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WO2018012940A1 - Anode et batterie rechargeable la comprenant - Google Patents

Anode et batterie rechargeable la comprenant Download PDF

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Publication number
WO2018012940A1
WO2018012940A1 PCT/KR2017/007610 KR2017007610W WO2018012940A1 WO 2018012940 A1 WO2018012940 A1 WO 2018012940A1 KR 2017007610 W KR2017007610 W KR 2017007610W WO 2018012940 A1 WO2018012940 A1 WO 2018012940A1
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WIPO (PCT)
Prior art keywords
active material
material layer
current collector
binder
stress relaxation
Prior art date
Application number
PCT/KR2017/007610
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English (en)
Korean (ko)
Inventor
이정필
이희원
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.)
Filing date
Publication date
Priority claimed from KR1020170089109A external-priority patent/KR102056455B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US15/771,276 priority Critical patent/US11094937B2/en
Priority to EP17828010.3A priority patent/EP3343674B1/fr
Priority to CN201780003923.4A priority patent/CN108352501B/zh
Priority to JP2018535279A priority patent/JP6665306B2/ja
Priority to PL17828010T priority patent/PL3343674T3/pl
Publication of WO2018012940A1 publication Critical patent/WO2018012940A1/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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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 negative electrode and a secondary battery including the same, wherein the negative electrode comprises a current collector; A first active material layer disposed on the current collector and including at least one recessed portion indented toward the current collector; A stress relaxation part disposed in the recess; And a second active material layer disposed on the first active material layer and spaced apart from the current collector.
  • a representative example of an electrochemical device using such electrochemical energy is a secondary battery, and its use area is gradually increasing.
  • a secondary battery is composed of a positive electrode, a negative electrode, an electrolyte, and a separator, and reciprocates positive and negative electrodes such that lithium ions from the positive electrode active material are inserted into a negative electrode active material such as carbon particles and are detached again when discharged. Since it plays a role of transmitting energy, charging and discharging becomes possible.
  • the capacity of the negative electrode in the cell must be large.
  • Group 14 and Group 15 transition metals and oxides thereof are used as the negative electrode active material.
  • the active material layer including the above materials since the volume is excessively expanded due to charge and discharge, stress is excessively applied to the electrode current collector and the active material layer, so that detachment of the active material particles or peeling of the active material layer may occur. For this reason, a problem may occur in that the life of the battery is shortened or the stability is lowered.
  • One problem to be solved by the present invention is to provide a negative electrode capable of alleviating the stress applied to the electrode current collector and the active material layer while maintaining a high capacity.
  • One embodiment of the invention the current collector; A first active material layer disposed on the current collector and including at least one recessed portion indented toward the current collector; A stress relaxation part disposed in the recess; And a second active material layer disposed on the first active material layer and spaced apart from the current collector.
  • Another embodiment of the present invention provides a secondary battery including the negative electrode.
  • the negative electrode according to the exemplary embodiment of the present invention uses a transition metal, an alloy thereof, and an oxide of each of the transition metal and their alloy as an active material, a high capacity battery may be derived.
  • the stress relaxation portion is disposed in the concave portion of the first active material layer, the stress applied to the current collector and the active material layer can be alleviated, so that detachment of the active material particles and peeling of the active material layer can be prevented.
  • FIG. 1 is a schematic cross-sectional view of a negative electrode according to an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view of a negative electrode according to another embodiment of the present invention.
  • FIG 3 is a schematic cross-sectional view of a negative electrode according to another embodiment of the present invention.
  • FIG. 4 is a schematic cross-sectional view of a negative electrode according to another embodiment of the present invention.
  • the terms “comprise”, “comprise” or “have” are intended to indicate that there is a feature, number, step, component, or combination thereof, that is, one or more other features, It should be understood that it does not exclude in advance the possibility of the presence or addition of numbers, steps, components, or combinations thereof.
  • the "upper” is disposed not only in the case where two components are in contact, but also in a structure disposed up and down at a predetermined interval.
