WO2016208949A1 - Électrode pour pile rechargeable au lithium et son procédé de préparation, ensemble électrode pour pile rechargeable au lithium la comprenant et pile rechargeable au lithium le comprenant - Google Patents

Électrode pour pile rechargeable au lithium et son procédé de préparation, ensemble électrode pour pile rechargeable au lithium la comprenant et pile rechargeable au lithium le comprenant Download PDF

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WO2016208949A1
WO2016208949A1 PCT/KR2016/006591 KR2016006591W WO2016208949A1 WO 2016208949 A1 WO2016208949 A1 WO 2016208949A1 KR 2016006591 W KR2016006591 W KR 2016006591W WO 2016208949 A1 WO2016208949 A1 WO 2016208949A1
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electrode
formula
group
carbon atoms
secondary battery
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PCT/KR2016/006591
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English (en)
Korean (ko)
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송기석
정병효
박성은
양두경
권기영
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주식회사 엘지화학
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Priority claimed from KR1020160076868A external-priority patent/KR102006721B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US15/543,387 priority Critical patent/US10418633B2/en
Priority to EP16814662.9A priority patent/EP3232498B1/fr
Priority to JP2017541649A priority patent/JP6441492B2/ja
Priority to CN201680009473.5A priority patent/CN107210446B/zh
Publication of WO2016208949A1 publication Critical patent/WO2016208949A1/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
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 an electrode for a lithium secondary battery comprising a crosslinked aqueous binder, a method of manufacturing the same, an electrode assembly for a lithium secondary battery comprising the same, and a lithium secondary battery including the same.
  • lithium secondary batteries include lithium ion batteries, lithium sulfur batteries, lithium-air batteries and the like.
  • the lithium-sulfur systems, 16Li + S 8 ⁇ A system for the reaction of 8Li 2 S, the conventional Li-ion battery (500Whkg - 1) - a system that can achieve a very high energy (1 2,500Whkg) than.
  • the lithium sulfur battery uses sulfur and lithium metal, which is a large-capacity material, than the materials (cathode lithium cobalt oxide / cathode carbon) that lithium ion batteries and lithium ion polymer batteries mainly use for positive and negative electrodes. It is attracting attention as a next-generation secondary battery because it can have a large capacity of 3 to 5 times or more than a lithium ion polymer battery, and the material is inexpensive and environmentally friendly.
  • the lithium sulfur battery generally uses a sulfur-based material having an SS bond (Sulfur-Sulfur linkage) as a cathode active material, and an alkali metal such as lithium, or a carbon-based material capable of inserting / deinserting metal ions such as lithium ions. Used as negative electrode active material.
  • the lithium sulfur battery uses an oxidation-reduction reaction in which the oxidation of S decreases as the SS bond is broken during the reduction reaction (discharge), and the SS bond is formed again as the oxidation number of S increases during the oxidation reaction (charging). Store and generate electrical energy.
  • the lithium sulfur battery is difficult to maintain the structure of the sulfur / carbon charge / discharge composite using the aqueous / non-aqueous polymers, the electrode loading per area is low due to the low adhesion between the contact electrode and the composite ( ⁇ 2 mAh / cm 2 ), There is a problem in that the ability to suppress the dissolution of lithium-polysulfide is insufficient.
  • Another object of the present invention is to provide a method for producing the electrode for a lithium secondary battery.
  • Still another object of the present invention is to provide an electrode assembly for a lithium secondary battery including the electrode for a lithium secondary battery.
  • Still another object of the present invention is to provide a lithium secondary battery including the electrode assembly for a lithium secondary battery.
  • the inventors of the present invention by adding a cross-linker in the manufacturing process of the lithium secondary battery electrode, by improving the physical properties of the aqueous binder, the life of the lithium secondary battery, preferably lithium sulfur battery
  • the present invention was completed to find that it is possible to improve the performance, improve the low initial charge / discharge efficiency, and improve the area capacity of the electrode.
  • an electrode active material, an aqueous binder, and a lithium secondary battery electrode including a compound represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2 are provided.
