WO2019190128A1 - Procédé de fabrication d'un accumulateur de type poche - Google Patents

Procédé de fabrication d'un accumulateur de type poche Download PDF

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Publication number
WO2019190128A1
WO2019190128A1 PCT/KR2019/003403 KR2019003403W WO2019190128A1 WO 2019190128 A1 WO2019190128 A1 WO 2019190128A1 KR 2019003403 W KR2019003403 W KR 2019003403W WO 2019190128 A1 WO2019190128 A1 WO 2019190128A1
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WO
WIPO (PCT)
Prior art keywords
secondary battery
pouch
type secondary
polymer electrolyte
pouch type
Prior art date
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PCT/KR2019/003403
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English (en)
Korean (ko)
Inventor
신원경
이재원
안경호
이철행
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority claimed from KR1020190032175A external-priority patent/KR102255539B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US16/766,324 priority Critical patent/US11114698B2/en
Priority to CN201980005669.0A priority patent/CN111344889A/zh
Priority to EP19774534.2A priority patent/EP3699993A4/fr
Publication of WO2019190128A1 publication Critical patent/WO2019190128A1/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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • 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
    • H01M10/04—Construction or manufacture in general
    • 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
    • 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

Definitions

  • the present invention relates to a method of manufacturing a pouch type secondary battery with improved electrolyte impregnation.
  • the lithium secondary battery may be classified into a square lithium secondary battery and a pouch type lithium secondary battery according to its shape.
  • the rectangular lithium secondary battery has a fixed shape, the design is limited, and in view of safety, the effect of venting gas or liquid is not smooth, and heat and gas accumulate inside the battery, so there is a high risk of explosion. have.
  • the pouch-type lithium secondary battery has no advantages in shape and size, easy to assemble through heat fusion, and has the advantage of high safety because it is easy to export the gas or liquid when abnormal behavior occurs.
  • the pouch-type lithium secondary battery is manufactured by inserting an electrode assembly having a porous separator between a positive electrode and a negative electrode in a pouch-shaped case of a predetermined size and shape, and then injecting and impregnating an electrolyte containing lithium salt.
  • the electrolyte is impregnated as it penetrates between the positive electrode, the negative electrode, and the separator by capillary force, and the electrode constituting the electrode assembly must be rapidly and completely impregnated with the electrolyte to optimize the cell performance.
  • the positive electrode, the negative electrode and the separator are all hydrophobic materials, since the electrolyte is a hydrophilic material, considerable time and demanding process conditions are required for the electrolyte to be sufficiently impregnated in the electrode assembly.
  • the present invention is to provide a method of manufacturing a pouch type secondary battery with improved impregnation of the composition for the gel polymer electrolyte to the electrode assembly.
  • Degassing comprising;
  • the ultrasonic member maintains a temperature of 30 °C to 80 °C
  • Pressing the pouch-type preliminary secondary battery provides a method of manufacturing a pouch-type secondary battery that is performed while applying a pressure of 0.1 Kgf / cm 2 to 3,000 kgf / cm 2 per area of the pouch-type preliminary secondary battery.
  • the ultrasonic member used in the method of the present invention may be made of a metal material selected from the group consisting of stainless steel, iron, aluminum, copper, nickel and two or more alloys thereof, and specifically, may be made of stainless steel or aluminum.
  • the ultrasonic member may be formed in a structure surrounding the front surface of the pouch type secondary battery.
  • the ultrasonic member may maintain a temperature of 30 °C to 60 °C.
  • the step of pressurizing the pouch type preliminary secondary battery may be a pressure of 0.1 Kgf / cm 2 to 500 kgf / cm 2, specifically 0.1 Kgf / cm 2 to 100 kgf / cm 2 per pouch type secondary battery. You can do it while.
  • the step of applying the ultrasonic vibration in the method of the present invention can be carried out by applying a vibration having a frequency of 20kHz to 200MHz.
  • the step of applying the ultrasonic vibration may be performed simultaneously with the step of injecting the gel polymer electrolyte composition.
  • the method of the present invention may further comprise the step of applying an ultrasonic vibration after the step of forming and before the step of curing the composition for gel polymer electrolyte.
  • the gel polymer electrolyte composition is effectively dispersed by applying pressure at a temperature of 30 ° C. or more using an ultrasonic member made of a metal material or by applying ultrasonic vibrations at the time of injection or after injection of the gel polymer electrolyte composition. Not only can the impregnation of the composition for electrolyte be improved, but also the wetting time can be shortened. As a result, a pouch type secondary battery having an improved initial capacity and a lower initial resistance can be manufactured.
  • FIG. 1 is a cross-sectional view of a pouch type secondary battery in which an ultrasonic member is disposed in a method of manufacturing a pouch type secondary battery according to an exemplary embodiment of the present invention.
  • Degassing comprising;
  • the ultrasonic member maintains a temperature of 30 °C to 80 °C
  • Pressing the pouch type preliminary secondary battery may be performed while applying a pressure of 0.1 Kgf / cm 2 to 3,000 kgf / cm 2 per area of the pouch type secondary battery.