  • a negative electrode according to an embodiment of the present invention, referring to Figure 1, the current collector 100; A first active material layer 110 disposed on the current collector 100 and including at least one concave portion 110a recessed toward the current collector 100; A stress relaxation part 120 disposed in the recess 110a; And a second active material layer disposed on the first active material layer 110 and including the second active material layer 130 spaced apart from the current collector 100.
  • the current collector is conductive without causing chemical change in the secondary battery, and includes, for example, copper, stainless steel, aluminum, nickel, titanium, calcined carbon, or carbon, nickel, on the surface of aluminum or stainless steel.
  • the surface-treated with titanium, silver, etc. can be used.
  • the first active material layer may be disposed on the current collector, and the first active material layer may be disposed on the current collector, and specifically, may be disposed on one or both surfaces of the current collector.
  • the first active material layer may include first active material particles and a first binder.
  • the first active material particles may be at least one active material particle selected from the group consisting of graphite-based materials, transition metals, transition metal oxides, transition metal alloys, oxides of transition metal alloys, and transition metal-containing composites.
  • the graphite material may be at least one selected from the group consisting of artificial graphite, natural graphite, graphitized carbon fibers and graphitized mesocarbon microbeads.
  • the transition metal may be any one of Group 14 and Group 15 transition metals, and specifically, the transition metal may be any one of a silicon-based material, a tin-based material, and a germanium-based material.
  • the transition metal oxide, the transition metal alloy, the oxide of the transition metal alloy, and the transition metal included in the transition metal-containing composite may be the above-described transition metal.
  • the first active material particles and the second active material particles are Si, SiOx (0 ⁇ x ⁇ 2), Si-C composite and Si-Y alloy (where Y is At least one selected from the group consisting of alkali metals, alkaline earth metals, transition metals, group 13 elements, group 14 elements, rare earth elements, and combinations thereof.
  • the first binder may include at least one of an aqueous binder and an oily binder.
  • the first binder is polyvinylidene fluoride (PVdF), carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), polyacrylonitrile, polymethyl Polymethylmethacrylate, Polyvinyl alcohol, Starch, Hydroxypropylcellulose, Regenerated cellulose, Polyvinyl pyrrolidone, Tetrafluoroethylene, Polyethylene , Polypropylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, fluororubber and hydrogens thereof by Li, Na or Ca Polymers, or various copolymers such as polyvinylidene fluoride, carboxymethyl cellulose, styrene-butadiene rubber Luer binary may be at least one and hexafluorotitanate different types of binder such as a copolymer of propylene (
  • the first active material layer may include at least one concave portion.
  • the recess may be indented toward the current collector. Specifically, referring to FIG. 1, the recess may be indented to the current collector to penetrate the first active material layer. That is, the concave portion may be indented toward the current collector as much as the entire thickness of the first active material layer.
  • the concave portion may have a hole shape surrounded by the first active material layer. Alternatively, the concave portion may correspond to the spaced space when the first active material layer includes two or more portions spaced apart from each other.
  • the recesses may be formed at regular intervals, or may be formed at random intervals.
  • the concave portion may be formed in a constant shape, or may be formed in a non-uniform shape.
  • the stress relaxation part may be disposed in the recess.
  • the stress relief part may fill part or all of the recess.
  • the stress relaxation part 120 of the cathode according to the present exemplary embodiment may fill all of the recesses 110a.
  • the stress relaxation part and the first active material layer may contact each other while the stress relaxation part is disposed in the recess.
  • the first active material layer includes two or more portions spaced apart by the concave portion, one surface of the stress relaxation part contacts a portion of the first active material layer, and the other surface of the stress relaxation part is a portion of the first active material layer. Can touch other parts.
  • the stress relaxation part absorbs the stress generated by the volume expansion of the first active material layer and the second active material layer during charging and discharging of the battery, thereby alleviating the stress applied to the current collector, the first active material layer, and the second active material layer. can do. Thereby, desorption of the 1st active material particle and the 2nd active material particle of the 2nd active material layer mentioned later can be prevented, and peeling of a 1st active material layer and a 2nd active material layer can be prevented.
  • the stress relaxation part may include at least one of an aqueous polymer and an organic polymer.