  • R 1 to R 3 are each independently selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a halogen atom, wherein R 4 is H, N (R 7 ) 2 , CO 2 R 7 , R 8 SH, R 8 Si (OR 7 ) 3 and any one selected from the group consisting of alkyl groups having 1 to 3 carbon atoms, wherein R 5 to R 7 are each independently Hydrogen or an alkyl group having 1 to 3 carbon atoms, R 8 is an alkylene group having 1 to 3 carbon atoms, and n is an integer of 1 to 6;
  • the compound represented by Chemical Formula 1, the compound represented by Chemical Formula 2, and any one compound selected from the group consisting of a combination thereof may be a crosslinking reaction material for crosslinking the aqueous binder.
  • the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 may be chemically combined and represented by the following Chemical Formula 3.
  • R 1 to R 3 are each independently selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a halogen atom, wherein R 4 is H, N (R 7 ) 2 , CO 2 R 7 , R 8 SH, R 8 Si (OR 7 ) 3 And any one selected from the group consisting of alkyl groups having 1 to 3 carbon atoms, wherein R 5 to R 7 are each independently hydrogen or An alkyl group having 1 to 3 carbon atoms, R 8 is an alkylene group having 1 to 3 carbon atoms, and n is an integer of 1 to 6 carbon atoms.
  • R 1 to R 3 are all an alkoxy group having 1 to 3 carbon atoms, and R 4 is N (R 7 ) 2 , CO 2 R 7 , R 8 SH and R 8 Si (OR 7 ) 3 may be any one selected from the group consisting of.
  • the aqueous binder may be any one selected from the group consisting of carboxymethyl cellulose (CMC), alginate, carbonyl- ⁇ -cyclodextrine, and nafion. .
  • CMC carboxymethyl cellulose
  • alginate alginate
  • carbonyl- ⁇ -cyclodextrine alginate
  • nafion nafion
  • the electrode for a lithium secondary battery includes 0.1 to 40 wt% of the aqueous binder, 0.1 to 20 wt% of the compound represented by Chemical Formula 1, and 0.1 to 20 wt% of the compound represented by Chemical Formula 2 with respect to the total weight of the electrode. can do.
  • the lithium secondary battery electrode may be a positive electrode.
  • the lithium secondary battery is a lithium sulfur battery
  • the cathode active material may be any one selected from the group consisting of elemental sulfur (S 8 ), a sulfur-based compound, and a mixture thereof.
  • preparing an electrode forming slurry by mixing an electrode active material, an aqueous binder, a compound represented by the following Formula 1, and a compound represented by the following Formula 2, and the slurry for forming the electrode It provides a method for producing an electrode for a lithium secondary battery comprising the step of manufacturing an electrode by coating on at least one surface of the current collector.
  • R 1 to R 3 are each independently selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a halogen atom, wherein R 4 is H, N (R 7 ) 2 , CO 2 R 7 , R 8 SH, R 8 Si (OR 7 ) 3 and any one selected from the group consisting of alkyl groups having 1 to 3 carbon atoms, wherein R 5 to R 7 are each independently Hydrogen or an alkyl group having 1 to 3 carbon atoms, R 8 is an alkylene group having 1 to 3 carbon atoms, and n is an integer of 1 to 6;
  • the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 may be chemically combined and represented by the following Chemical Formula 3.
  • R 1 to R 3 are each independently selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a halogen atom, wherein R 4 is H, N (R 7 ) 2 , CO 2 R 7 , R 8 SH, R 8 Si (OR 7 ) 3 And any one selected from the group consisting of alkyl groups having 1 to 3 carbon atoms, wherein R 5 to R 7 are each independently hydrogen or An alkyl group having 1 to 3 carbon atoms, R 8 is an alkylene group having 1 to 3 carbon atoms, and n is an integer of 1 to 6 carbon atoms.
  • the preparing of the slurry for forming an electrode may include mixing the aqueous binder, the compound represented by Chemical Formula 1, and the compound represented by Chemical Formula 2, and then mixing the electrode active material.