  • the pouch type preliminary secondary battery of the present invention includes an electrode assembly and a pouch type case in which the electrode assembly is accommodated, and may be manufactured according to a conventional method known in the art.
  • the positive electrode, the separator, and the negative electrode may be sequentially stacked to form an electrode assembly, and then may be housed in a pouch-type (battery) case.
  • the electrode assembly is accommodated in the inner space, and then the remaining three corners except for one corner into which the gel polymer electrolyte composition is injected are first pouch-shaped.
  • a spare secondary battery can be manufactured.
  • the electrode assembly may be sequentially stacked in a state in which the separator is interposed between the positive electrode and the negative electrode and insulated from each other, and may be formed in various structures such as a winding type, a stack type, or a stack / fold type according to an embodiment. Can be.
  • the positive electrode may be manufactured by forming a positive electrode mixture layer on the positive electrode current collector.
  • the cathode mixture layer may be formed by coating a cathode slurry including a cathode active material, a binder, a conductive material, a solvent, and the like on a cathode current collector, followed by drying and rolling.
  • the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes in the battery.
  • the positive electrode current collector may be formed of stainless steel, aluminum, nickel, titanium, calcined carbon, or carbon on the surface of aluminum or stainless steel. Surface treated with nickel, titanium, silver, or the like may be used.
  • the cathode active material is a compound capable of reversible intercalation and deintercalation of lithium, and specifically, may include a lithium metal oxide including lithium and one or more metals such as cobalt, manganese, nickel, or aluminum. Can be.
  • the lithium metal oxide may be lithium-manganese oxide (eg, LiMnO 2 , LiMn 2 O 4, etc.), lithium-cobalt oxide (eg, LiCoO 2, etc.), lithium-nickel oxide (for example, LiNiO 2, etc., lithium-nickel-manganese oxides (eg, LiNi 1-Y Mn Y O 2 (here, 0 ⁇ Y ⁇ 1), LiMn 2-z Ni z O 4 (here 0 ⁇ Z ⁇ 2) and the like, lithium-nickel-cobalt-based oxide (for example, LiNi 1-Y1 Co Y1 O 2 (here, 0 ⁇ Y1 ⁇ 1) and the like), lithium-manganese-cobalt-based Oxides (e.g., LiCo 1-Y2 Mn Y2 O 2 (here, 0 ⁇ Y2 ⁇ 1), LiMn 2-z1 Co z1 O 4 (here, 0 ⁇ Z1 ⁇ 2), etc.
  • the binder is a component that assists in bonding the active material, the conductive material, and the like to the current collector, and may generally be added in an amount of 1 to 30 wt% based on the total weight of solids in the positive electrode slurry.
  • binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoro Low ethylene, polyethylene, polypropylene, ethylene-propylene-diene monomers, sulfonated ethylene-propylene-diene monomers, styrene-butadiene rubbers, fluororubbers, various copolymers, and the like.
  • the conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and may be added in an amount of 1 to 20 wt% based on the total weight of solids in the positive electrode slurry.
  • Such conductive materials include, for example, carbon powders such as carbon black, acetylene black (or denka black), Ketjen black, channel black, furnace black, lamp black, or thermal black; Graphite powders such as natural graphite, artificial graphite, or graphite with very advanced crystal structure; Conductive fibers such as carbon fibers and metal fibers; Conductive powders, such as carbon fluoride powder, aluminum powder, and nickel powder, etc. can be used.
  • the solvent may include an organic solvent such as N-methyl-2-pyrrolidone (NMP), and may be used in an amount that becomes a desirable viscosity when including the positive electrode active material and optionally a binder and a conductive material.
  • NMP N-methyl-2-pyrrolidone
  • the concentration of the solids in the slurry including the positive electrode active material and optionally the binder and the conductive material may be 10 wt% to 60 wt%, preferably 20 wt% to 50 wt%.
  • the positive electrode may include a positive electrode current collector region, that is, a positive electrode non-coating portion, in which the positive electrode active material layer is not formed, and the positive electrode is bonded to a positive electrode tab formed of a metal material such as aluminum (Al) at one end of the non-coating portion.
  • a positive electrode current collector region that is, a positive electrode non-coating portion, in which the positive electrode active material layer is not formed, and the positive electrode is bonded to a positive electrode tab formed of a metal material such as aluminum (Al) at one end of the non-coating portion.
  • Al aluminum
  • the negative electrode may be prepared by forming a negative electrode mixture layer on the negative electrode current collector.
  • the negative electrode mixture layer may be formed by coating a negative electrode slurry including a negative electrode active material, a binder, a conductive material, a solvent, and the like on a negative electrode current collector, followed by drying and rolling.
  • the negative electrode current collector generally has a thickness of 3 to 500 ⁇ m.
  • Such a negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver, and the like on the surface, aluminum-cadmium alloy and the like can be used.
  • the negative electrode active material is a lithium metal, a carbon material capable of reversibly intercalating / deintercalating lithium ions, a metal or an alloy of these metals with lithium, a material capable of doping and undoping lithium, and a transition It may include at least one selected from the group consisting of metal oxides.