  • the aqueous polymer is polyvinylpyrrolidone (poly (vinyl pyrrolidone)), polyacrylamide (polyacrylamide), polyacrylic acid (polyacrylic acid), polyvinyl methyl ether (poly (vinyl methyl ether)), polypropylene glycol (poly ( propylene glycol), cellulose, cellulose, polyN-isopropylmethacrylamide (poly (N-isopropylmethacrylamide)), and at least one selected from the group consisting of polyethylene oxide.
  • the aqueous polymer is dispersed in an aqueous solvent to form the stress relaxation part.
  • the stress relaxation part is preferably an aqueous polymer.
  • the organic polymer is polystyrene, poly (methylmethacrylate), polyethylene, polypropylene, polyethylene oxide, polyvinyl alcohol, poly Polyvinyl chloride, polyimide, polyamide, polyamide, polyamide imide, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene -co-hexafluoropropylene, polyvinylidene fluoride-co-trichloroethylene, polybutylacrylate, polyacrylonitrile, polyvinylacetate, ethylene vinyl acetate Copolymer (polyethylene-co-vinyl acetate), polyethylene oxide , Polyarylate, and at least one selected from the group consisting of copolymers thereof.
  • the organic polymer In the case of using the organic polymer, it is possible to minimize the change of the electrode structure during electrode coating or wet etching in the production of the aqueous cathode.
  • the organic polymer When the organic polymer is used as the stress relaxation part, the organic polymer is dispersed in an organic solvent to form the stress relaxation part.
  • the stress relaxation part is preferably an organic polymer.
  • the stress relaxation part and the first active material layer may be included in the negative electrode in a volume ratio of 1:99 to 50:50, specifically 5:95 to 30:70, and more specifically 10:90 to 20: 80 may be.
  • the volume ratio is satisfied, the stress relaxation effect is more excellent, and an excessive increase in electrode resistance can be prevented.
  • the stress relaxation unit may be a square column, a cylinder, a cone, a pyramid, or the like, but is not necessarily limited thereto.
  • the second active material layer may be disposed on the first active material layer.
  • the second active material layer may cover the stress relaxation part.
  • the second active material layer and the stress relaxation portion may or may not be in contact.
  • the second active material layer may be spaced apart from the current collector with the first active material layer and the stress relaxation part interposed therebetween.
  • the second active material layer may serve to prevent desorption of the first active material particles and desorption of constituent materials of the stress relaxation unit.
  • the second active material layer may include second active material particles and a second binder.
  • the second active material particles may be at least one active material particle selected from the group consisting of graphite-based materials, transition metals, transition metal oxides, transition metal alloys, oxides of transition metal alloys, and transition metal-containing composites.
  • the graphite material may be at least one selected from the group consisting of artificial graphite, natural graphite, graphitized carbon fibers and graphitized mesocarbon microbeads.
  • the transition metal may be any one of Group 14 and Group 15 transition metals, and specifically, the transition metal may be any one of a silicon-based material, a tin-based material, and a germanium-based material.
  • the transition metal oxide, the transition metal alloy, the oxide of the transition metal alloy, and the transition metal included in the transition metal-containing composite may be the above-described transition metal.
  • the first active material particles and the second active material particles are Si, SiOx (0 ⁇ x ⁇ 2), Si-C composite and Si-Y alloy (where Y is At least one selected from the group consisting of alkali metals, alkaline earth metals, transition metals, group 13 elements, group 14 elements, rare earth elements, and combinations thereof.
  • the second binder is polyvinylidene fluoride (PVdF), carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), polyacrylonitrile, polymethyl Polymethylmethacrylate, Polyvinyl alcohol, Starch, Hydroxypropylcellulose, Regenerated cellulose, Polyvinyl pyrrolidone, Tetrafluoroethylene, Polyethylene , Polypropylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, fluororubber and hydrogens thereof by Li, Na or Ca Polymers, or various copolymers such as polyvinylidene fluoride, carboxymethyl cellulose, styrene-butadiene rubber Luer binary may be at least one and hexafluorotitanate different types of binder such as a copolymer of propylene (Hexafluoropropylene, HFP) is selected from the group.