  • a positive electrode and a negative electrode are alternately stacked at the boundary of the separator, and at least one of the positive electrode and the negative electrode provides an electrode assembly for a lithium secondary battery.
  • a lithium secondary battery including the electrode assembly is provided.
  • the crosslinking reaction material is combined with the aqueous binder to improve the physical properties of the aqueous binder, thereby improving the initial charge / discharge efficiency and lifetime of the lithium secondary battery, preferably lithium sulfur battery, and the area capacity of the electrode. Can improve.
  • FIG. 1 is a schematic diagram showing the structure of an improved aqueous binder due to the addition of a crosslinking reaction material.
  • Example 2 is a graph showing the cycle characteristics of the lithium sulfur battery prepared in Example 1, Comparative Example 1 and Comparative Example 2.
  • Example 3 is a graph showing the initial charge / discharge efficiency of the lithium sulfur battery prepared in Example 1, Comparative Example 1 and Comparative Example 2.
  • halogen atom means any one selected from the group consisting of fluorine, chlorine, bromine and iodine.
  • an alkyl group includes a primary alkyl group, a secondary alkyl group, and a tertiary alkyl group.
  • the substituted Iran hydrogen is a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an amino group, a thio group, a methylthio group, an alkoxy group, a nitrile group, an aldehyde group, an epoxy group, an ether group, an ester group, a carbonyl group, Substituted with any one selected from the group consisting of acetal groups, ketone groups, alkyl groups, perfluoroalkyl groups, cycloalkyl groups, heterocycloalkyl groups, allyl groups, benzyl groups, aryl groups, heteroaryl groups, derivatives thereof, and combinations thereof Means that.
  • an alkylene group is a divalent atomic group formed by excluding two hydrogen atoms bonded to two other carbon atoms in an aliphatic saturated hydrocarbon, and represented by the general formula -C n H 2n- . Can be.
  • An electrode for a rechargeable lithium battery includes an electrode active material, an aqueous binder, a compound represented by Formula 1, and a compound represented by Formula 2 below.
  • the compound represented by Chemical Formula 1, the compound represented by Chemical Formula 2, and any one compound selected from the group consisting of a combination thereof may be a cross-linker crosslinking the aqueous binder.
  • the lithium secondary battery electrode may include the crosslinking reaction material, thereby improving physical properties of the aqueous binder.
  • the lithium secondary battery electrode includes an electrode active material, and an aqueous binder crosslinked by any one compound selected from the group consisting of a compound represented by Formula 1, a compound represented by Formula 2, and a combination thereof. can do.
  • the crosslinked aqueous binder it is possible to improve the life of the lithium secondary battery, improve the low initial charge / discharge efficiency, and improve the area capacity of the electrode.
  • R 1 to R 3 may each independently be any one selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a halogen atom, preferably R All 1 to R 3 may be an alkoxy group having 1 to 3 carbon atoms.
  • the crosslinking reaction material is capable of self-crosslinking reaction even in the monomolecular state while maintaining water solubility, and forming the electrode when self-crosslinking reaction is possible in the monomolecular state It does not affect the physical properties of the slurry.
  • R 4 may be any one selected from the group consisting of H, N (R 7 ) 2 , CO 2 R 7 , R 8 SH, R 8 Si (OR 7 ) 3, and an alkyl group having 1 to 3 carbon atoms.
  • N (R 7 ) 2 , CO 2 R 7 , R 8 SH and R 8 Si (OR 7 ) 3 It may be any one selected from the group consisting of.
  • R 4 is any one selected from the group consisting of N (R 7 ) 2 , CO 2 R 7 , R 8 SH and R 8 Si (OR 7 ) 3 , the water solubility of the crosslinking reaction material may be increased.
  • R 1 to R 3 may be applied to the R 1 to R 3 in addition to the alkoxy group while maintaining the water solubility of the crosslinking reaction material.
  • R 4 it is possible to impart various physical properties to the crosslinking reaction material and the electrode through the change of R 4 .