  • any carbon-based negative electrode active material generally used in a lithium ion secondary battery may be used without particular limitation. Examples thereof include crystalline carbon, Amorphous carbons or these may be used together.
  • the metals or alloys of these metals with lithium include Cu, Ni, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al And a metal selected from the group consisting of Sn or an alloy of these metals with lithium may be used.
  • Examples of the material capable of doping and undoping lithium include Si, SiO x (0 ⁇ x ⁇ 2), Sn, or SnO 2 , and may be used by mixing at least one of these with SiO 2 .
  • transition metal oxide examples include lithium-containing titanium oxide (LTO), vanadium oxide, lithium vanadium oxide, and the like.
  • the binder and the conductive material may be the same or different materials as the binder and the conductive material used in the positive electrode mixture layer as described above.
  • the solvent may include an organic solvent such as water or NMP, alcohol, etc., and may be used in an amount that becomes a desirable viscosity when including the negative electrode active material and optionally a binder and a conductive material.
  • concentration of the solids in the slurry including the negative electrode active material and, optionally, the binder and the conductive material may be 50 wt% to 75 wt%, preferably 50 wt% to 65 wt%.
  • the negative electrode may have a negative electrode current collector region, ie, a negative electrode non-coating portion, in which negative electrode active material layers are not formed at both sides.
  • the negative electrode may be bonded to a negative electrode tab formed of a metal material, such as nickel (Ni), at one end thereof.
  • Each of the positive electrode tab and the negative electrode tab extends from the electrode assembly, and each of the tabs may be partially or entirely connected to the positive electrode lead negative electrode lead, respectively, for electrical connection with an external terminal or device.
  • the positive lead and the negative lead are electrically connected to the electrode tabs by welding, and a part thereof may be exposed to the outside of the battery case.
  • the positive lead and the negative lead may be located in opposite directions in the battery case, or may be located side by side in the same direction.
  • the separator is positioned between the positive electrode and the negative electrode to electrically insulate the positive electrode and the negative electrode from each other, and may be formed in the form of a porous membrane to allow lithium ions to pass between the positive electrode and the negative electrode.
  • a separator may be made of, for example, a porous membrane using polyethylene (PE) or polypropylene (PP) or a composite film thereof.
  • the ultrasonic member of the metal material surrounding the front surface of the pouch type preliminary secondary battery may be disposed on both sides of the pouch type preliminary secondary battery manufactured as described above.
  • FIG. 1 is a cross-sectional view of a pouch-type preliminary secondary battery 100 in which an ultrasonic member is disposed in close contact with a method of manufacturing a pouch-type secondary battery according to an embodiment of the present invention.
  • the method of the present invention may be disposed in close contact with the ultrasonic member surrounding the front surface of the pouch-type secondary battery 100 on both sides of the pouch-type secondary battery 100, the electrode assembly accommodated.
  • the ultrasonic member may be a pair of ultrasonic members including the first ultrasonic member 110-1 and the second ultrasonic member 110-2 independently separated as shown in FIG. 1, or the first ultrasonic member. It may be an integrated ultrasonic member in which at least one surface of the ultrasonic member and the second ultrasonic member are coupled.
  • the ultrasonic member is preferably in contact with the side surface of the case of the pouch type preliminary secondary battery to facilitate the transmission of ultrasonic vibration, instead of using the adhesive member.
  • the ultrasonic member is preferably made of a metal material to facilitate temperature control and pressure control.
  • the metal material may include at least one metal selected from the group consisting of stainless steel, iron, aluminum, copper, nickel and two or more alloys thereof.
  • the ultrasonic member may be made of stainless steel or aluminum, more specifically aluminum in consideration of cost and heat transfer efficiency.
  • the ultrasonic member maintains a temperature of 30 ° C to 80 ° C, specifically 30 ° C to 60 ° C using a temperature control device (not shown) including a heating wire and the like coupled to a portion. It is preferable.
  • the ultrasonic member maintains the temperature range, it is possible to improve the impregnation effect during subsequent injection of the composition for the gel polymer electrolyte, and when ultrasonic vibration is applied, the temperature rises excessively in the pouch-type secondary battery, or internally by ultrasonic application. Desorption and damage of a substance such as an active material of an electrode can be prevented from occurring.
  • the viscosity of the gel polymer electrolyte composition may be increased during subsequent injection of the composition for gel polymer electrolyte, impregnation may be reduced, and if it exceeds 80 °C, the temperature rise inside the pouch type secondary battery This may cause damage due to chemical and physical side reactions between the composition for gel polymer electrolyte and the electrode or separator upon subsequent injection of the composition for gel polymer electrolyte, thereby causing an internal short circuit of the cell.
  • the electrode assembly after placing the ultrasonic member surrounding the front surface of the pouch-type preliminary secondary battery in close contact with both sides of the pouch-type preliminary secondary battery, the electrode assembly through one corner of the pouch-type case in an open state
  • the gel polymer electrolyte composition may be injected into the pouch-type case in which is stored.
