WO2022019642A1 - Composition de précurseur d'électrolyte polymère solide, électrolyte polymère solide et batterie tout solide le comprenant - Google Patents

Composition de précurseur d'électrolyte polymère solide, électrolyte polymère solide et batterie tout solide le comprenant Download PDF

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WO2022019642A1
WO2022019642A1 PCT/KR2021/009404 KR2021009404W WO2022019642A1 WO 2022019642 A1 WO2022019642 A1 WO 2022019642A1 KR 2021009404 W KR2021009404 W KR 2021009404W WO 2022019642 A1 WO2022019642 A1 WO 2022019642A1
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polymer electrolyte
solid polymer
solid
carbon atoms
group
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Korean (ko)
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강영구
김동욱
김도엽
석정돈
만 응우엔티엔
김현진
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Korea Research Institute of Chemical Technology KRICT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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 solid polymer electrolyte precursor composition, and more particularly, to a solid polymer electrolyte precursor composition for forming a solid polymer electrolyte usable in an all-solid battery, a solid polymer electrolyte formed therefrom, and an all-solid battery comprising the same it's about
  • the lithium ion secondary battery using a liquid electrolyte is mainly used.
  • a lithium ion secondary battery using a liquid electrolyte is generally separated by a separator in which a negative electrode and a positive electrode are formed of a polymer, and a liquid electrolyte is used as the electrolyte.
  • the electrolyte exists in a liquid state in the battery, the liquid electrolyte evaporates due to temperature changes depending on the usage environment of the battery to cause expansion of the battery, leakage of the liquid electrolyte by external impact, or damage to the separator
  • the negative electrode and the positive electrode may be short-circuited by the , and thus explosion and ignition of the battery may occur.
  • an All Solid State Battery is a battery in which all components of the battery are solid while including a negative electrode, a positive electrode, and a solid electrolyte, and does not contain liquid in the battery, so liquid evaporation or external shock due to temperature change It is safe from explosion and fire as there is no problem such as leakage.
  • the all-solid-state battery does not require a safety device to prevent leakage, explosion, or ignition that may occur in a lithium ion secondary battery using a liquid electrolyte, there is an advantage in that the weight and volume of the battery can be reduced. .
  • a polyethylene oxide (PEO)-based polymer electrolyte is known as one of the solid polymer electrolytes with the highest potential for commercialization. Since the PEO-based polymer electrolyte does not use a flammable solvent, the possibility of explosion due to ignition is low, and it exhibits high chemical and electrochemical stability. However, since the PEO-based polymer electrolyte has low oxidation voltage stability, it is difficult to apply a 4V-class high voltage cathode material such as LCO (LiCoO 2 ), NMC (LiNiMnCoO 2 ), NCA (LiNiCoAlO 2 ), etc. As a material, only LFP (LiFePO 4 ) with a low voltage is used limitedly.
  • LCO LiCoO 2
  • NMC LiNiMnCoO 2
  • NCA LiNiCoAlO 2
  • An object to be solved by the present invention is to provide a solid polymer electrolyte that can be applied to a high voltage cathode material in an all-solid-state battery.
  • an object of the present invention is to provide a solid polymer electrolyte precursor composition for forming the solid polymer electrolyte.
  • Another object of the present invention is to provide a solid polymer electrolyte that is formed from the solid polymer electrolyte precursor composition and can be applied to a high voltage cathode material when used in an all-solid-state battery.
  • Another object of the present invention is to provide an all-solid-state battery having excellent cycle life and capacity characteristics, including the solid polymer electrolyte and the high voltage cathode material.
  • the present invention provides a compound represented by the following formula (1);
  • a solid polymer electrolyte precursor composition comprising a plasticizer and a lithium salt is provided.
  • X 1 is -CR 1 R 2 - or -NR 7 -
  • X 2 is -CR 3 R 4 - or -NR 8 -
  • X 3 is -CR 5 R 6 - or -NR 9 -
  • X 1 At least one or more of to X 3 is -NR 7 -, -NR 8 - or -NR 9 -
  • R 1 to R 9 are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms.