  • R 5 to R 7 may be each independently hydrogen or an alkyl group having 1 to 3 carbon atoms, and R 8 may be an alkylene group having 1 to 3 carbon atoms.
  • N is an integer of 1-6.
  • n is greater than 6, the water solubility of the crosslinking reaction material is lowered, and thus it may be difficult to apply to the aqueous binder.
  • the compound represented by the formula (1) and the compound represented by the formula (2) may be represented by the formula (3) is chemically bonded. That is, the crosslinking reaction material may be a compound represented by Chemical Formula 1 or a compound represented by Chemical Formula 2, a mixture thereof, or a compound represented by Chemical Formula 3, which is a chemical combination thereof.
  • the compound represented by Formula 1 or the compound represented by Formula 2 is a crosslinking reaction material, the other compound may be included as an additive.
  • R 1 to R 3 , R 4 , R 5 to R 7 , R 8 , and n are the same as in Formula 1 and Formula 2, and thus repeated descriptions thereof will be omitted. .
  • the crosslinking reaction material may be included in an amount of 0.1 to 20 wt%, preferably 2 to 10 wt%, based on the total weight of the electrode.
  • the content of the crosslinking reaction material is less than 0.1 wt% with respect to the total weight of the electrode, the crosslinking degree between the aqueous binders may not be sufficient, and the effect may be insignificant. Due to the extreme crosslinking reaction of the entire electrode, the electrode is hardened more than necessary, and the battery performance may be reduced as a whole due to the concentration of the conductive material and the active material.
  • FIG. 1 is a schematic view showing the structure of the water-based binder polymer material improved by the addition of the crosslinking reaction material.
  • a high-loading electrode may be realized by preventing the microscopic or macroscopic cracking of the electrode, and the molecular weight of the aqueous binder material. This can be improved to improve the post-fabrication properties.
  • the electrode for lithium secondary batteries containing the said crosslinking reaction substance is demonstrated concretely.
  • the electrode for a lithium secondary battery may be a positive electrode in a lithium sulfur battery, a lithium air battery, a lithium selenium battery, a lithium tellurium battery or a lithium flonium battery, except that the crosslinking reaction material is further included. It can be manufactured according to the conventional manufacturing method of the positive electrode for lithium secondary batteries.
  • the crosslinking reaction material is applied to a lithium sulfur battery positive electrode will be mainly described.
  • the present invention is not limited thereto, and the crosslinking reaction material may be applied to a general lithium secondary battery electrode, and may also be applied to a negative electrode. .
  • the positive electrode may include, for example, a positive electrode current collector and a positive electrode active material layer positioned on the positive electrode current collector and including a positive electrode active material, an aqueous binder, the crosslinking reaction material, and optionally a conductive material.
  • the cathode current collector it may be preferable to use foamed aluminum, foamed nickel, and the like, which have excellent conductivity.
  • the cathode active material layer may include elemental sulfur (S 8 ), a sulfur-based compound, or a mixture thereof as a cathode active material.
  • the positive electrode active material layer may include a conductive material for smoothly moving electrons in the positive electrode together with the positive electrode active material, and a binder for increasing the binding force between the positive electrode active material or between the positive electrode active material and the positive electrode current collector.
  • the conductive material may be a carbon-based material such as carbon black, acetylene black, ketjen black, or a conductive polymer such as polyaniline, polythiophene, polyacetylene, or polypyrrole, and may be included in an amount of 2 to 40 wt% based on the total weight of the positive electrode active material layer. It may be desirable. If the content of the conductive material is less than 2% by weight, the conductivity improvement effect by the use of the conductive material is insignificant, whereas if the content of the conductive material exceeds 40% by weight, the content of the positive electrode active material is relatively low, which may lower the capacity characteristics.
  • the binder may be poly (vinyl acetate), polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, alkylated polyethylene oxide, crosslinked polyethylene oxide, polyvinyl ether, poly (methyl methacrylate), poly Vinylidene fluoride, copolymer of polyhexafluoropropylene and polyvinylidene fluoride (trade name: Kynar), poly (ethyl acrylate), polytetrafluoroethylene, polyvinylchloride, polyacrylonitrile, polyvinylpyridine , Polystyrene, derivatives thereof, blends, copolymers and the like can be used.
