WO2017061807A1 - 전극조립체를 구성하는 분리막의 기공 내에 겔화 전해액 성분을 포함하고 있는 전지셀 - Google Patents
전극조립체를 구성하는 분리막의 기공 내에 겔화 전해액 성분을 포함하고 있는 전지셀 Download PDFInfo
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- WO2017061807A1 WO2017061807A1 PCT/KR2016/011219 KR2016011219W WO2017061807A1 WO 2017061807 A1 WO2017061807 A1 WO 2017061807A1 KR 2016011219 W KR2016011219 W KR 2016011219W WO 2017061807 A1 WO2017061807 A1 WO 2017061807A1
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- battery cell
- electrolyte
- separator
- pores
- liquid
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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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- 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
-
- 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
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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
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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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
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic 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
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a battery cell containing a gelling electrolyte component in the pores of the separator constituting the electrode assembly.
- lithium secondary batteries such as lithium ion batteries and lithium ion polymer batteries is high.
- secondary batteries are classified according to the structure of an electrode assembly having a structure in which a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode are formed.
- Jelly-roll type electrode assembly having a structure wound in a state where a separator is interposed, a stack type electrode assembly in which a plurality of anodes and cathodes cut in units of a predetermined size are sequentially stacked with a separator therebetween
- an electrode assembly having an advanced structure which is a mixed form of the jelly-roll type and the stack type has a predetermined unit.
- Stacked / foldable electrode having a structure in which positive and negative electrodes are sequentially wound in a state in which unit cells stacked on a separator film are stacked with a separator interposed therebetween Developed body lip.
- the secondary battery is a cylindrical battery and a rectangular battery in which the electrode assembly is embedded in a cylindrical or rectangular metal can according to the shape of the battery case, and a pouch type battery in which the electrode assembly is embedded in a pouch type case of an aluminum laminate sheet. Are classified.
- a pouch-type battery having a stacked or stacked / folding electrode assembly in a pouch-type battery case of an aluminum laminate sheet has attracted much attention due to its low manufacturing cost, small weight, and easy shape deformation. And its usage is gradually increasing.
- such a secondary battery is coated with an electrode mixture containing an electrode active material, a conductive agent, a binder, and the like on an electrode current collector, followed by drying to prepare an electrode, and stacking the prepared electrode together with a separator, followed by an electrolyte solution. It is completed by being built and sealed in a battery case together with it.
- the separator is an insulating thin film having high ion permeability and mechanical strength, and has a structure including pores having a predetermined diameter, and in detail, an olefin polymer such as polypropylene having chemical resistance and hydrophobicity ; Sheets or non-woven fabrics made of glass fibers or polyethylene are used.
- an olefin polymer such as polypropylene having chemical resistance and hydrophobicity
- Sheets or non-woven fabrics made of glass fibers or polyethylene are used.
- the solid electrolyte such as a polymer
- the solid electrolyte may also serve as a separator.
- Such a separator may be advantageous for the movement of lithium ions when the pore size or the porosity is high, but the insulation performance exerted between the positive electrode and the negative electrode may be deteriorated, thereby degrading the safety of the battery. Can be.
- the solid electrolyte also serves as a separator, there is an advantage in that gas generation in the battery is reduced or safety is improved.
- impregnation and ion conductivity are low, and thus battery performance is deteriorated.
- the present invention aims to solve the problems of the prior art as described above and the technical problems that have been requested from the past.
- the inventors of the present application configure the gelated electrolyte component to be included in the plurality of pores formed in the separator, so that the pores having a large diameter can be obtained.
- the separator by improving the insulation between the positive electrode and the negative electrode, it is possible to ensure the safety of the battery cell, to prevent the deterioration of ionic conductivity due to the closing of the pores, and to maintain a high electrolyte solution impregnation, Completion of the present invention confirms that it is possible to prevent the performance degradation of the cell, and to improve the stability by preventing the heat shrinkage of the separator according to the temperature change of the battery cell, compared to the structure containing only the liquid electrolyte solution, Reached.
- It includes an electrode assembly having a structure interposed between the anode and the cathode, the separator is formed with a plurality of pores, the pores may be a structure containing a gelated electrolyte component in the pores have.
- the pores formed in the separator may have an average diameter of 0.01 ⁇ m to 100 ⁇ m, more specifically, may be 1 ⁇ m to 10 ⁇ m.
- the separator may have a porosity of 40% to 90%.