  • an alkynyl group having 2 to 30 carbon atoms a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroalkyl group having 1 to 30 carbon atoms, or a heterocyclic group having 5 to 30 ring atoms, but at least one or more is an alkenyl group having 2 to 30 carbon atoms.
  • the present invention provides a cross-linkable polymer comprising a compound unit represented by Formula 1;
  • a solid polymer electrolyte comprising a plasticizer and a lithium salt is provided.
  • the present invention is a negative electrode; anode; and a solid polymer electrolyte interposed between the negative electrode and the positive electrode, wherein the solid polymer electrolyte comprises: a cross-linkable polymer including a compound unit represented by Formula 1; It provides an all-solid-state battery comprising a plasticizer and a lithium salt.
  • solid polymer electrolyte formed from the solid polymer electrolyte precursor composition according to the present invention is used as an electrolyte for an all-solid-state battery, a high-voltage cathode material can be applied, thereby improving cycle life and capacity characteristics of the all-solid-state battery.
  • FIG. 2 is a graph showing charge/discharge characteristic curves according to charge/discharge rates of all-solid-state batteries prepared in Examples 1 to 4 of the present invention.
  • FIG 3 is a graph showing the capacity retention rate according to the rate of the all-solid-state batteries prepared in Examples 1 to 4 of the present invention.
  • all solid state battery' used in the present invention refers to a battery in which all components of the battery are solid, and a liquid electrolyte secondary battery using a liquid electrolyte such as an electrolyte, and a polymer electrolyte instead of a separator It is distinguished from a gel polymer secondary battery that uses a liquid electrolyte while using it.
  • Solid State Polymer Electrolyte' used in the present invention refers to a solid electrolyte formed of a polymer, and a non-aqueous liquid electrolyte such as an electrolyte, and a non-aqueous liquid electrolyte by gelling the polymer. It is distinguished from the gel polymer electrolyte used.
  • the term 'alkyl group' may refer to a monovalent aliphatic saturated hydrocarbon, and linear alkyl groups such as methyl, ethyl, propyl and butyl and isopropyl, sec-butyl, ter It may mean including all branched alkyl groups such as tert-butyl and neopentyl.
  • alkenyl group' may mean a monovalent aliphatic unsaturated hydrocarbon including one or two or more double bonds.
  • the term 'alkynyl group' may mean a monovalent aliphatic unsaturated hydrocarbon including one or two or more triple bonds.
  • the term 'cycloalkyl group' may refer to a monovalent aliphatic saturated or unsaturated cyclic hydrocarbon.
  • the unsaturated cyclic hydrocarbon includes one or two or more unsaturated bonds in a ring structure formed from the hydrocarbon, but may mean a cyclic hydrocarbon other than an aromatic hydrocarbon.
  • the term 'aryl group' may mean a cyclic aromatic hydrocarbon, and also a monocyclic aromatic hydrocarbon in which one ring is formed, or a polycyclic aromatic hydrocarbon in which two or more rings are bonded. It may mean including all hydrocarbon).
  • the term 'heteroalkyl group' may mean including one or two or more heteroatoms, ie, atoms other than carbon and hydrogen, in a monovalent aliphatic saturated or unsaturated hydrocarbon.
  • the hetero atom may be an oxygen (O), nitrogen (N), or sulfur (S) atom.
  • the heteroalkyl group may mean including all of an alkoxy group, an amino group, and a sulfide group.
  • the term 'heterocyclic group' may mean including both a cycloalkyl group or an aryl group in which a carbon atom in a cycloalkyl group or an aryl group is substituted with one or more hetero atoms.
  • the hetero atom may be an oxygen (O), nitrogen (N), or sulfur (S) atom.
  • the number of ring atoms of the heterocyclic group may mean the number of atoms forming a ring including carbon and hetero atoms.
  • composition includes reaction products and decomposition products formed from materials of the composition, as well as mixtures of materials comprising the composition.
  • the present invention relates to an all-solid-state battery, and more particularly, to an all-solid-state lithium secondary battery using lithium ions.
