d'imide, un composé ayant une liaison Si-N, un composé à base de nitrile, un composé à base de phosphate et un composé à base de borate.
PCT/KR2018/015122 2017-11-30 2018-11-30 Composition pour électrolyte polymérique en gel, électrolyte polymérique en gel préparé au moyen de celle-ci, et batterie secondaire au lithium le comprenant WO2019108031A1 (fr)

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PL18883233.1T PL3660971T3 (pl) 2017-11-30 2018-11-30 Kompozycja żelowego elektrolitu polimerowego, wytworzony z niej żelowy elektrolit polimerowy i zawierający go akumulator litowy
US16/638,673 US20210194052A1 (en) 2017-11-30 2018-11-30 Composition for gel polymer electrolyte, gel polymer electrolyte prepared therefrom, and lithium secondary battery including the same
EP18883233.1A EP3660971B1 (fr) 2017-11-30 2018-11-30 Composition d'électrolyte gel polymère, électrolyte gel polymère préparé à partir de celui-ci, et batterie secondaire au lithium comprenant celui-ci
CN201880053720.0A CN111386624B (zh) 2017-11-30 2018-11-30 用于凝胶聚合物电解质的组合物、由该组合物制备的凝胶聚合物电解质和包括该凝胶聚合物电解质的锂二次电池

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111430780A (zh) * 2020-04-28 2020-07-17 孚能科技(赣州)股份有限公司 电解液原料组合物，电解液及锂离子二次电池及其制备方法
CN111430779A (zh) * 2020-04-28 2020-07-17 孚能科技(赣州)股份有限公司 电解液原料组合物，电解液及锂离子二次电池及其制备方法
CN114388886A (zh) * 2021-12-28 2022-04-22 广东马车动力科技有限公司 一种聚合物电解质及其制备方法、二次电池
CN114725504A (zh) * 2022-04-29 2022-07-08 远景动力技术(江苏)有限公司 凝胶电解质及其应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060075970A (ko) * 2004-12-29 2006-07-04 주식회사 엘지화학 니트릴기 함유 화합물이 첨가된 전해액을 포함하는 리튬이차 전지 및 이의 제조방법
KR20090030237A (ko) 2007-09-19 2009-03-24 주식회사 엘지화학 비수 전해액 리튬 이차전지
KR20140099864A (ko) * 2011-10-05 2014-08-13 원드 매터리얼 엘엘씨 리튬 이온 배터리용 실리콘 나노구조체 활물질, 및 그에 관련된 공정, 조성물, 구성요소 및 디바이스
KR20150014185A (ko) * 2013-07-29 2015-02-06 주식회사 엘지화학 이차전지용 액체 전해질 및 이를 포함하는 리튬 이차전지
KR20160040128A (ko) * 2014-10-02 2016-04-12 주식회사 엘지화학 젤 폴리머 전해질 및 이를 포함하는 리튬 이차전지
KR20170034313A (ko) * 2015-09-18 2017-03-28 울산과학기술원 리튬 이차 전지용 전해질 첨가제 및 이의 제조 방법, 상기 첨가제를 포함하는 전해질 및 이의 제조 방법, 및 상기 첨가제를 포함하는 리튬 이차 전지리튬 이차 전지

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060075970A (ko) * 2004-12-29 2006-07-04 주식회사 엘지화학 니트릴기 함유 화합물이 첨가된 전해액을 포함하는 리튬이차 전지 및 이의 제조방법
KR20090030237A (ko) 2007-09-19 2009-03-24 주식회사 엘지화학 비수 전해액 리튬 이차전지
KR20140099864A (ko) * 2011-10-05 2014-08-13 원드 매터리얼 엘엘씨 리튬 이온 배터리용 실리콘 나노구조체 활물질, 및 그에 관련된 공정, 조성물, 구성요소 및 디바이스
KR20150014185A (ko) * 2013-07-29 2015-02-06 주식회사 엘지화학 이차전지용 액체 전해질 및 이를 포함하는 리튬 이차전지
KR20160040128A (ko) * 2014-10-02 2016-04-12 주식회사 엘지화학 젤 폴리머 전해질 및 이를 포함하는 리튬 이차전지
KR20170034313A (ko) * 2015-09-18 2017-03-28 울산과학기술원 리튬 이차 전지용 전해질 첨가제 및 이의 제조 방법, 상기 첨가제를 포함하는 전해질 및 이의 제조 방법, 및 상기 첨가제를 포함하는 리튬 이차 전지리튬 이차 전지

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111430780A (zh) * 2020-04-28 2020-07-17 孚能科技(赣州)股份有限公司 电解液原料组合物，电解液及锂离子二次电池及其制备方法
CN111430779A (zh) * 2020-04-28 2020-07-17 孚能科技(赣州)股份有限公司 电解液原料组合物，电解液及锂离子二次电池及其制备方法
CN111430780B (zh) * 2020-04-28 2023-03-28 孚能科技(赣州)股份有限公司 电解液原料组合物，电解液及锂离子二次电池及其制备方法
CN114388886A (zh) * 2021-12-28 2022-04-22 广东马车动力科技有限公司 一种聚合物电解质及其制备方法、二次电池
CN114388886B (zh) * 2021-12-28 2022-09-27 广东马车动力科技有限公司 一种聚合物电解质及其制备方法、二次电池
CN114725504A (zh) * 2022-04-29 2022-07-08 远景动力技术(江苏)有限公司 凝胶电解质及其应用
CN114725504B (zh) * 2022-04-29 2023-10-31 远景动力技术(江苏)有限公司 凝胶电解质及其应用

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