- the average diameter and porosity of the pores is too small out of the above range, the effect of preventing ion conductivity deterioration may not be exhibited, or the gelled electrolyte component may not be sufficiently contained, and electrolyte solution impregnation may be deteriorated.
- the electrolyte component may be a structure that is polymerized or cured after the liquid mixture is impregnated into the pores of the membrane by impregnating the separator in a liquid mixture including a liquid monomer and / or oligomer electrolyte component and a polymerization initiator.
- the electrolyte component contained in the pores of the separation membrane is not a structure that is inserted into the pores after gelation, and a mixed solution containing a monomer and / or oligomer electrolyte composition of the liquid phase and a polymerization initiator After being inserted into the pores of the separator, polymerization or curing can be performed to form a stably gelled structure in the pores of the separator.
- the pores of the separator may be a structure connected to each other in a three-dimensional network structure, whereby a mixed solution containing a liquid monomer and / or oligomer electrolyte component and a polymerization initiator into the pores of the separator more easily. Can be inserted.
- the polymerized or cured electrolyte components may be connected to each other in a three-dimensional network structure, thereby improving structural stability.
- the pores of the separator may be a structure formed independently of course.
- the electrolyte and component of the monomer and / or oligomer state of the liquid phase is a polyethylene derivative, polyethylene oxide derivative, polypropylene oxide derivative, phosphate ester polymer, poly etchation lysine, polyester sulfide, At least one selected from the group consisting of polyvinyl alcohol, polyvinylidene fluoride, or a polymer containing an ionic dissociation group.
- the electrolyte component is not limited thereto, and in detail, Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Li 4 SiO 4 -LiI-LiOH, Li 3 PO 4 -Li 2 It may contain one or more selected from the group consisting of a halide, sulfate of Li, such as S-SiS 2 . .
- the electrolyte solution component may include the same component as the organic solid electrolyte or the inorganic solid electrolyte.
- the polymerization initiator may gel the electrolyte solution component in the monomer and / or oligomer state of the liquid phase by heat or light applied from the outside.
- the polymerization initiator serves to polymerize or cure an electrolyte component in a monomer and / or oligomer state in a liquid phase by a stimulus applied from the outside, and specifically, gel the electrolyte component by heat or light.
- the polymerization initiator may gel the electrolyte component by heat.
- the liquid electrolyte component inserted into the pores of the separator may be a structure that is polymerized or cured for 1 to 20 hours in the temperature range of 40 °C to 90 °C.
- the separator may not be impregnated with the mixed solution containing the electrolyte component in a liquid state.
- the cost and time for polymerizing or curing the electrolyte component may increase.
- the polymerization initiator may be polymerized or cured under the conditions of the temperature and time, so as to maintain a stable gelled state in the pores of the separator, while not impairing the electrochemical performance of the battery cell.
- benzoyl peroxide BPO
- acetyl peroxide Dilauryl peroxide, Di-tertbutylperoxide, cumyl Cumulative hydroperoxide, Hydrogen peroxide, 2,2-Azobis (2-cyanobutane), 2,2-Azobis (Methylbutyronitrile), AIBN (Azobis (iso-butyronitrile), and AMVN (Azobisdimethyl -Valeronitrile)
- AIBN Azobis (iso-butyronitrile)
- AMVN Azobisdimethyl -Valeronitrile
- the content of the polymerization initiator may be 0.01 wt% to 5 wt% with respect to the electrolyte solution component in the monomer and / or oligomer state made of a liquid phase.
- the content of the polymerization initiator is less than 0.01% by weight based on the monomer and / or oligomer electrolyte components in the liquid phase, the monomer and / or oligomer electrolyte components in the liquid phase may be sufficiently polymerized or cured. If the content is greater than 5% by weight, and the content is excessively large, the content of the electrolyte solution component is relatively low, so that the desired effect may not be exhibited.
- the battery cell may have a structure further comprising a liquid electrolyte.
- the liquid electrolyte may be a structure sealed in the battery case in the state of impregnating the electrode assembly.
- the battery cell includes an electrode assembly having a structure in which a separator including a gelled electrolyte component in a plurality of pores is interposed between an anode and a cathode, and a separate liquid electrolyte impregnates the electrode assembly.
- a separator including a gelled electrolyte component in a plurality of pores is interposed between an anode and a cathode, and a separate liquid electrolyte impregnates the electrode assembly.
- the gelled electrolyte component may be a structure further comprising a liquid electrolyte.