  • PVdF polyvin
  • Each of the first active material layer and the second active material layer may further include a conductive material.
  • the conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • Examples of the conductive material include graphite such as natural graphite and artificial graphite; Carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, farnes black, lamp black and thermal black; Conductive fibers such as carbon fibers and metal fibers; Conductive tubes such as carbon nanotubes; Metal powders such as fluorocarbon, aluminum and nickel powders; Conductive whiskers 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 cathode according to another embodiment of the present invention is similar to the cathode according to the embodiment described with reference to FIG. 1, but the stress relief part 120 may fill a part of the recess 110a. The difference is that there is.
  • differences from the embodiment described with reference to FIG. 1 will be mainly described.
  • an area other than the region filled with the stress relaxation portion in the recess portion may exist as an empty space.
  • the empty space may serve to reduce a stress caused by volume expansion by securing a region in which the first active material layer and the second active material layer which are volume expanded during charge / discharge of the battery may be located.
  • the stress relaxation part may contact at least one of the first active material layer, the second active material layer, and the current collector.
  • the negative electrode of the embodiment according to FIG. 2 may include not only a recess partially filled with the stress relaxed part but also a recess partially filled with the stress relaxed part.
  • the negative electrode according to another embodiment of the present invention is similar to the negative electrode according to the exemplary embodiment described with reference to FIG. 1, except that some recesses are not filled by the stress relaxation unit.
  • some recesses are not filled by the stress relaxation unit.
  • the cathode of the embodiment according to FIG. 3 may include a plurality of recesses, and the stress relaxation unit may fill some of the recesses of the plurality of recesses. At least one recess of the portion may be at least one. Accordingly, the concave portion, in which the stress relaxation portion is not filled, may secure a region in which the first active material layer and the second active material layer may be located when the battery is charged and discharged, thereby reducing the stress caused by the volume expansion. have.
  • the stress relaxation portion disposed in the recessed portion absorbs the stress generated by the volume expansion of the first active material layer and the second active material layer during charge and discharge of the battery, so that the current collector, the first active material layer and the second active material layer It can serve to relieve the stress applied.
  • the negative electrode according to another embodiment of the present invention is similar to the negative electrode according to the exemplary embodiment described with reference to FIG. 1, except that the recess does not penetrate the first active material layer.
  • the recess does not penetrate the first active material layer.
  • the recess may be indented toward the current collector, but the current collector and the recess may not be connected to each other.
  • the first active material layer may be positioned between the concave portion and the current collector in a direction perpendicular to the current collector. In this case, while the effect of preventing the active material detachment by the stress relaxation unit is maintained at a certain level, the content of the first active material particles can be maintained at a high level, thereby further improving the battery capacity.
  • the negative electrode according to the embodiments of the present invention can be manufactured by the following method.
  • the first active material layer may be manufactured by applying a slurry for preparing the first active material layer prepared by mixing the electrode mixture including the first active material particles, the binder, and the conductive material to a solvent, followed by drying and rolling.
  • the manufactured first active material layer may be selectively etched through a mask to form at least one concave portion. Thereafter, after the stress relief portion is formed in the manufactured recess, the mask may be removed.
  • the stress relaxation part may be formed by applying a slurry in which the material for forming the stress relaxation part is dispersed in a solvent and then drying.
  • a slurry for preparing the second active material layer prepared by mixing the electrode mixture including the second active material particles, the binder, and the conductive material in a solvent is applied on the first active material layer and the stress relaxation part, and then dried and By rolling, a second active material layer may be produced.
  • a screen printing method an inkjet method, a spray method, a gravure printing method, a thermal transfer method, a plate printing method, an intaglio printing method, and an offset printing method may be used to form the first active material layer, the stress relaxation part, and the second active material layer.
  • a screen printing method an inkjet method, a spray method, a gravure printing method, a thermal transfer method, a plate printing method, an intaglio printing method, and an offset printing method may be used to form the first active material layer, the stress relaxation part, and the second active material layer.
  • One or more may be used.