  • the all-solid-state battery may include a negative electrode, a positive electrode, and a solid polymer electrolyte interposed between the negative electrode and the positive electrode.
  • the present invention provides a solid polymer electrolyte precursor composition for forming a solid polymer electrolyte.
  • a solid polymer electrolyte precursor composition for forming a solid polymer electrolyte includes a compound represented by the following Chemical Formula 1; It may include a plasticizer and a lithium salt.
  • X 1 is -CR 1 R 2 - or -NR 7 -
  • X 2 is -CR 3 R 4 - or -NR 8 -
  • X 3 is -CR 5 R 6 - or -NR 9 -However, at least one of X 1 to X 3 is -NR 7 -, -NR 8 - or -NR 9 -
  • R 1 to R 9 are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, and 2 carbon atoms.
  • the compound represented by Formula 1 is crosslinkable to form a polymer forming a semi-interpenetrating network together with a plasticizer when forming a solid polymer electrolyte from a solid polymer electrolyte precursor composition It may be a compound.
  • the solid polymer electrolyte is formed by including the compound represented by Formula 1 according to the present invention, the polymerization reaction can be simplified while preventing shrinkage, and a structurally homogeneous polymer network can be formed.
  • X 1 is -NR 7 -
  • X 2 is -NR 8 -
  • X 3 is -NR 9 -
  • R 7 to R 9 are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a hetero group having 1 to 30 carbon atoms
  • X 1 is -NR 7 -
  • X 2 is -NR 8 -
  • X 3 is -NR 9 -
  • R 7 to R 9 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a hetero group having 1 to 20 carbon atoms
  • X 1 is -NR 7 -
  • X 2 is -NR 8 -
  • X 3 is -NR 9 -
  • R 7 to R 9 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a hetero group having 1 to 10 carbon atoms
  • X 1 is -NR 7 -
  • X 2 is -NR 8 -
  • X 3 is -NR 9 -
  • R 7 to R 9 are Each independently may be an alkenyl group having 2 to 30 carbon atoms, and as a more specific example, R 7 to R 9 may each independently be a vinyl group or an allyl group.
  • the compound represented by Formula 1 may be a compound represented by Formula 1-1 below.
  • the solid polymer electrolyte precursor composition may include a thiol-based crosslinking agent.
  • the crosslinkable polymer when the solid polymer electrolyte precursor composition includes a thiol-based crosslinking agent, when the crosslinkable polymer is formed from the compound represented by Formula 1, the crosslinkable polymer is formed by a crosslinking reaction between the compound represented by Formula 1 and the thiol-based crosslinking agent. can be formed.
  • the crosslinking reaction may be a thiol-ene crosslinking reaction between a double bond of an alkenyl group having 2 to 30 carbon atoms of the compound represented by Formula 1 and a thiol group of a thiol-based crosslinking agent.
  • the solid polymer electrolyte precursor composition includes a thiol-based crosslinking agent
  • the compound represented by Formula 1 forms a polymer forming a semi-interpenetrating network together with a plasticizer
  • the compound represented by Formula 1 and the thiol-based crosslinking agent may form a polymer forming a semi-interpenetrating network together with a plasticizer.
  • the polymerization reaction can be simplified while preventing shrinkage, and while forming a structurally homogeneous polymer network, oxygen sensitivity It has the effect of improving the oxidation voltage stability of the plasticizer by reducing the
  • the thiol-based crosslinking agent is 1,3-propanedithiol, 2,3-butanedithiol, 2-mercaptopropionic acid, 3-mercaptopropionic acid, pentaerythritol tetrakis(3-mer) captopropionate), trimethylolpropane tris(3-mercaptopropionate), and 2,2'-(ethylenedioxy)diethanethiol may be at least one selected from the group consisting of, as a specific example, pentaerythritol tetrakis (3-mercaptopropionate).
  • the thiol-based crosslinking agent may be a thiol compound represented by the following formula (2).