- the battery cell can improve the impregnation of the electrode assembly with respect to the electrolyte, and can supplement the additional electrolyte in addition to the gelled electrolyte component, it is possible to improve the electrical performance of the battery cell.
- the liquid electrolyte may be a different component from the gelled electrolyte component located in the pores of the separator, and in particular, N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate , Butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butylo lactone, 1,2-dimethoxy ethane, tetrahydroxy franc, 2-methyl tetrahydrofuran, dimethyl sulfoxide , 1,3-dioxolon, formamide, dimethylformamide, dioxolon, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphate triester, trimethoxy methane, dioxolon derivatives, sulfolane, methyl Any one selected from the group consisting of sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivative, te
- the battery cell is not particularly limited in its kind, but as a specific example, a lithium secondary battery such as a lithium ion battery, a lithium ion polymer battery, etc. having advantages such as high energy density, discharge voltage, and output stability, etc. It may be a battery.
- a lithium secondary battery such as a lithium ion battery, a lithium ion polymer battery, etc. having advantages such as high energy density, discharge voltage, and output stability, etc. It may be a battery.
- a lithium secondary battery is composed of a positive electrode, a negative electrode, a separator, and a lithium salt-containing nonaqueous electrolyte.
- the positive electrode is prepared by, for example, applying a mixture of a positive electrode active material, a conductive material, and a binder to a positive electrode current collector, followed by drying, and optionally, a filler is further added to the mixture.
- the conductive material is typically added in an amount of 1 to 30 wt% based on the total weight of the mixture including the positive electrode active material.
- a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite such as natural graphite and artificial graphite; Carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys 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 binder is a component that assists the bonding of the active material and the conductive material to the current collector, and is generally added in an amount of 1 to 30 wt% based on the total weight of the mixture including the positive electrode active material.
- binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene , Polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butylene rubber, fluorine rubber, various copolymers and the like.
- the filler is optionally used as a component for inhibiting expansion of the positive electrode, and is not particularly limited as long as it is a fibrous material without causing chemical change in the battery.
- the filler include olefinic polymers such as polyethylene and polypropylene; Fibrous materials, such as glass fiber and carbon fiber, are used.
- the negative electrode is manufactured by coating and drying a negative electrode active material on a negative electrode current collector, and optionally, the components as described above may optionally be further included.
- carbon such as hardly graphitized carbon and graphite type carbon
- Me: Mn, Fe, Pb, Ge; Me' Metal complex oxides such as Al, B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, halogen, 0 ⁇ x ⁇ 1; 1 ⁇ y ⁇ 3; 1 ⁇ z ⁇ 8); Lithium metal; Lithium alloys; Silicon-based alloys; Tin-based alloys; SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 , and metal oxides such as Bi 2
- the separator and the separation film may be an SRS (Safety-Reinforcing Separators) separator of organic / inorganic composite porous to improve battery safety.
- SRS Safety-Reinforcing Separators
- the SRS separator is manufactured using inorganic particles and a binder polymer as an active layer component on a polyolefin-based separator substrate, wherein the pore structure included in the separator substrate itself and the interstitial volume between the inorganic particles as the active layer component are used. It has a uniform pore structure formed.
- the organic / inorganic composite porous separator may exhibit excellent adhesion characteristics by controlling the content of the inorganic particles and the binder polymer, which are the active layer components in the separator, and thus may have an easy battery assembly process.
- the inorganic particles are not particularly limited as long as they are electrochemically stable. That is, the inorganic particles that can be used in the present invention are not particularly limited as long as the oxidation and / or reduction reactions do not occur in the operating voltage range of the battery to be applied (for example, 0 to 5 V on the basis of Li / Li +).
- the inorganic particles having the ion transfer ability since the ion conductivity in the electrochemical device can be improved to improve the performance, it is preferable that the ion conductivity is as high as possible.
- the inorganic particles have a high density, it is not only difficult to disperse during coating, but also has a problem of weight increase during battery manufacturing, and therefore, it is preferable that the density is as small as possible.
- an inorganic material having a high dielectric constant it is possible to contribute to an increase in the degree of dissociation of an electrolyte salt such as lithium salt in the liquid electrolyte, thereby improving the ionic conductivity of the electrolyte solution.
- the lithium salt is a good material to be dissolved in the non-aqueous electrolyte, for example, LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, lithium tetraphenyl borate and imide have.
- the non-aqueous electrolyte solution includes, for example, pyridine, triethyl phosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, and hexaphosphate triamide.