  • the binder may preferably be an aqueous binder, and the aqueous binder may be carboxymethyl cellulose (CMC), alginate, carbonyl- ⁇ -cyclodextrine And nafion (nafion) can be used any one selected from the group consisting of.
  • CMC carboxymethyl cellulose
  • alginate alginate
  • carbonyl- ⁇ -cyclodextrine And nafion nafion
  • the binder may be included in 0.1 to 40% by weight based on the total weight of the positive electrode active material layer.
  • the content of the binder is less than 0.1% by weight, the effect of improving the binding strength between the positive electrode active material or between the positive electrode active material and the positive electrode current collector according to the use of the binder is insignificant, whereas when the content of the binder exceeds 40% by weight, the content of the positive electrode active material is relatively There is a possibility that the capacity characteristics are lowered due to the decrease.
  • the positive electrode as described above may be manufactured according to a conventional method, and specifically, a positive electrode current-forming slurry prepared by mixing a positive electrode active material, a binder and the crosslinking reaction material, and optionally a conductive material on an organic solvent, and the positive electrode current collector It can be prepared by applying over and drying and optionally rolling.
  • the positive electrode active material, the binder, and the crosslinking reaction material may be mixed all at once, and the aqueous binder and the crosslinking reaction material may be mixed first, and then mixed with the positive electrode active material.
  • the crosslinking reaction material may be a compound represented by Chemical Formula 1 or a compound represented by Chemical Formula 2, a mixture thereof, or a compound represented by Chemical Formula 3, which is a chemical combination thereof.
  • the organic solvent the cathode active material, the binder, the crosslinking reaction material, and the conductive material may be uniformly dispersed, and it is preferable to use one that is easily evaporated. Specifically, acetonitrile, methanol, ethanol, tetrahydrofuran, water, isopropyl alcohol, etc. are mentioned.
  • the negative electrode is a negative electrode active material can be reversibly intercalated or deintercalated lithium ions, and may react with lithium ions to form a lithium-containing compound reversibly And a material selected from the group consisting of lithium metal and lithium alloy.
  • a carbon-based negative electrode active material generally used in a lithium secondary battery may be used, and specific examples thereof include crystalline carbon and amorphous materials. Carbon or these can be used together.
  • a representative example of a material capable of reacting with lithium ions to reversibly form a lithium-containing compound may include, but is not limited to, tin oxide (SnO 2 ), titanium nitrate, silicon (Si), and the like.
  • the alloy of the lithium metal may be an alloy of lithium with a metal of Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, or Cd.
  • the negative electrode may optionally further include a binder and a conductive material together with the negative electrode active material. Since the binder and the conductive material are the same as described for the anode, repeated descriptions thereof will be omitted.
  • the negative electrode may further include the crosslinking reaction material together with the binder.
  • the negative electrode may further include a negative electrode current collector for supporting the negative electrode active layer including the negative electrode active material.
  • the negative electrode current collector may be specifically selected from the group consisting of copper, aluminum, stainless steel, titanium, silver, palladium, nickel, alloys thereof, and combinations thereof.
  • the stainless steel may be surface treated with carbon, nickel, titanium, or silver, and an aluminum-cadmium alloy may be used as the alloy.
  • calcined carbon, a nonconductive polymer surface-treated with a conductive material, or a conductive polymer may be used.
  • an electrode assembly comprising the above electrode is provided.
  • the electrode assembly is a positive electrode and a negative electrode is laminated alternately at the boundary of the separator, wherein at least one of the positive electrode and the negative electrode includes a crosslinking reaction material according to an embodiment of the present invention.
  • the separator is interposed between the positive electrode and the negative electrode to insulate between the positive electrode and the negative electrode, and may be used without particular limitation as long as it is commonly used in the art.