  • each X is independently S or NR 10
  • R 10 is hydrogen or an alkyl group having 1 to 7 carbon atoms
  • n is each independently an integer selected from 1 to 12
  • Y is a single bond or a carbon number 1 to 7 may be an alkylene group.
  • R 10 is an alkyl group having 1 to 3 carbon atoms
  • n is an integer selected from 2 to 7
  • Y may be a single bond or an alkylene group having 1 to 3 carbon atoms.
  • the thiol compound represented by Formula 2 includes a triazine-based parent nucleus, a side chain including an ether group, and a thiol group formed at the end of the side chain, and the thiol compound is a solid comprising a thiol-based crosslinking agent.
  • the thiol compound represented by Formula 2 may be a compound represented by Formula 2-1 or Formula 2-2.
  • n is each independently an integer selected from 1 to 12, and Y may be a single bond or an alkylene group having 1 to 7 carbon atoms.
  • n is an integer selected from 2 to 10
  • Y may be a single bond or an alkylene group having 1 to 3 carbon atoms.
  • n may be an integer selected from 2 to 7
  • Y may be a single bond or an alkylene group having 1 to 3 carbon atoms.
  • the compound represented by Formula 1 and the thiol-based crosslinking agent may have a molar ratio of 10:1 to 1:10, 5:1 to 1:5, or 4:1 to 1:4. And, as a specific example, it may be 4:3 to 3:4.
  • the molar ratio may be determined such that the molar ratio of the crosslinking site of the compound represented by Formula 1 to the crosslinking site of the thiol-based crosslinking agent is 1:1.
  • the crosslinking agent composition including the compound represented by Formula 1 and the thiol-based crosslinking agent is 1 wt% to 30 wt%, 5 wt% to 5 wt% based on the total content of the solid polymer electrolyte precursor composition It may be 25 wt%, or 10 wt% to 20 wt%, and within this range, the oxidation voltage stability of the plasticizer is improved by reducing the oxygen sensitivity of the solid polymer electrolyte, and the ionic conductivity is sufficiently secured to charge and discharge the all-solid-state battery. There is an effect of improving capacity and efficiency.
  • the plasticizer may be an ion conductive plasticizer, and may be a polyether plasticizer exhibiting ion conductivity as a matrix for a lithium salt in a solid polymer electrolyte.
  • the plasticizer is polyethylene glycol dimethyl ether, polyethylene glycol diethyl ether, polyethylene glycol dipropyl ether, polyethylene glycol dibutyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol dimethyl ether, polypropylene glycol diglycidyl.
  • It may be at least one selected from the group consisting of ether, dibutyl ether-terminated polypropylene glycol/polyethylene glycol copolymer, and dibutyl ether-terminated polyethylene glycol/polypropylene glycol/polyethylene glycol block copolymer, and more specifically, polyethylene glycol It may be dimethyl ether.
  • the plasticizer may be included in an amount of 40 wt% to 80 wt%, 45 wt% to 75 wt%, or 50 wt% to 70 wt%, based on the total content of the solid polymer electrolyte precursor composition. and may be included in the same content in the solid polymer electrolyte formed from the solid polymer electrolyte precursor composition, and within this range, the ionic conductivity of the solid polymer electrolyte is sufficiently secured, thereby improving the charge/discharge capacity and efficiency of the solid polymer electrolyte.
  • the lithium salt is a medium for transferring lithium ions in the solid polymer electrolyte, lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluoro Roantimonate (LiSbF 6 ), lithium hexafluoroacetate (LiAsF 6 ), lithium difluoromethanesulfonate (LiC 4 F 9 SO 3 ), lithium perchlorate (LiClO 4 ), lithium aluminate (LiAlO 2 ) , lithium tetrachloroaluminate (LiAlCl 4 ), lithium chloride (LiCl), lithium iodide (LiI), lithium bisoxalato borate (LiB(C 2 O 4 ) 2 ), lithium difluoro(oxalato) borate (LiBF) 2 (C 2 O 4 )), lithium bis(
  • the lithium salt is included in an amount of 1 wt% to 40 wt%, 5 wt% to 35 wt%, or 10 wt% to 30 wt%, based on the total content of the solid polymer electrolyte precursor composition. and may be included in the same amount in the solid polymer electrolyte formed from the solid polymer electrolyte precursor composition, and within this range, the ionic conductivity of the solid polymer electrolyte is sufficiently secured, thereby improving the charge/discharge capacity and efficiency of the solid polymer electrolyte. .