  • the surface in which the injection hole of the composition for the gel polymer electrolyte is formed is adjacent to the surface of the sealing portion in which the negative electrode tab and the positive electrode tab, but is preferably a different surface.
  • the composition for gel polymer electrolyte used in the secondary battery manufacturing method of the present invention comprises (a) a lithium salt, (b) an organic solvent, (c) a polymerizable monomer, (d) a polymerization initiator and optionally (e) an additive. It can use to include.
  • the (a) lithium salt may be used without limitation those conventionally included in the gel polymer electrolyte, for example, include Li + as a cation, F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , NO 3 -, N (CN) 2 -, ClO 4 -, BF 4 -, B 10 Cl 10 -, PF 6 -, CF 3 SO 3 -, CH 3 CO 2 -, CF 3 CO 2 -, AsF 6 - , SbF 6 -, AlCl 4 - , AlO 4 -, CH 3 SO 3 -, BF 2 C 2 O 4 -, BC 4 O 8 -, PF 4 C 2 O 4 -, PF 2 C 4 O 8 -, ( CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, C 4 F 9 SO 3 -, CF 3 CF 2 SO
  • the lithium salt is LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCH 3 CO 2 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , LiAlO 4 , LiCH 3 SO 3 , LiFSI (lithium fluorosulfonyl imide, LiN (SO 2 F) 2 ), LiTFSI (lithium (bis) trifluoromethanesulfonimide, LiN (SO 2 CF 3 ) 2 ) and LiBETI (lithium bisperfluoroethanesulfonimide, LiN (SO 2 C 2 F 5) may comprise a 2) danilmul or in combination of two or more thereof selected from the group consisting of.
  • the lithium salt may include a single substance or a mixture of two or more selected from the group consisting of LiBF 4 , LiPF 6 , LiCH 3 CO 2 , LiCF 3 CO 2 , LiCH 3 SO 3 , LiFSI, LiTFSI, and LiBETI.
  • lithium salts commonly used in electrolytes for lithium secondary batteries can be used without limitation.
  • the lithium salt may be appropriately changed within a range generally available, but in order to obtain an effect of forming an anti-corrosion coating on the surface of the electrode, a concentration of 0.8 M to 4.0 M in the composition for gel polymer electrolyte, specifically 1.0 M to 3.0 It may be included in M concentration.
  • the concentration of the lithium salt is less than 0.8M, the effect of improving the low temperature output and the cycle characteristics of the lithium secondary battery during high temperature storage is insignificant, and when the concentration exceeds 4.0M, the gel polymer electrolyte increases as the viscosity of the gel polymer electrolyte composition increases. Impregnation of the composition may decrease.
  • the organic solvent (b) may be minimized as long as the organic solvent may be decomposed by an oxidation reaction or the like during the charging and discharging process of the secondary battery, and may be a non-aqueous organic solvent capable of exhibiting desired properties with an additive.
  • a carbonate solvent, an ether solvent, an ester solvent, etc. can be used individually or in mixture of 2 or more types, respectively.
  • Examples of the carbonate solvent in the organic solvent include a cyclic carbonate solvent or a linear carbonate solvent.
  • cyclic carbonate solvent examples include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate , 2,3-pentylene carbonate, vinylene carbonate, and fluoroethylene carbonate (FEC), any one selected from the group consisting of, or two or more solvents thereof.
  • the linear carbonate solvent is selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethylmethyl carbonate (EMC), methylpropyl carbonate and ethylpropyl carbonate Any one or two or more of these solvents can be mentioned.
  • the ether solvent may be any one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methyl propyl ether, and ethyl propyl ether or two or more of them.
  • the ester solvent may include a linear ester solvent or a cyclic ester solvent, and examples of the linear ester solvent include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, and propyl.
  • cyclic ester solvent examples include ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -valerolactone or ⁇ -caprolactone.
  • the (c) polymerizable monomer is a multifunctional acrylate compound containing at least one acrylate group in the molecule, and a multifunctional methacrylate containing at least one methacrylate group so as to polymerize with each other to form a polymer.
  • the polymerizable monomer may be a compound represented by the following formula (1).
  • a and A ' are each independently an acrylate group, a methacrylate group, an alkylene group having 1 to 10 carbon atoms containing at least one or more acrylate groups or methacrylate groups, or -OR 1 , wherein R 1 is An alkylene group having 1 to 10 carbon atoms or at least one or more acrylate groups or methacrylate groups, or -OR 2 -OR 3 , wherein R 2 and R 3 are each at least one acrylate group or methacrylate group; It is a C1-C10 alkylene group containing,
  • B is an oxyalkylene group.
  • a and A ' may each independently include at least one or more of the units represented by Formulas A-1 to A-5.
  • An acrylate group or methacrylate group positioned at the terminal of the polymerizable monomer may form a polymer network by a polymerization reaction with an organic binder including an ethylenically unsaturated group.
  • Such compounds can be derived from monomers comprising mono or polyfunctional acrylate groups or methacrylate groups.
  • the B may include a unit represented by the following formula (B-1).