  • the solvent used to prepare the negative electrode may be a solvent generally used in the art, dimethyl sulfoxide (dimethyl sulfoxide, DMSO), isopropyl alcohol (isopropyl alcohol), N-methylpyrrolidone (NMP ), Acetone (acetone) or water, and the like, one of these may be used alone or a mixture of two or more thereof.
  • DMSO dimethyl sulfoxide
  • NMP N-methylpyrrolidone
  • Acetone acetone
  • water and the like, one of these may be used alone or a mixture of two or more thereof.
  • the first active material layer and the concave portion may be formed by another method.
  • the slurry for producing the first active material layer before applying the slurry for producing the first active material layer, after placing a mask on the current collector, the slurry for producing the first active material layer is applied, dried and rolled to prepare a first active material layer.
  • the recess may be formed by removing the mask.
  • the production of a cathode in which only a part of the recess is filled with the stress relaxation portion may be as follows. There is no difference in the point of forming a 1st active material layer and a recessed part by the same method as mentioned above. However, polymers such as polymethyl methacrylate, polyethylene, and polyethyloxide may be formed before the stress relaxation portion is formed or after the stress relaxation portion is formed only in a part of the recess portion. You can fill in the remaining areas. Thereafter, after the second active material layer is formed in the same manner as described above, the polymer may be removed by wet etching or the like to form a recessed space.
  • some of the plurality of recesses may be filled only with the polymer, not the stress relaxation part, and then the polymer may be removed in the same manner after the second active material layer is formed. Accordingly, the recess may be formed without filling the stress relaxation portion.
  • a secondary battery according to another embodiment of the present invention may include a negative electrode, a positive electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte, and the negative electrode may be an electrode according to an embodiment of the present invention.
  • the positive electrode may be formed on the positive electrode current collector and the positive electrode current collector, and may include a positive electrode active material layer including the positive electrode active material.
  • the positive electrode current collector is not particularly limited as long as it is conductive without causing chemical change in the battery.
  • the positive electrode current collector is made 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 positive electrode current collector may have a thickness of about 3 to 500 ⁇ m, and may form fine irregularities on the surface of the current collector to increase adhesion of the positive electrode active material.
  • it can be used in various forms, such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven body.
  • the cathode active material may be a cathode active material that is commonly used.
  • the cathode active material may be a layered compound such as lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ), or a compound substituted with one or more transition metals; Lithium iron oxides such as LiFe 3 O 4 ; Lithium manganese oxides such as Li 1 + c1 Mn 2 - c1 O 4 (0 ⁇ c1 ⁇ 0.33), LiMnO 3 , LiMn 2 O 3 , LiMnO 2 ; Lithium copper oxide (Li 2 CuO 2 ); Vanadium oxides such as LiV 3 O 8 , V 2 O 5 , Cu 2 V 2 O 7, and the like; Formula LiNi 1 - c2 M c2 O 2 ( where, M is a least one selected from the group consisting of Co, Mn, Al, Cu, Fe, Mg, B and Ga, satisfies
  • the cathode active material layer may include a cathode conductive material and a cathode binder together with the cathode active material described above.
  • the cathode conductive material is used to impart conductivity to the electrode, and in the battery constituted, the cathode conductive material may be used without particular limitation as long as it has electron conductivity without causing chemical change.
  • Specific examples thereof include graphite such as natural graphite and artificial graphite; Carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, summer black and carbon fiber; Metal powder or metal fibers such as copper, nickel, aluminum, and silver; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Or conductive polymers such as polyphenylene derivatives, and the like, or a mixture of two or more kinds thereof may be used.
  • the positive electrode binder serves to improve adhesion between the positive electrode active material particles and the positive electrode active material and the positive electrode current collector.
  • specific examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethyl cellulose (CMC).
  • the separator separates the negative electrode from the positive electrode and provides a passage for lithium ions, and can be used without particular limitation as long as the separator is used as a separator in a secondary battery. In particular, it has a low resistance to ion migration of the electrolyte and an excellent ability to hydrate the electrolyte. It is preferable.
  • a porous polymer film for example, a porous polymer film made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer or the like Laminate structures of two or more layers may be used.
  • porous nonwoven fabrics such as nonwoven fabrics made of high melting point glass fibers, polyethylene terephthalate fibers and the like may be used.