  • Specific examples thereof include sheets, nonwoven fabrics and kraft papers made of olefinic polymer glass fibers or polyethylene such as polypropylene having chemical resistance and hydrophobicity, and more specifically, high density polyethylene, low density polyethylene, linear low density polyethylene, ultrahigh Molecular Weight Polyethylene, Polypropylene, Polyethylene terephthalate, Polybutylene terephthalate, Polyester, Polyacetal, Polyamide, Polycarbonate, Polyimide ), Polyetheretherketone, polyethersulfone, polyphenyleneoxide, polyphenylenesulfidro or polyethylenenaphthalene, and any one of them, or More than one Mixtures of may be used.
  • a lithium secondary battery including the electrode assembly is provided.
  • the lithium secondary battery may be a lithium air battery, a lithium-sulfur battery, a lithium-selenium battery, a lithium-tellurium (Li-Te) battery or a lithium fluorium (Li-Po) battery, and the like.
  • the electrolyte may be appropriately selected according to the type of the lithium secondary battery.
  • the electrolyte may further include a non-aqueous organic solvent and a lithium salt.
  • the non-aqueous organic solvent may be a polar solvent such as an aryl compound, bicyclic ether, acyclic carbonate, sulfoxide compound, lactone compound, ketone compound, ester compound, sulfate compound, sulfite compound, and the like.
  • a polar solvent such as an aryl compound, bicyclic ether, acyclic carbonate, sulfoxide compound, lactone compound, ketone compound, ester compound, sulfate compound, sulfite compound, and the like.
  • the non-aqueous organic solvent may be 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, dioxolane (Dioxolane, DOL), 1,4-dioxane, tetra Hydrofuran, 2-methyltetrahydrofuran, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC), ethyl propyl carbonate, dipropyl carbonate, butyl ethyl carbonate, ethyl Propanoate (EP), toluene, xylene, dimethyl ether (dimethyl ether, DME), diethyl ether, triethylene glycol monomethyl ether (TEGME), diglyme, tetraglyme, hexamethyl phosph Hexamethyl phosphoric triamide, gamma butyrolactone (
  • the lithium salt may be used without particular limitation as long as it is a compound capable of providing lithium ions used in a lithium secondary battery.
  • the lithium salt is LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAl0 4 , LiAlCl 4 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN (C 2 F 5 SO 3 ) 2 LiN (C 2 F 5 SO 2 ) 2 (Lithium bis (perfluoroethylsulfonyl) imide, BETI), LiN (CF 3 SO 2 ) 2 (Lithium bis (Trifluoromethanesulfonyl) imide, LiTFSI), LiN (C a F 2a + 1 SO 2 ) (C b F 2b + 1 SO 2 ) (where a and b are natural numbers, preferably 1 ⁇ a ⁇ 20 and 1 ⁇ b ⁇ 20), lithium poly [4,4
  • the lithium salt may be included at a concentration of 0.6 to 2M in the electrolyte. If the concentration of the lithium salt is less than 0.6M, the conductivity of the electrolyte is lowered and the performance of the electrolyte is lowered. If the concentration of the lithium salt is higher than 2M, the viscosity of the electrolyte is increased to reduce the mobility of lithium ions.
  • the electrolyte further includes additives (hereinafter, referred to as 'other additives') that can be generally used in the electrolyte for the purpose of improving the life characteristics of the battery, suppressing the reduction of the battery capacity, and improving the discharge capacity of the battery. can do.
  • additives hereinafter, referred to as 'other additives'
  • the lithium secondary battery according to the present invention improves the charge delay phenomenon and the charge overvoltage phenomenon and improves the initial discharge capacity characteristics, such as mobile phones, notebook computers, digital cameras, camcorders, etc., which require fast charging speed. It is useful in the field of portable vehicles, hybrid electric vehicles (HEVs), plug-in HEVs (PHEVs), electric vehicles, and medium to large energy storage systems.
  • HEVs hybrid electric vehicles
  • PHEVs plug-in HEVs
  • electric vehicles and medium to large energy storage systems.