  • R is an alkylene group having 1 to 10 carbon atoms
  • R 3 is O or an alkylene group having 1 to 5 carbon atoms
  • k1 is an integer of any one of 1 to 30,
  • n is an integer of any one of 0-3.
  • R may be each independently -CH 2 CH 2 -or -CH 2 CH 2 CH 2- .
  • Chemical Formula 1 More specifically, the compound represented by Chemical Formula 1 may be represented by the following Chemical Formula 1a.
  • the polymerizable monomer may be included in an amount of 0.5 wt% to 20 wt%, specifically 0.7 wt% to 15 wt%, and more specifically 1.0 wt% to 10 wt%, based on the total weight of the gel polymer electrolyte composition.
  • the content of the polymerizable monomer is 0.5% by weight or more, the effect of forming a gel reaction can be improved to secure sufficient mechanical strength of the gel polymer electrolyte, and when the content is 20% by weight or less, an increase in resistance according to the oligomer content and a lithium ion It is possible to avoid disadvantages such as the limitation of (limiting ion conductivity).
  • the polymerization initiator (d) may be used a conventional polymerization initiator known in the art.
  • the polymerization initiator may be used by selecting one or more selected from the group consisting of a UV polymerization initiator, a photo polymerization initiator, and a thermal polymerization initiator.
  • the UV polymerization initiator is a representative example of 2-hydroxy-2-methylpropiophenone, 1-hydroxy-cyclohexylphenyl-ketone, benzophenone, 2-hydroxy-1- [4- (2-hydroxy Oxyethoxy) phenyl] -2-methyl-1-propaneone, oxy-phenylacetic acid 2- [2-oxo-2 phenyl-acetoxy-ethoxy] -ethyl ester, oxy-phenyl-acetic 2- [2-hydroxyethoxy] -ethyl ester, alpha-dimethoxy-alpha-phenylacetophenone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1 -Butanone, 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone, diphenyl (2,4,6-trimethylbenzoyl) -phos
  • the photo or thermal polymerization initiator is a typical example of benzoyl peroxide, acetyl peroxide, acetyl peroxide, dilauryl peroxide, di-tert-butyl peroxide.
  • the polymerization initiator is a compound which can be decomposed by UV or heat in a battery at 30 ° C. to 100 ° C. or decomposed by light at room temperature (5 ° C. to 30 ° C.) to form radicals. It can be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polymer (A) to be displayed. When the polymerization initiator is included in 10 parts by weight or less, it is possible to control the polymerization rate in the polymer electrolyte, thereby preventing the disadvantage that the unreacted polymerization initiator remains and later adversely affects the battery performance. In addition, the polymerization initiator should be included 0.1 parts by weight or more to facilitate the polymerization reaction between the polymer (A) compound represented by the formula (1), a polymer electrolyte having a uniform thickness can be prepared.
  • the additive may be used without limitation those conventionally used in the gel polymer electrolyte, and representative examples thereof include vinylene carbonate (VC), propane sultone (PS), succinonitrile (SN), adiponitrile, Ethylene sulfite (ESa), 1,3-propane sultone (PRS), propylene ethylene carbonate (FEC), LiPO 2 F 2 , LiODFB, LiBOB, tetramethyl trimethyl silyl phosphate (TMSPa), trimethyl silyl phosphite (TMSPi), Lithium difluoro (bisoxalato) phosphate, lithium difluorophosphate, lithium oxalyldifluoroborate, tris (2,2,2-trifluoroethyl) phosphate (TFEPa) or tris (trifluoroethyl Phosphite (TFEPi) and the like.
  • VC vinylene carbonate
  • PS propane sultone
  • the opened sealing parts may be adhered to each other and sealed, followed by a subsequent step.
  • the gel polymer electrolyte composition injection port is sealed before the ultrasonic vibration is applied, so that the gel polymer electrolyte composition may be volatilized, or the inside of the battery may be prevented from occurring in the pouch-type case.
  • the sealing may be performed for 1 second to 10 seconds at 130 ° C. to 160 ° C., specifically for 2 seconds to 3 seconds at 140 ° C. to 150 ° C., so that the polymer layers of the pouch type case may be adhered to each other.
  • the step of applying the ultrasonic vibration may be performed by applying a vibration having a frequency of 20kHz to 200MHz, specifically 31kHz to 200MHz.
  • a vibration having a frequency of 20kHz to 200MHz specifically 31kHz to 200MHz.
  • 0.1 Kgf / cm2 to 3,000 kgf / cm2 pressure specifically 0.1 Kgf / cm2 to 500 kgf / cm2 pressure, more specifically 0.1 Kgf / per pouch type secondary battery by using the hydraulic press, etc. while applying the ultrasonic vibration
  • the pouch type secondary battery may be pressurized while applying a pressure of cm 2 to 100 kgf / cm 2, more specifically, 0.1 Kgf / cm 2 to 50 kgf / cm 2.
  • the dispersion effect of the composition for gel polymer electrolytes can be improved more.