  • a coated separator including a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength, and may be optionally used as a single layer or a multilayer structure.
  • Examples of the electrolyte include an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel polymer electrolyte, a solid inorganic electrolyte, a molten inorganic electrolyte, and the like that can be used in manufacturing a lithium secondary battery, but are not limited thereto.
  • the electrolyte may include a non-aqueous organic solvent and a metal salt.
  • non-aqueous organic solvent for example, N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butylo lactone, 1,2-dime Methoxy ethane, tetrahydroxy franc, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolon, formamide, dimethylformamide, dioxoron, acetonitrile, nitromethane, methyl formate, Methyl acetate, phosphate triester, trimethoxy methane, dioxorone derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ethers, pyrion
  • An aprotic organic solvent such as methyl acid or ethyl
  • ethylene carbonate and propylene carbonate which are cyclic carbonates among the carbonate-based organic solvents, may be preferably used as high-viscosity organic solvents because they have high dielectric constants to dissociate lithium salts well, such as dimethyl carbonate and diethyl carbonate.
  • high-viscosity organic solvents because they have high dielectric constants to dissociate lithium salts well, such as dimethyl carbonate and diethyl carbonate.
  • an electrolyte having a high electrical conductivity can be made, and thus it can be more preferably used.
  • the metal salt may be a lithium salt
  • the lithium salt is a material that is readily soluble in the non-aqueous electrolyte, for example, is in the lithium salt anion F -, Cl -, I - , NO 3 -, N (CN ) 2 -, BF 4 -, ClO 4 -, PF 6 -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF - , (CF 3) 6 P - , CF 3 SO 3 -, CF 3 CF 2 SO 3 -, (CF 3 SO 2) 2 N -, (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2 ) 2 CH -, (SF 5) 3 C -, (CF 3 SO 2) 3 C -, CF 3 (CF 2) 7 SO 3 -, CF 3 CO 2 -, CH 3 CO 2 -
  • the electrolyte includes, for example, haloalkylene carbonate-based compounds such as difluoro ethylene carbonate, pyridine, tri, etc. for the purpose of improving battery life characteristics, reducing battery capacity, and improving discharge capacity of the battery.
  • haloalkylene carbonate-based compounds such as difluoro ethylene carbonate, pyridine, tri, etc.
  • Ethyl phosphite triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N, N-substituted imida
  • One or more additives such as zolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxy ethanol or aluminum trichloride may be included.
  • a battery module including the secondary battery as a unit cell and a battery pack including the same are provided. Since the battery module and the battery pack include the secondary battery having high capacity, high rate characteristics, and cycle characteristics, a medium-large device selected from the group consisting of an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, and a power storage system It can be used as a power source.
  • Production Example 1 first Active material layer Slurry for Formation
  • SBR styrene-butadiene rubber
  • CMC carboxymethyl cellulose
  • the slurry for forming the first active material layer prepared in Preparation Example 1 was applied to a copper thin film, which is a negative electrode current collector having a thickness of 20 ⁇ m, and dried and roll pressed to have a thickness of 18 ⁇ m and a loading amount of 2.1 mAh / cm 2.
  • the first active material layer of was formed.
  • the first active material layer was partially etched by lithography to remove a portion reaching 30% of the volume of the first active material layer. Thereafter, a solution of 2.5% by weight of polyvinylidene fluoride (PVdF) dissolved in N-methylpyrrolidone (NMP) was applied to the etched portion and dried to form a stress relaxation part. The stress relaxation part filled all of the inside of the etching region.
  • PVdF polyvinylidene fluoride
  • NMP N-methylpyrrolidone
  • the slurry for forming the second active material layer was applied onto the first active material layer and the stress relaxation part, and dried. Thereafter, roll pressing was performed to form a second active material layer having a thickness of 20 ⁇ m and a loading amount of 0.3 mAh / cm 2 to prepare a negative electrode.
  • Li metal was used as the counter electrode.