- halogen-containing solvents such as carbon tetrachloride and ethylene trifluoride may be further included, and carbon dioxide gas may be further included to improve high temperature storage characteristics.
- the present invention provides a method for manufacturing the battery cell, the method for manufacturing the battery cell,
- step b) impregnating the electrode assembly prepared in step a) into a mixed solution comprising a liquid monomer and / or oligomer electrolyte component and a polymerization initiator;
- the battery cell is immersed in the electrode assembly prepared by interposing the separator between the positive electrode and the negative electrode in a mixed solution containing a monomer and / or oligomer electrolyte composition and a polymerization initiator in a liquid phase, the electrode assembly is again liquid After impregnation with the electrolyte solution in the battery case, it is prepared by sealing, by aging the battery cell, it can be prepared by polymerizing or curing the electrolyte component inserted into the pores of the separator.
- the separator is impregnated separately in the mixed solution including the monomer and / or oligomer electrolyte solution and the polymerization initiator, and then polymerized or cured, due to the electrolyte component included in the separator, between the positive electrode and the negative electrode, The assembly process of the electrode assembly via the separator may not be easy.
- the battery cell manufacturing method according to the present invention it is possible to assemble the electrode assembly more easily, can save the cost and time required for the process, it is possible to improve the structural stability of the electrode assembly more.
- the electrolyte component of the monomer and / or oligomer state inserted into the pores of the separator in step d) is sufficiently gelled, so that it can be stably included in the pores of the separator, in a temperature range of 40 °C to 90 °C, 1 May be polymerized or cured for hours to 20 hours.
- the polymerization or curing process is carried out for a short time at a temperature that is too low out of the range of temperature and time, the monomer and / or oligomer electrolyte components inserted into the pores of the separator cannot be sufficiently gelled.
- the battery cell may act as a factor of deteriorating the electrical performance of the battery cell.
- the battery cell manufacturing method may further include a degas process to discharge the gas generated in the battery cell in the aging process for the polymerization or curing of the electrolyte component.
- the present invention also provides a battery pack including the battery cell and a device including the battery pack as a power source, the device is a mobile phone, tablet computer, notebook computer, power tools, wearable electronics, electric vehicles, hybrids It may be any one selected from the group consisting of an electric vehicle, a plug-in hybrid electric vehicle, and a power storage device.
- FIG. 1 is a schematic diagram schematically showing the structure of a battery cell according to an embodiment of the present invention
- FIG. 2 is a schematic diagram schematically showing a process of manufacturing the battery cell of FIG.
- FIG. 1 is a schematic diagram schematically showing the structure of a battery cell according to an embodiment of the present invention.
- the battery cell 100 includes an electrode assembly 110, and the electrode assembly 110 is sealed in the battery case 120 in a state of being impregnated with a liquid electrolyte 130.
- the electrode assembly 110 has a structure in which the anode 111 and the cathode 112 are alternately stacked, and a separator 113 is interposed between the anode 111 and the cathode 112.
- a plurality of pores 114 are formed in the separator 113, and the gelated electrolyte component 115 is included in the pores 114.
- the gelled electrolyte component 115 contained in the pores 114 can stably support the separator 113, and thus the anode 111 Insulation between the anode and the cathode 112 can be ensured, and structural stability can be improved.
- the pores 114 have different sizes from each other in consideration of ease of manufacture, but are not limited thereto, and the pores 114 may be formed of the same size.
- the pores 114 are each formed individually, but are not limited thereto. As the three-dimensional network structure, the pores 114 are connected to each other and are more stable by the gelled electrolyte component 115 included in the pores 114. Of course, the separation membrane 113 may be supported.
- FIG. 2 is a schematic diagram schematically showing a process of manufacturing the battery cell of FIG.
- the electrode assembly 110 is impregnated with a mixed solution including an electrolyte solution component 211 and a polymerization initiator 212 in a monomer and / or oligomer state made of a liquid phase.
- the mixed solution 210 may be sufficiently inserted into the plurality of pores 114 formed in the separator 113 of the electrode assembly 110.
- the electrode assembly 110 in which the mixed solution 210 is inserted into the pores 114 of the separator 113 is impregnated in the battery case 120 together with the liquid electrolyte 130, and the battery case 120 is By sealing, the battery cell 100 is manufactured.