  • the pressure when the pressure is applied to less than 0.1 Kgf / cm2 per area of the pouch type secondary battery, it may be difficult to transmit the ultrasonic vibration to the inside of the cell, when applying a pressure exceeding 3,000 kgf / cm2 per area of the pouch type secondary battery pouch type secondary Excessively high pressure may be applied to the cell causing cell damage.
  • the step of applying the ultrasonic vibration is a cycle having a rest for 5 seconds to 10 seconds after applying ultrasonic vibration for 5 seconds to 10 seconds, the cycle about 50 to 150 times, specifically about 100 times Can be repeated.
  • the ultrasonic member is formed to completely surround the front surface of the pouch-type preliminary secondary battery, it is possible to prevent the heat loss inside the pouch-type preliminary secondary battery and more stably maintain the cell temperature.
  • uniform pressure and ultrasonic vibration may be applied to the front surface of the pouch type preliminary secondary battery, and the working environment may be improved by reducing noise generated when ultrasonic vibration is applied.
  • the step of applying the ultrasonic vibration in the method of the present invention may be performed at the same time as the injection of the composition for the gel polymer electrolyte, or may be performed after the injection of the composition for the gel polymer electrolyte is completed, sealed.
  • the viscosity of the gel polymer electrolyte composition is lowered and the mobility of the molecules is improved to form an electrode plate and a separator constituting the electrode assembly. Since it is easier to impregnate, the impregnability (wetting) of the composition for gel polymer electrolyte can be greatly improved. Thus, after the injection of the gel polymer electrolyte composition, it is possible to shorten the wetting time and the manufacturing time of the pouch type secondary battery.
  • pre-gelling reactivity of the gel polymer electrolyte composition can be suppressed by injecting and sealing the gel polymer electrolyte composition and then applying ultrasonic vibration.
  • the pouch type secondary battery manufacturing method of the present invention when the ultrasonic vibration is applied, it is possible to control the heat generation temperature range inside the pouch type secondary battery caused by the ultrasonic vibration using the ultrasonic member.
  • the step of forming the pouch type secondary battery may be performed after the step of applying the ultrasonic vibration.
  • the formation step may be charged and discharged up to 1.7V to 4.4V at 100C to 200mA at 0.05C to 0.1C at 70 ° C or less, and specifically, may be performed to 0.05V at 0.05C.
  • the method of the present invention may further perform the aging step after the forming step.
  • the aging step is carried out within 1 hour to 72 hours (3 days) at room temperature of 25 °C to 60 °C, specifically 30 °C to 40 °C room temperature to prevent pregelation and sufficiently wet the electrode in the composition for gel polymer electrolyte can do.
  • the formation By carrying out the process and the aging process at 70 ° C. or less, a sufficient SEI film can be formed, and side reactions can be prevented by controlling the wetting property improving effect and the electrolyte salt decomposition reaction.
  • the method of the present invention may further perform a vacuum wetting step after the aging step to improve the wettability.
  • the vacuum wetting step is preferably exposed for a short period of time under a weaker vacuum pressure than the conventional wetting conditions. Specifically, the vacuum wetting step may be repeated three times while reducing the pressure for 10 to 20 seconds in a vacuum chamber. It may be repeated three times while reducing the pressure for 15 to 20 seconds.
  • a large amount of gas generated due to the side reaction of the gas resulting from the positive electrode active material and the composition for the positive electrode active material and the gel polymer electrolyte may occur. If the gas generated in the battery cell is not efficiently removed in the formation step, the gas occupies a certain space in the battery cell, thereby preventing the formation of uniformly, adversely affecting battery performance and battery life such as capacity and output. Get mad. In addition, there is a problem that the capacity of the battery decreases rapidly as the number of charge / discharge increases due to the gas remaining inside the battery cell, or the battery cell swells.
  • the method of the present invention may further include degassing the gas generated in the formation step by opening a portion of the case after the formation step.
  • the method may further comprise applying ultrasonic vibration after the degassing step.
  • the step of applying the ultrasonic vibration can be carried out under the same conditions as the step of applying the ultrasonic vibration described above.
  • the dispersibility of the composition for the gel polymer electrolyte is improved to increase the impregnation, thereby making it more uniform and stable.
  • the gel polymer electrolyte can be cured.
  • a step of curing (gelling) the gel polymer electrolyte composition may be performed after the formation step.
  • the curing (gelling) step may be carried out through a photocuring process by conventional heat, e-beam, gamma irradiation.
  • the curing (gelling) step may be carried out by thermal curing for 5 hours to 24 hours in a temperature range of 30 °C to 70 °C, specifically 40 °C to 65 °C under inert conditions (inert condition).
  • the inert atmosphere may be a gas having low reactivity known in the art, in particular one or more inert gases selected from the group consisting of nitrogen, argon, helium and xenon.
  • the polymerizable monomers may be crosslinked with each other to form a polymer network in a gel form, and electrolyte salts dissociated from the composition for gel polymer electrolyte may be uniformly impregnated in the polymer network.
  • the method of the present invention may further comprise the step of aging for 1 hour to 24 hours under the curing step, 25 °C to 70 °C, specifically 30 °C to 60 °C conditions.