  • An electrode assembly was prepared by interposing a polyolefin separator between the cathode and the Li metal. Meanwhile, 0.5 wt% of vinylene carbonate (VC) was dissolved in a mixed solution in which ethylene carbonate (EC) and ethylmethyl carbonate (EMC) were mixed at a volume ratio of 7: 3, and LiPF 6 was dissolved (1M concentration) in an electrolyte solution. was prepared. The electrolyte solution was injected into the electrode assembly to prepare a coin-type half cell.
  • VC vinylene carbonate
  • EMC ethylmethyl carbonate
  • Example 2 manufacture of a battery
  • Example 2 was prepared in the same manner as in Example 1, except that polyvinylidene fluoride (PVdF) was dissolved in 1% by weight of N-methylpyrrolidone (NMP). Coin-type half cells were prepared.
  • the cathode included a structure in which the stress relaxation part filled only a part of the inside of the etching region.
  • a first active material layer was formed in the same manner as in Example 1.
  • the first active material layer was partially etched by lithography to remove a portion reaching 15% of the volume of the first active material layer. Thereafter, a solution of 2.5% by weight of polyvinylidene fluoride (PVdF) dissolved in N-methylpyrrolidone (NMP) was applied to the etched portion and dried to form a stress relaxation part. Subsequently, an unetched portion of the first active material layer was etched through lithography to further remove 15% of the volume of the first active material layer.
  • PVdF polyvinylidene fluoride
  • NMP N-methylpyrrolidone
  • a second active material layer was formed in the same manner as in Example 1.
  • a coin-type half cell of Example 3 was prepared in the same manner as in Example 1.
  • the negative electrode slurry was applied to a copper thin film, which is a negative electrode current collector having a thickness of 20 ⁇ m, and dried and roll pressed to prepare a negative electrode having an active material layer having a thickness of 38 ⁇ m and a loading amount of 1.7 mAh / cm 2 .
  • Li metal was used as the counter electrode.
  • An electrode assembly was prepared by interposing a polyolefin separator between the cathode and the Li metal. Meanwhile, 0.5 wt% of vinylene carbonate (VC) was dissolved in a mixed solution in which ethylene carbonate (EC) and ethylmethyl carbonate (EMC) were mixed at a volume ratio of 7: 3, and LiPF 6 was dissolved (1M concentration) in an electrolyte solution. was prepared. The electrolyte solution was injected into the electrode assembly to prepare a coin-type half cell.
  • VC vinylene carbonate
  • EMC ethylmethyl carbonate
  • Comparative example 2 manufacture of a battery
  • the slurry for forming the first active material layer prepared in Preparation Example 1 was applied to a copper thin film, which is a negative electrode current collector having a thickness of 20 ⁇ m, and dried and roll pressed to have a thickness of 18 ⁇ m and a loading amount of 1.4 mAh / cm 2.
  • the first active material layer of was formed.
  • the slurry for forming the second active material layer was applied onto the first active material layer and dried. Thereafter, roll pressing was performed to form a second active material layer having a thickness of 20 ⁇ m and a loading amount of 0.3 mAh / cm 2 to prepare a negative electrode.
  • Li metal was used as the counter electrode.
  • An electrode assembly was prepared by interposing a polyolefin separator between the cathode and the Li metal. Meanwhile, 0.5 wt% of vinylene carbonate (VC) was dissolved in a mixed solution in which ethylene carbonate (EC) and ethylmethyl carbonate (EMC) were mixed at a volume ratio of 7: 3, and LiPF 6 was dissolved (1M concentration) in an electrolyte solution. was prepared. The electrolyte solution was injected into the electrode assembly to prepare a coin-type half cell.
  • VC vinylene carbonate
  • EMC ethylmethyl carbonate
  • Cycle characteristics were evaluated for the batteries of Examples 1 to 3 and Comparative Examples 1 and 2, respectively.
  • One cycle and two cycles were charged and discharged at 0.1C, and charged and discharged at 0.5C from three cycles to 30 cycles. Thereafter, the discharge capacity after 10 cycles and 30 cycles was evaluated relative to the discharge capacity after one cycle, and the results are shown in Table 1.
  • the battery of Examples 1 to 3 shows excellent cycle characteristics compared to the batteries of Comparative Examples 1 and 2. This is considered to be based on the relaxation of the stress generated in the active material layer during charge and discharge by the stress relaxation unit.