- the battery cell 100 In order to polymerize or cure the electrolyte component 211 in the monomer and / or oligomer state inserted into the pores of the separator 113, the battery cell 100 is in a temperature range of 40 ° C. to 90 ° C. for 1 hour to 20 hours. During the aging process, the gelled electrolyte component 211 may be stably included in the pores 114 of the separator 113.
- the battery cell according to the present invention is configured to include a gelled electrolyte component in a plurality of pores formed in the separator, thereby using a separator having a large diameter pores,
- the insulation between the anode and the cathode can be improved to ensure the safety of the battery cell.
- the ion conductivity can be prevented from being deteriorated due to the closing of the pores, and the electrolyte can be prevented from being degraded by maintaining high electrolyte impregnation.
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Abstract
Description
Claims (19)
- 양극과 음극 사이에 분리막이 개재되어 있는 구조의 전극조립체를 포함하고 있고, 상기 분리막에는 복수의 기공들이 형성되어 있으며, 상기 기공들 내에는 겔(gel)화 된 전해액 성분이 포함되어 있는 것을 특징으로 하는 전지셀.
- 제 1 항에 있어서, 상기 분리막에 형성된 기공들은 평균 직경이 0.01 ㎛ 내지 100 ㎛인 것을 특징으로 하는 전지셀.
- 제 1 항에 있어서, 상기 분리막은 공극률이 40% 내지 90%인 것을 특징으로 하는 전지셀.
- 제 1 항에 있어서, 상기 전해액 성분은 액상으로 이루어진 모노머 및/또는 올리고머 상태의 전해액 성분과 중합 개시제를 포함하는 혼합액에 분리막을 함침하여 분리막의 기공들 내로 혼합액이 삽입된 후, 중합 또는 경화 되는 것을 특징으로 하는 전지셀.
- 제 4 항에 있어서, 상기 액상으로 이루어진 모노머 및/또는 올리고머 상태의 전해액 성분은 폴리에틸렌 유도체, 폴리에틸렌 옥사이드 유도체, 폴리프로필렌 옥사이드 유도체, 인산 에스테르 폴리머, 폴리 에지테이션 리신(agitation lysine), 폴리에스테르 술파이드, 폴리비닐 알코올, 폴리 불화 비닐리덴, 또는 이온성 해리기를 포함하는 중합체로 이루어진 군으로부터 선택되는 어느 하나 이상인 것을 특징으로 하는 전지셀.
- 제 4 항에 있어서, 상기 전해액 성분은 Li3N, LiI, Li5NI2, Li3N-LiI-LiOH, LiSiO4, LiSiO4-LiI-LiOH, Li2SiS3, Li4SiO4, Li4SiO4-LiI-LiOH, Li3PO4-Li2S-SiS2 등의 Li의 질화물, 할로겐화물, 황산염으로 이루어진 군으로부터 선택되는 어느 하나 이상을 포함하고 있는 것을 특징으로 하는 전지셀.
- 제 4 항에 있어서, 상기 중합 개시제는 외부에서 인가되는 열 또는 빛에 의해 액상으로 이루어진 모노머 및/또는 올리고머 상태의 전해액 성분을 겔화시키는 것을 특징으로 하는 전지셀.
- 제 4 항에 있어서, 상기 분리막의 기공 내로 삽입된 액상의 전해액 성분은 40℃ 내지 90℃의 온도 범위에서, 1시간 내지 20시간 동안 중합 또는 경화되는 것을 특징으로 하는 전지셀.
- 제 4 항에 있어서, 상기 중합 개시제는 벤조일 퍼옥사이드(Benzoyl peroxide; BPO), 아세틸 퍼옥사이드(Acetyl peroxide), 디라우릴 퍼옥사이드(Dilauryl peroxide), 디터트부틸퍼옥사이드(Di-tertbutylperoxide), 쿠밀 하이드로퍼옥사이드(Cumyl hydroperoxide), 하이드로겐 퍼옥사이드(Hydrogen peroxide), 2,2-Azobis(2-cyanobutane), 2,2-Azobis(Methylbutyronitrile), AIBN(Azobis(iso-butyronitrile), 및 AMVN(Azobisdimethyl-Valeronitrile)로 이루어진 군으로부터 선택되는 어느 하나 이상인 것을 특징으로 하는 전지셀.
- 제 4 항에 있어서, 상기 중합 개시제의 함량은 액상으로 이루어진 모노머 및/또는 올리고머 상태의 전해액 성분에 대해, 0.01 중량% 내지 5 중량%인 것을 특징으로 하는 전지셀.