  • an additional SEI film may be formed by leaving the battery, which has been charged and discharged and cured, at a room temperature for a period of time, thereby inducing additional gas generation.
  • the step of curing the gel polymer electrolyte composition it may be carried out a step of degassing.
  • the degassing step may be performed while applying pressure to the battery case.
  • the degassing step can be carried out at a pressure of -85 kPa to -95 kPa.
  • the opened area of the pouch type case may be sealed at a temperature of 120 ° C. to 150 ° C. for about 2 seconds to 5 seconds.
  • the ultrasonic member is placed in close contact with the pouch-type secondary battery during manufacture of the pouch-type secondary battery, and the gel polymer electrolyte composition is injected, or simultaneously with the gel polymer electrolyte composition injection.
  • the composition for gel polymer electrolyte can be effectively dispersed to improve the impregnation of the composition for gel polymer electrolyte.
  • LiCoO 2 as a positive electrode active material, carbon black as a conductive material, and PVDF as a binder were added to N-methyl-2-pyrrolidone (NMP) as a solvent in a 94: 3: 3 weight ratio to obtain a positive electrode mixture slurry (solid content). 65 wt%) was prepared.
  • the positive electrode mixture slurry was applied to a thin film of aluminum (Al), which is a positive electrode current collector having a thickness of about 20 ⁇ m, and dried, followed by roll press to prepare a positive electrode.
  • an electrode assembly was manufactured by winding and compressing a separator having a thickness of 20 ⁇ m between polyethylene electrodes, and inserting the same into a pouch-type battery case, thereby preparing a pouch-type secondary battery. .
  • an ultrasonic member made of aluminum (Al) covering the entire surface of the pouch type preliminary secondary battery was disposed on both surfaces of the pouch type preliminary secondary battery.
  • the prepared composition for gel polymer electrolyte was injected, and the composition injection hole for the gel polymer electrolyte was sealed at 140 ° C.
  • the formation process was performed for 3 hours at 200 mA at 0.1 C, then aged at room temperature for 2 days, and the curing process was performed at 65 ° C. for 5 hours to prepare a gel polymer electrolyte.
  • a degassing step was performed while applying a -85 kPa pressure to remove the gas generated therein, thereby manufacturing the pouch type secondary battery of the present invention.
  • composition for gel polymer electrolyte was inject
  • the ultrasonic member is used to pressurize a pressure of 10 Kgf / cm2 per area of the pouch type preliminary secondary battery, and apply 25 KHz of ultrasonic vibration for 100 cycles (1 cycle: 5 seconds of ultrasonic vibration / 5 seconds of rest). Then, a pouch type secondary battery was manufactured in the same manner as in Example 1.
  • the composition for gel polymer electrolyte is injected at room temperature (25 ° C.), the composition injection hole for the gel polymer electrolyte is sealed at 140 ° C., and then the formation process and the ultrasonic wave process are not performed.
  • a pouch type secondary battery was manufactured in the same manner as in Example 1, except that the curing step was performed.
  • the composition for gel polymer electrolyte was infused while maintaining the ultrasonic member temperature at 40 ° C., the composition injection hole for the gel polymer electrolyte was sealed at 140 ° C., and then the ultrasonic wave and the addition step were not performed.
  • a pouch type secondary battery was manufactured in the same manner as in Example 1, except that the formation step and the curing step were performed.
  • the composition for gel polymer electrolyte was inject
  • a pouch type secondary battery was manufactured in the same manner as in Example 1 except that an ultrasonic process was not performed using an ultrasonic member and a pressure of 5 Kgf / cm 2 per area was applied to the pouch type secondary battery.
  • a pouch type secondary battery was manufactured in the same manner as in Example 1 except that the ultrasonic member temperature was maintained at room temperature (25 ° C).
  • a pouch type secondary battery was manufactured in the same manner as in Example 2 except that the ultrasonic member temperature was maintained at room temperature (25 ° C).
  • the ultrasonic vibration at 20 KHz was performed 100 cycles (1 cycle: 5) without pressurization using the ultrasonic member.
  • Pouch-type secondary battery was manufactured in the same manner as in Example 1, except that the ultrasonic wave was subjected to ultrasonic vibration / 5 second rest period).
  • a pouch type secondary battery was manufactured in the same manner as in Example 1 except that the ultrasonic member temperature was maintained at 100 ° C.
  • the ultrasonic member temperature is maintained at room temperature (25 ° C.), except for pressurizing at a pressure of 3,500 Kgf / cm2 per area of the pouch type preliminary secondary battery using the ultrasonic member during pressurization.
  • a pouch type secondary battery was manufactured in the same manner as in 1.
  • Impregnation of the pouch-type secondary battery including the gel polymer electrolytes prepared in Example 1 and Comparative Example 1 was measured using AC impedance measurement at 25 ° C. At this time, the ion conductivity was measured in the frequency band 0.05Hz to 100MHz using VMP3 measuring equipment and 4294A. The results are shown in FIG. 2. 2, the horizontal axis represents a real value Z re of the impedance Z calculated by the impedance calculator, and the vertical axis represents an imaginary value Z im of impedance.