  • Example 2 in which only a part of the etching region (corresponding to the concave described in the detailed description) is filled with the stress relaxation portion and in Example 3 where the some etching region does not include the stress relaxation portion, the stress relaxation effect is more excellent. have.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne une anode et une batterie rechargeable la comprenant et, plus particulièrement, une anode comprenant : un collecteur de courant ; une première couche de matière active disposée sur le collecteur de courant et comprenant au moins une partie concave qui expose une partie du collecteur de courant ; une partie de relaxation de contrainte disposée dans la partie concave ; et une seconde couche de matière active disposée sur la première couche de matière active et sur la partie de relaxation de contrainte et espacée du collecteur de courant, et une batterie rechargeable la comprenant.
PCT/KR2017/007610 2016-07-15 2017-07-14 Anode et batterie rechargeable la comprenant WO2018012940A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US15/771,276 US11094937B2 (en) 2016-07-15 2017-07-14 Negative electrode and secondary battery including the same
EP17828010.3A EP3343674B1 (fr) 2016-07-15 2017-07-14 Anode et batterie rechargeable la comprenant
CN201780003923.4A CN108352501B (zh) 2016-07-15 2017-07-14 负极和包含它的二次电池
JP2018535279A JP6665306B2 (ja) 2016-07-15 2017-07-14 負極およびこれを含む二次電池
PL17828010T PL3343674T3 (pl) 2016-07-15 2017-07-14 Anoda i zawierający ją akumulator

Applications Claiming Priority (4)

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KR20160089735 2016-07-15
KR10-2016-0089735 2016-07-15
KR10-2017-0089109 2017-07-13
KR1020170089109A KR102056455B1 (ko) 2016-07-15 2017-07-13 음극 및 이를 포함하는 이차 전지

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Cited By (1)

* Cited by examiner, † Cited by third party
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CN115939315A (zh) * 2023-03-08 2023-04-07 中创新航材料科技(四川)有限公司 电极片及包含它的电池

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US20100003544A1 (en) * 2006-08-04 2010-01-07 Koninklijke Philips Electronics N.V. Electrochemical energy source, electronic device, and method manufacturing such an electrochemical energy source
JP2010176980A (ja) * 2009-01-28 2010-08-12 Nissan Motor Co Ltd リチウムイオン二次電池用負極およびこれを用いたリチウムイオン二次電池
JP2012038528A (ja) * 2010-08-05 2012-02-23 Toyota Motor Corp 負極板、リチウムイオン二次電池及び負極板の製造方法
WO2014116029A1 (fr) * 2013-01-25 2014-07-31 주식회사 엘지화학 Anode destinée à une batterie secondaire au lithium et batterie secondaire au lithium incluant ladite anode
KR20160059408A (ko) * 2014-11-18 2016-05-26 에스케이이노베이션 주식회사 리튬 이차 전지용 전극 및 이를 포함하는 리튬 이차 전지

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Publication number Priority date Publication date Assignee Title
US20100003544A1 (en) * 2006-08-04 2010-01-07 Koninklijke Philips Electronics N.V. Electrochemical energy source, electronic device, and method manufacturing such an electrochemical energy source
JP2010176980A (ja) * 2009-01-28 2010-08-12 Nissan Motor Co Ltd リチウムイオン二次電池用負極およびこれを用いたリチウムイオン二次電池
JP2012038528A (ja) * 2010-08-05 2012-02-23 Toyota Motor Corp 負極板、リチウムイオン二次電池及び負極板の製造方法
WO2014116029A1 (fr) * 2013-01-25 2014-07-31 주식회사 엘지화학 Anode destinée à une batterie secondaire au lithium et batterie secondaire au lithium incluant ladite anode
KR20160059408A (ko) * 2014-11-18 2016-05-26 에스케이이노베이션 주식회사 리튬 이차 전지용 전극 및 이를 포함하는 리튬 이차 전지

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115939315A (zh) * 2023-03-08 2023-04-07 中创新航材料科技(四川)有限公司 电极片及包含它的电池

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