  • Denka black was added to 1.2 wt% aqueous CMC (4.17 g), and then mixed with PDM mixer at 1500 rpm and 1000 rpm for 5 to 10 minutes, followed by Zirconia ball ( ⁇ 12 g), followed by S / Super-P (9/1 weight ratio) complex (1.5 g) was added and mixed under the same conditions as above.
  • R 1 to R 3 are all ethoxy groups
  • R 5 and R 6 are all hydrogen
  • n is 3
  • R 4 is R 8 SH
  • R 8 is an ethylene group compound was added and mixed (50% by weight in water, 0.10 g), and then mixed under the same conditions.
  • aqueous CMC (4.17 g) in Formula 1 wherein R 1 to R 3 are all ethoxy groups, the R 5 to R 6 are all hydrogen, n is 3 compound and in Formula 2
  • the R 4 is CO 2 H
  • the R 8 is a mixture of methylene groups, and then added (50% by weight in water, 0.10 g), and then Denka black is further added, and rotated by a PDM mixer 1500 rpm, idle 1000 rpm After mixing for 5 to 10 minutes, Zirconia ball ( ⁇ 12 g) was added and then S / Super-P (9/1 weight ratio) composite (1.5 g) was added and mixed under the same conditions.
  • Example 1 in Formula 3, R 1 to R 3 are all ethoxy groups, R 4 is R 8 SH, R 5 to R 6 are all hydrogen, R 8 is an ethylene group, N was set to 3 in the same manner as in Example 1 except for using the compound represented by Formula 1 and Formula 2 to prepare a positive electrode.
  • Example 1 Except for not using the compounds represented by Formula 1 and Formula 2 in Example 1 was prepared in the same manner as in Example 1 to prepare a positive electrode.
  • Example 1 in Formula 1, R 1 to R 3 are all ethoxy groups, R 5 and R 6 are all hydrogen, and n is 3, using only a compound represented by Formula 2 Except not used, was carried out in the same manner as in Example 1 to prepare a positive electrode.
  • a lithium sulfur battery was manufactured using the cathodes prepared in Examples and Comparative Examples.
  • lithium metal having a thickness of 150 ⁇ m was used as the negative electrode.
  • An electrode assembly was manufactured by interposing a separator of porous polyethylene between the prepared positive electrode and the negative electrode, and the electrode assembly was placed in a case, and an electrolyte solution (TD2) was injected into the case to prepare a lithium sulfur battery.
  • TEGDME triethylene glycol monomethyl ether
  • DOL dioxolane
  • DME dimethyl ether
  • the lithium sulfur battery prepared in Examples and Comparative Examples was subjected to 100 cycles of charging / discharging under conditions of 0.1 C / 0.1 C at a temperature of 1.5 to 2.8 V at a normal temperature (25 ° C.). And charge and discharge efficiency were respectively evaluated. The results are shown in FIGS. 2 and 3, respectively.
  • FIG. 2 is a graph showing the cycle characteristics of the lithium sulfur battery prepared in Example 1, Comparative Example 1 and Comparative Example 2,
  • Figure 3 is a lithium sulfur battery of Example 1, Comparative Example 1 and Comparative Example 3 A graph showing initial charge / discharge efficiency.
  • the battery prepared in Example 1 to which the crosslinking reaction material was added maintains 600mAh even after 20 charge / discharge cycles, so that the battery capacity of the battery is maintained as compared with the battery manufactured in Comparative Example 1.
  • the capacity of the battery began to differ after 6 cycles, and the difference was confirmed to increase gradually (FIG. 2).
  • the initial charge and discharge efficiency was significantly improved compared to the battery prepared in Comparative Example 1, it was confirmed that the coulombic efficiency is improved compared to the batteries prepared in Comparative Examples 1 and 2 ( 3).
  • the coulombic efficiency is closer to 100, the better, but the low coulombic efficiency of Comparative Example 1 means that overcharging occurs, and the coulombic efficiency of more than 100 of Comparative Example 2 suggests that side reactions occur.
  • the present invention relates to an electrode for a lithium secondary battery, a method of manufacturing the same, an electrode assembly for a lithium secondary battery including the same, and a lithium secondary battery comprising the same, wherein the electrode for a lithium secondary battery has a crosslinking reaction material combined with an aqueous binder to form an aqueous binder.