  • the solid polymer electrolyte precursor composition may include an electrolyte additive.
  • the electrolyte additive is to further improve the ionic conductivity of the solid polymer electrolyte, and may be at least one selected from the group consisting of a cyclic carbonate-based compound, a cyclic sulfur-based compound, and a nitrile-based compound.
  • the solid polymer electrolyte formed therefrom may include the electrolyte additive, and there is an effect of improving the charge/discharge capacity and efficiency of the all-solid-state battery.
  • the cyclic carbonate-based compound is vinylene carbonate (Vinylene Carbonate, VC), catechol carbonate (Catechol Carbonate, CC), fluoroethylene carbonate (Fluoro Ethylene Carbonate, FEC), or vinyl It may be ethylene carbonate (Vinyl Ethylene Carbonate, VEC), the cyclic sulfur-based compound may be propane sultone (PS) or glycol sulfite (Glycol Sulfite, GS), and the nitrile-based compound is succinonitrile ( Succinonitrile, SN) or adiponitrile (AN).
  • the electrolyte additive may be vinylene carbonate, fluoroethylene carbonate, or vinyl ethylene carbonate, and in this case, there is an effect of achieving excellent charge/discharge capacity and efficiency.
  • the electrolyte additive may be included in an amount of 0.1 wt% to 10 wt%, 1 wt% to 8 wt%, or 1 wt% to 5 wt%, based on the total content of the solid polymer electrolyte precursor composition. and while maintaining the solid characteristics of the all-solid-state battery within this range, there is an effect of improving the charge/discharge capacity and efficiency.
  • the solid polymer electrolyte precursor composition is a curing initiator for inducing a crosslinking reaction of the compound represented by Formula 1 or the crosslinking agent composition including the compound represented by Formula 1 and a thiol-based crosslinking agent may include.
  • the curable initiator may be a peroxide-based initiator or an azo-based initiator capable of providing radicals for initiating a crosslinking reaction from a crosslinkable functional group of the crosslinking agent.
  • the curing initiator is benzoyl peroxide, di-tert-butyl peroxide, di-tert-amyl peroxide, a-cumyl peroxyneodecanoate, a-cumyl peroxyneopeptanoate, t-amyl peroxide Oxyneodecanoate, di-(2-ethylhexyl) peroxy-dicarbonate, t-amyl peroxypivalate, t-butyl peroxypivalate, 2,5-dimethyl-2,5 bis(2-ethyl -hexanoylperoxy) hexane, dibenzoyl peroxide, t-amyl peroxy-2-ethy
  • the curing initiator is 0.01 parts by weight to 1.00 parts by weight based on 100 parts by weight of the crosslinking agent composition including the compound represented by Formula 1 or the compound represented by Formula 1 and the thiol-based crosslinking agent It may be included in parts by weight, 0.01 parts by weight to 0.50 parts by weight, or 0.01 parts by weight to 0.10 parts by weight.
  • the present invention provides a solid polymer electrolyte formed from the solid polymer electrolyte precursor composition.
  • the solid polymer electrolyte formed from the solid polymer electrolyte precursor composition may be formed through a direct crosslinking reaction by thermal curing of the solid polymer electrolyte precursor composition.
  • crosslinkable polymers comprising compound units; It may include a plasticizer and a lithium salt.
  • the crosslinkable polymer when the solid polymer electrolyte precursor composition includes a thiol-based crosslinking agent, may include a thiol-based crosslinking agent unit.
  • the crosslinking polymer when a crosslinking polymer is formed by a crosslinking reaction from the compound represented by Formula 1 or a crosslinking agent composition including the compound represented by Formula 1 and the thiol-based crosslinking agent, the crosslinking The sexual polymer forms a semi-interpenetrating network together with the plasticizer, wherein the lithium salt of the solid polyelectrolyte precursor composition may be dispersed on the network.