- 제 1 항에 있어서, 상기 전지셀은 액상의 전해액을 더 포함하는 것을 특징으로 하는 전지셀.
- 제 11 항에 있어서, 상기 액상의 전해액은 전극조립체를 함침시킨 상태에서, 전지케이스 내에 밀봉되는 것을 특징으로 하는 전지셀.
- 제 11 항에 있어서, 상기 액상의 전해액은 N-메틸-2-피롤리디논, 프로필렌 카르보네이트, 에틸렌 카르보네이트, 부틸렌 카르보네이트, 디메틸 카르보네이트, 디에틸 카르보네이트, 감마-부틸로 락톤, 1,2-디메톡시 에탄, 테트라히드록시 프랑(franc), 2-메틸 테트라하이드로푸란, 디메틸술폭시드, 1,3-디옥소런, 포름아미드, 디메틸포름아미드, 디옥소런, 아세토니트릴, 니트로메탄, 포름산 메틸, 초산메틸, 인산 트리에스테르, 트리메톡시 메탄, 디옥소런 유도체, 설포란, 메틸 설포란, 1,3-디메틸-2-이미다졸리디논, 프로필렌 카르보네이트 유도체, 테트라하이드로푸란 유도체, 에테르, 피로피온산 메틸, 및 프로피온산 에틸로 이루어진 군으로부터 선택되는 어느 하나 이상인 것을 특징으로 특징으로 하는 전지셀.
- 제 1 항에 있어서, 상기 전지셀은 리튬 이차전지인 것을 특징으로 하는 전지셀.
- 제 1 항에 따른 전지셀을 제조하는 방법으로서,a) 분리막을 양극과 음극 사이에 개재하여 전극조립체를 제조하는 단계;b) 액상으로 이루어진 모노머 및/또는 올리고머 상태의 전해액 성분과 중합 개시제를 포함하는 혼합액에 상기 a) 단계에서 제조된 전극조립체를 함침시키는 단계;c) 상기 전극조립체를 액상의 전해액과 함께 전지케이스 내에 함침시킨 후, 상기 전지케이스를 밀봉하는 단계;d) 상기 분리막의 기공 내에 삽입된 모노머 및/또는 올리고머 상태의 전해액 성분을 중합 또는 경화시키는 단계;를 포함하는 것을 특징으로 하는 전지셀 제조 방법.
- 제 15 항에 있어서, 상기 d) 단계에서 분리막의 기공 내에 삽입된 모노머 및/또는 올리고머 상태의 전해액 성분은 40℃ 내지 90℃의 온도 범위에서, 1시간 내지 20시간 동안 중합 또는 경화되는 것을 특징으로 하는 전지셀 제조 방법.
- 제 1 항에 따른 전지셀을 포함하는 것을 특징으로 하는 전지팩.
- 제 17 항에 따른 전지팩을 전원으로서 포함하는 디바이스.
- 제 18 항에 있어서, 상기 디바이스는 휴대폰, 태블릿 컴퓨터, 노트북 컴퓨터, 파워 툴, 웨어러블 전자기기, 전기자동차, 하이브리드 전기자동차, 플러그-인 하이브리드 전기자동차, 및 전력저장 장치로 이루어진 군에서 선택되는 어느 하나인 것을 특징으로 하는 디바이스.