  • the reference example in Figure 2 shows the AC impedance measured immediately after the injection of the composition for the gel polymer electrolyte in Example 1.
  • the resistance decreases because the composition for the gel polymer electrolyte is less impregnated with the pore inside the battery. Therefore, when the AC impedance is measured, the bulk resistance is measured to be small, and the resistance value converges as the impregnation proceeds.
  • the pouch type secondary battery of Comparative Example 1 in which the pouch type secondary battery of Example 1, which performed the step of applying ultrasonic vibration based on the value of the pouch type secondary battery of the reference example, was not subjected to the step of applying the ultrasonic vibration. It can be seen that the bulk resistance value is significantly reduced than the battery.
  • the rate of 0.3 C in the constant current-constant voltage (CC-CV) method At a current of 333mA to charge a constant current (CC) until the battery's voltage reaches 4.2V, and after the battery's voltage reaches 4.2V, it cuts off at a current of 0.05C while maintaining the constant voltage (CV) of 4.2V. -off) and charged once.
  • the first charged battery was repeated three times in one cycle of constant current (CC) discharge at a constant current of 333 mA at a rate of 0.3 C until the battery voltage reached 3 V, and the third discharge capacity was selected as the initial capacity. It was.
  • Table 2 The results are shown in Table 2 below.
  • the rate of 0.3 C in the constant current-constant voltage (CC-CV) method At a current of 333mA to charge a constant current (CC) until the battery's voltage reaches 4.2V, and after the battery's voltage reaches 4.2V, it cuts off at a current of 0.05C while maintaining the constant voltage (CV) of 4.2V. -off) and charged once.
  • the first charged battery was repeated three times in a cycle of performing constant current (CC) discharge at a constant current of 333 mA at a rate of 0.3 C until the battery voltage reached 3 V, and a current of 2 A (2 C) was 10 times.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention concerne un procédé de production d'un accumulateur de type poche. Plus particulièrement, la présente invention porte sur un procédé de production d'un accumulateur de type poche comprenant les étapes suivantes consistant : à placer un ensemble électrode dans un espace interne d'un logement de type poche de façon à produire une électrode de type poche préliminaire ; à placer un élément ultrasonore de matériau métallique contre les deux côtés d'un accumulateur de type poche préliminaire ; à injecter une composition d'électrolyte polymère en gel dans l'accumulateur de type poche préliminaire ; à presser l'accumulateur de type poche préliminaire à l'aide de l'élément ultrasonore et à appliquer des vibrations ultrasonores à l'accumulateur de type poche préliminaire ; à former l'accumulateur de type poche préliminaire ; à faire durcir la composition d'électrolyte polymère en gel ; et à réaliser un dégazage, l'élément ultrasonore étant maintenu à une température de 30 à 80 °C et l'étape consistant à presser l'accumulateur de type poche préliminaire étant réalisée tout en appliquant une pression de 0,1 à 3 000 kgf/cm2 par unité de surface de l'accumulateur de type poche préliminaire.
PCT/KR2019/003403 2018-03-26 2019-03-22 Procédé de fabrication d'un accumulateur de type poche WO2019190128A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US16/766,324 US11114698B2 (en) 2018-03-26 2019-03-22 Method of preparing pouch type secondary battery
CN201980005669.0A CN111344889A (zh) 2018-03-26 2019-03-22 制备袋型二次电池的方法
EP19774534.2A EP3699993A4 (fr) 2018-03-26 2019-03-22 Procédé de fabrication d'un accumulateur de type poche

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KR20180034688 2018-03-26
KR10-2018-0034688 2018-03-26
KR1020190032175A KR102255539B1 (ko) 2018-03-26 2019-03-21 파우치형 이차전지의 제조 방법
KR10-2019-0032175 2019-03-21

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KR20140059746A (ko) 2012-11-08 2014-05-16 주식회사 엘지화학 이차전지 제조 방법
KR101626064B1 (ko) * 2013-10-07 2016-05-31 주식회사 엘지화학 이차 전지 및 이를 제조하는 방법
KR101747909B1 (ko) * 2014-02-13 2017-06-15 주식회사 엘지화학 전해액 함침 장치
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JP3806505B2 (ja) * 1998-03-31 2006-08-09 三洋電機株式会社 高分子固体電解質電池の製造方法
KR20140018014A (ko) * 2012-08-03 2014-02-12 에스케이이노베이션 주식회사 파우치형 이차전지의 제조방법
KR20140059746A (ko) 2012-11-08 2014-05-16 주식회사 엘지화학 이차전지 제조 방법
KR101626064B1 (ko) * 2013-10-07 2016-05-31 주식회사 엘지화학 이차 전지 및 이를 제조하는 방법
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113871706A (zh) * 2021-08-31 2021-12-31 湖南立方新能源科技有限责任公司 一种凝胶电解质电芯的制备方法及其应用
CN113871706B (zh) * 2021-08-31 2023-03-28 湖南立方新能源科技有限责任公司 一种凝胶电解质电芯的制备方法及其应用

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