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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)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne une électrode pour pile rechargeable au lithium et son procédé de préparation, un ensemble électrode pour pile rechargeable au lithium la comprenant et une pile rechargeable au lithium le comprenant, l'électrode comprenant un matériau actif d'électrode, un liant aqueux et un composé représenté par la formule 1 et un composé représenté par la formule 2. La formule 1 et la formule 2 sont les mêmes que celles données dans la description. L'électrode pour pile rechargeable au lithium améliore les propriétés physiques du liant aqueux par combinaison d'une substance à réaction de réticulation avec le liant aqueux, de sorte que l'électrode peut améliorer le rendement de charge/décharge initial et la durée de vie d'une pile rechargeable au lithium, de préférence une pile lithium-soufre, ainsi que la capacité surfacique de l'électrode.
PCT/KR2016/006591 2015-06-22 2016-06-22 Électrode pour pile rechargeable au lithium et son procédé de préparation, ensemble électrode pour pile rechargeable au lithium la comprenant et pile rechargeable au lithium le comprenant WO2016208949A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US15/543,387 US10418633B2 (en) 2015-06-22 2016-06-22 Electrode for lithium secondary battery, method for preparing same, electrode assembly for lithium secondary battery comprising same, and lithium secondary battery comprising same
EP16814662.9A EP3232498B1 (fr) 2015-06-22 2016-06-22 Électrode pour pile rechargeable au lithium et son procédé de préparation, ensemble électrode pour pile rechargeable au lithium la comprenant et pile rechargeable au lithium le comprenant
JP2017541649A JP6441492B2 (ja) 2015-06-22 2016-06-22 リチウム二次電池用電極、その製造方法、それを含むリチウム二次電池用電極アセンブリ、及びそれを含むリチウム二次電池
CN201680009473.5A CN107210446B (zh) 2015-06-22 2016-06-22 锂二次电池用电极、其制备方法、包含其的锂二次电池用电极组件和包含其的锂二次电池

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KR10-2015-0088190 2015-06-22
KR20150088190 2015-06-22
KR10-2016-0076868 2016-06-20
KR1020160076868A KR102006721B1 (ko) 2015-06-22 2016-06-20 리튬 이차 전지용 전극, 이의 제조 방법, 이를 포함하는 리튬 이차 전지용 전극 조립체, 및 이를 포함하는 리튬 이차 전지

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CN114976011A (zh) * 2022-06-21 2022-08-30 深圳名飞远科技有限公司 一种锂离子电池负极浆料及负极片的制备方法

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KR20120006667A (ko) * 2010-07-13 2012-01-19 주식회사 엘지화학 접착력과 사이클 특성이 우수한 이차전지용 바인더
KR20120034686A (ko) * 2009-01-06 2012-04-12 주식회사 엘지화학 리튬 이차전지용 양극 활물질
WO2012066600A1 (fr) * 2010-11-18 2012-05-24 株式会社日立製作所 Batterie lithium-ion et son procédé de fabrication
KR20150061874A (ko) * 2013-11-28 2015-06-05 주식회사 엘지화학 리튬-황 전지용 양극 및 이의 제조방법

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KR20120006667A (ko) * 2010-07-13 2012-01-19 주식회사 엘지화학 접착력과 사이클 특성이 우수한 이차전지용 바인더
WO2012066600A1 (fr) * 2010-11-18 2012-05-24 株式会社日立製作所 Batterie lithium-ion et son procédé de fabrication
KR20150061874A (ko) * 2013-11-28 2015-06-05 주식회사 엘지화학 리튬-황 전지용 양극 및 이의 제조방법

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114976011A (zh) * 2022-06-21 2022-08-30 深圳名飞远科技有限公司 一种锂离子电池负极浆料及负极片的制备方法
CN114976011B (zh) * 2022-06-21 2024-03-15 东莞市众尚源科技有限公司 一种锂离子电池负极浆料及负极片的制备方法

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