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JP2018503234A JP6815381B2 (ja) | 2015-10-07 | 2016-10-07 | 電極アセンブリを構成する分離膜の気孔内にゲル化電解質成分を含む電池セル |
PL16853923T PL3316380T3 (pl) | 2015-10-07 | 2016-10-07 | Ogniwo baterii, w którym składnik roztworu elektrolitu żelującego jest zawarty w porach separatora konfigurującego zespół elektrody |
US15/744,488 US10490849B2 (en) | 2015-10-07 | 2016-10-07 | Battery cell in which gelation electrolyte solution component is included in pore of separator configuring electrode assembly |
CN201680046500.6A CN107851845B (zh) | 2015-10-07 | 2016-10-07 | 将凝胶电解液组分包括在构成电极组件的隔板的孔中的电池单元 |
EP20156874.8A EP3675266B1 (en) | 2015-10-07 | 2016-10-07 | Battery cell in which gelled electrolyte component is included in pore of separator configuring electrode assembly |
EP16853923.7A EP3316380B1 (en) | 2015-10-07 | 2016-10-07 | Battery cell in which gelation electrolyte solution component is included in pore of separator configuring electrode assembly |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20210028496A1 (en) * | 2018-04-09 | 2021-01-28 | Nissan Motor Co., Ltd. | Battery manufacturing method |
CN114284554A (zh) * | 2021-12-06 | 2022-04-05 | 合肥国轩高科动力能源有限公司 | 一种凝胶锂离子电池制备方法及制得的凝胶锂离子电池 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111435758A (zh) * | 2019-12-25 | 2020-07-21 | 蜂巢能源科技有限公司 | 固态电解质膜及其制作方法、固态电池和电动汽车 |
CN111092193B (zh) * | 2019-12-31 | 2023-04-07 | 深圳市豪鹏科技股份有限公司 | 一种镍电池的注液方式和镍电池 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20090012726A (ko) * | 2007-07-31 | 2009-02-04 | 주식회사 에이엠오 | 공기투과도가 높은 전기화학소자용 분리막 및 그의제조방법 |
KR20100016919A (ko) * | 2008-08-05 | 2010-02-16 | 주식회사 엘지화학 | 겔 폴리머 전해질 이차전지 제조방법 및 그에 의해 제조된겔 폴리머 전해질 이차전지 |
KR20110137567A (ko) * | 2010-06-17 | 2011-12-23 | 호남석유화학 주식회사 | 리튬 이차전지용 고분자 전해질 및 이를 포함하는 리튬 이차 전지 |
KR20150007907A (ko) * | 2013-07-12 | 2015-01-21 | 주식회사 아모그린텍 | 복합 다공성 분리막 및 그 제조방법과 이를 이용한 이차전지 |
KR20150016897A (ko) * | 2013-08-05 | 2015-02-13 | 주식회사 아모그린텍 | 플렉시블 집전체 및 그 제조방법과 이를 이용한 이차전지 |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69404602T2 (de) * | 1993-10-07 | 1998-01-29 | Matsushita Electric Ind Co Ltd | Herstellungsverfahren eines Separators für eine Lithium-Sekundärbatterie und eine Lithium-Sekundärbatterie mit organischem Elektrolyt, die einen solchen Separator verwendet |
JP3262708B2 (ja) * | 1996-03-26 | 2002-03-04 | 日本電信電話株式会社 | 複合高分子電解質膜 |
JP4074418B2 (ja) * | 1999-01-11 | 2008-04-09 | 三菱化学株式会社 | 薄膜型リチウム二次電池 |
CN1258830C (zh) * | 1999-11-11 | 2006-06-07 | 皇家菲利浦电子有限公司 | 含凝胶电解质的锂电池 |
KR100334240B1 (ko) | 2000-01-31 | 2002-05-02 | 김선욱 | 전기 에너지 저장 장치 및 그 제조방법 |
KR100440930B1 (ko) * | 2001-11-24 | 2004-07-21 | 삼성에스디아이 주식회사 | 세퍼레이터의 제조방법 및 이를 채용한 리튬2차 전지의제조방법 |
JP3904935B2 (ja) | 2002-01-29 | 2007-04-11 | 三菱化学株式会社 | リチウムポリマー二次電池の製造方法 |
JP4157056B2 (ja) | 2004-02-23 | 2008-09-24 | 三星エスディアイ株式会社 | ゲルポリマー電解質およびリチウム二次電池 |
KR20050116338A (ko) | 2004-06-07 | 2005-12-12 | 박권필 | 분자 전해질 막 제조방법 |
KR100739337B1 (ko) | 2004-09-02 | 2007-07-12 | 주식회사 엘지화학 | 유/무기 복합 다공성 필름 및 이를 이용한 전기 화학 소자 |
US8883354B2 (en) * | 2006-02-15 | 2014-11-11 | Optodot Corporation | Separators for electrochemical cells |
JP5187720B2 (ja) | 2007-05-15 | 2013-04-24 | Necエナジーデバイス株式会社 | リチウムイオンポリマー電池 |