  • the solid polymer electrolyte may be formed by including the components included in the solid polymer electrolyte precursor composition for forming the solid polymer electrolyte in the same amount, and the solid polymer electrolyte is used as an electrolyte for an all-solid-state battery.
  • the solid polymer electrolyte is used as an electrolyte for an all-solid-state battery.
  • the present invention provides an anode for an all-solid-state battery.
  • the anode for an all-solid-state battery may include a current collector and an anode active material layer formed on at least one surface of the current collector, and the anode active material layer may include an anode active material.
  • the anode for an all-solid-state battery includes a current collector and a negative active material layer formed on at least one surface of the current collector, and the negative active material layer includes a negative electrode active material and a first solid polymer electrolyte. It may be a composite negative electrode for an all-solid-state battery comprising.
  • the current collector is copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel surface-treated with carbon, nickel, titanium, silver, etc., or aluminum-cadmium It may be an alloy.
  • the current collector may be surface roughened in order to improve the bonding force between the current collector and the negative electrode active material layer through an anchor effect.
  • the current collector may be in the form of a film, a sheet, a foil, a net, a porous body, a foam body, or a nonwoven body.
  • the anode active material layer formed on at least one surface of the current collector may exist in a form in which the anode active material is dispersed in the anode active material layer by a binder.
  • the negative active material may be a plurality of negative active material particles.
  • the binder may exist in the form of a continuous phase including a plurality of negative active material particles as a dispersed phase in the negative electrode active material layer.
  • the negative active material layer formed on at least one surface of the current collector may exist in a dispersed form in which the negative active material and the first solid polymer electrolyte are mixed with each other in the negative active material layer.
  • the negative active material may be a plurality of negative active material particles.
  • the first solid polymer electrolyte may exist in the form of a continuous phase including a plurality of negative active material particles as a dispersed phase in the negative electrode active material layer.
  • the first solid polymer electrolyte may exist in the form of covering all or part of the plurality of negative active material particles between pores formed by the plurality of negative active material particles in the negative electrode active material layer.
  • the negative active material may be a carbon-based material
  • the carbon-based material is crystalline carbon, amorphous carbon, or a mixture thereof capable of intercalation and deintercalation with lithium.
  • the crystalline carbon may be amorphous, plate-like, scale-like, spherical or fibrous natural graphite or artificial graphite
  • the amorphous carbon may be soft carbon, hard carbon, mesophase pitch-based carbon fiber, or calcined coke.
  • the carbon-based material may be a carbon-based material that can be used in a liquid electrolyte secondary battery using a liquid electrolyte such as an electrolyte.
  • the anode active material layer includes the anode active material and the first solid polymer electrolyte, it is possible to secure high charge/discharge capacity and efficiency of the battery only with the carbon-based material, and thus there is an effect of excellent productivity.
  • the negative active material is 50% to 90% by weight, 55% to 85% by weight, or 60% to 80% by weight based on the total content of the components of the negative active material layer. It may be included, and within this range, the charge/discharge capacity and efficiency of the all-solid-state battery are excellent.
  • the anode active material layer may include a binder for binding the anode active material to the anode active material layer.
  • the binder is polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HEP), polyvinylidene fluoride (polyvinylidenefluoride), polyacrylonitrile (polyacrylonitrile), polymethyl methacrylate, polyvinyl alcohol, Carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, It may be at least one selected from the group consisting of styrene butyrene rubber (SBR) and fluororubber, and a specific example may be polyvinylidene fluoride
  • the binder may be included in an amount of 1 wt% to 40 wt%, 10 wt% to 35 wt%, or 15 wt% to 25 wt%, based on the total content of the components of the negative electrode active material layer. In this range, there is an excellent effect of binding force of the negative electrode active material.
  • the first solid polymer electrolyte may include a binder, a plasticizer, and a lithium salt.