US20110143184A1 (en) * | 2008-02-14 | 2011-06-16 | Firefly International Energy Group, Inc. | Battery with electrolyte diffusing separator |
JP5553170B2 (ja) * | 2011-01-12 | 2014-07-16 | トヨタ自動車株式会社 | リチウムイオン二次電池 |
JP2013051081A (ja) * | 2011-08-30 | 2013-03-14 | Sony Corp | 二次電池、電池パック、電動車両、電力貯蔵システム、電動工具および電子機器 |
CN102368562B (zh) * | 2011-09-13 | 2015-11-25 | 东莞新能源科技有限公司 | 一种锂离子电池 |
KR101639020B1 (ko) | 2013-01-15 | 2016-07-12 | 주식회사 아모그린텍 | 폴리머 전해질, 이를 이용한 리튬 이차 전지 및 그의 제조방법 |
WO2014112776A1 (ko) * | 2013-01-15 | 2014-07-24 | 주식회사 아모그린텍 | 폴리머 전해질, 이를 이용한 리튬 이차 전지 및 그의 제조방법 |
CN104919639B (zh) * | 2013-01-15 | 2019-02-01 | 阿莫绿色技术有限公司 | 聚合物电解质、利用其的锂二次电池及其制备方法 |
CN104098785B (zh) * | 2013-04-07 | 2017-02-08 | 中国科学院长春应用化学研究所 | Pvdf凝胶聚合物电解质及其制备方法 |
KR102220502B1 (ko) | 2014-06-09 | 2021-02-25 | 엘지이노텍 주식회사 | 카메라 모듈 및 이를 포함하는 차량 부품 |
-
2015
- 2015-10-07 KR KR1020150140927A patent/KR20170041470A/ko not_active Application Discontinuation
-
2016
- 2016-10-07 US US15/744,488 patent/US10490849B2/en active Active
- 2016-10-07 PL PL16853923T patent/PL3316380T3/pl unknown
- 2016-10-07 EP EP16853923.7A patent/EP3316380B1/en active Active
- 2016-10-07 WO PCT/KR2016/011219 patent/WO2017061807A1/ko active Application Filing
- 2016-10-07 EP EP20156874.8A patent/EP3675266B1/en active Active
- 2016-10-07 JP JP2018503234A patent/JP6815381B2/ja active Active
- 2016-10-07 HU HUE20156874A patent/HUE064536T2/hu unknown
- 2016-10-07 CN CN201680046500.6A patent/CN107851845B/zh active Active
- 2016-10-07 PL PL20156874.8T patent/PL3675266T3/pl unknown
- 2016-10-07 ES ES20156874T patent/ES2961256T3/es active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20090012726A (ko) * | 2007-07-31 | 2009-02-04 | 주식회사 에이엠오 | 공기투과도가 높은 전기화학소자용 분리막 및 그의제조방법 |
KR20100016919A (ko) * | 2008-08-05 | 2010-02-16 | 주식회사 엘지화학 | 겔 폴리머 전해질 이차전지 제조방법 및 그에 의해 제조된겔 폴리머 전해질 이차전지 |
KR20110137567A (ko) * | 2010-06-17 | 2011-12-23 | 호남석유화학 주식회사 | 리튬 이차전지용 고분자 전해질 및 이를 포함하는 리튬 이차 전지 |
KR20150007907A (ko) * | 2013-07-12 | 2015-01-21 | 주식회사 아모그린텍 | 복합 다공성 분리막 및 그 제조방법과 이를 이용한 이차전지 |
KR20150016897A (ko) * | 2013-08-05 | 2015-02-13 | 주식회사 아모그린텍 | 플렉시블 집전체 및 그 제조방법과 이를 이용한 이차전지 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20210028496A1 (en) * | 2018-04-09 | 2021-01-28 | Nissan Motor Co., Ltd. | Battery manufacturing method |
US11652241B2 (en) * | 2018-04-09 | 2023-05-16 | Nissan Motor Co., Ltd. | Battery manufacturing method |
CN114284554A (zh) * | 2021-12-06 | 2022-04-05 | 合肥国轩高科动力能源有限公司 | 一种凝胶锂离子电池制备方法及制得的凝胶锂离子电池 |
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KR20170041470A (ko) | 2017-04-17 |
PL3675266T3 (pl) | 2024-01-29 |
HUE064536T2 (hu) | 2024-03-28 |
EP3316380B1 (en) | 2020-04-15 |
JP6815381B2 (ja) | 2021-01-20 |
CN107851845A (zh) | 2018-03-27 |
PL3316380T3 (pl) | 2020-07-27 |
ES2961256T3 (es) | 2024-03-11 |
EP3316380A1 (en) | 2018-05-02 |
EP3316380A4 (en) | 2018-06-27 |
EP3675266B1 (en) | 2023-09-20 |
US10490849B2 (en) | 2019-11-26 |
JP2018521483A (ja) | 2018-08-02 |
CN107851845B (zh) | 2022-02-18 |
US20180212273A1 (en) | 2018-07-26 |
EP3675266A1 (en) | 2020-07-01 |
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