  • the first solid polymer electrolyte may be formed from the first solid polymer electrolyte precursor composition when the anode active material layer is formed by mixing the first solid polymer electrolyte precursor composition including the binder, the plasticizer and the lithium salt with the anode active material.
  • the first solid polymer electrolyte is 1 wt% to 40 wt%, 10 wt% to 35 wt%, or 15 wt% to 25 wt% based on the total content of the components of the negative electrode active material layer It may be included in weight %, and within this range, the charge/discharge capacity and efficiency of the all-solid-state battery are excellent.
  • the binder is for binding the negative active material as well as the first solid polymer electrolyte to each other in the negative active material layer, and is a polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co- HEP), polyvinylidenefluoride, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinyl blood It may be at least one selected from the group consisting of rolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, styrene butyrene rubber (SBR), and fluororubber. And, as a specific example, it may be polyvinylidene fluoride.
  • PVDF-co- HEP polyvinylidene fluor
  • the binder is used in an amount of 40 wt% to 80 wt%, 45 wt% to 75 wt%, or 50 wt% to 70 wt%, based on the total content of the first solid polymer electrolyte precursor composition. It may be included, and may be included in the same amount in the first solid polymer electrolyte formed from the first solid polymer electrolyte precursor composition, and within this range, the binding force of the first solid polymer electrolyte and the negative electrode active material is excellent.
  • the plasticizer may be an ion conductive plasticizer, and may be a polyether plasticizer exhibiting ion conductivity as a matrix for a lithium salt in the first solid polymer electrolyte.
  • the plasticizer is polyethylene glycol dimethyl ether, polyethylene glycol diethyl ether, polyethylene glycol dipropyl ether, polyethylene glycol dibutyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol dimethyl ether, polypropylene glycol diglycidyl.
  • It may be at least one selected from the group consisting of ether, dibutyl ether-terminated polypropylene glycol/polyethylene glycol copolymer, and dibutyl ether-terminated polyethylene glycol/polypropylene glycol/polyethylene glycol block copolymer, and more specifically, polyethylene glycol It may be dimethyl ether.
  • the plasticizer is 15% to 40% by weight, 20% to 35% by weight, or 25% to 35% by weight based on the total content of the first solid polymer electrolyte precursor composition.
  • the lithium salt is a medium for transferring lithium ions in the first solid polymer electrolyte, lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium Hexafluoroantimonate (LiSbF 6 ), lithium hexafluoroacetonate (LiAsF 6 ), lithium difluoromethanesulfonate (LiC 4 F 9 SO 3 ), lithium perchlorate (LiClO 4 ), lithium aluminate (LiAlO) 2 ), lithium tetrachloroaluminate (LiAlCl 4 ), lithium chloride (LiCl), lithium iodide (LiI), lithium bisoxalato borate (LiB(C 2 O 4 ) 2 ), lithium difluoro (oxalato) borate (LiBF 2 (C 2 O 4 )), lithium bis(flufluoro (LiBF 2
  • the lithium salt is 1 wt% to 20 wt%, 3 wt% to 18 wt%, or 5 wt% to 15 wt%, based on the total content of the first solid polymer electrolyte precursor composition and may be included in the same amount in the first solid polymer electrolyte formed from the first solid polymer electrolyte precursor composition, and within this range, the ionic conductivity of the first solid polymer electrolyte is sufficiently secured to provide a charge/discharge capacity of the all-solid-state battery And there is an effect that the efficiency is improved.
  • the negative active material layer may further include a conductive material.
  • the conductive material is to further improve the conductivity of the negative electrode, graphite such as natural graphite, artificial graphite; carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black and the like; conductive fibers such as carbon fibers, metal fibers, and the like; metal powders such as carbon fluoride, aluminum, nickel powder and the like; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; And it may be at least one selected from the group consisting of polyphenylene derivatives.
  • the conductive material when the conductive material is included in the anode active material layer, the conductive material is 1 wt% to 15 wt%, 1 wt% to 10 wt%, based on the total content of the components of the anode active material layer %, or may be included in an amount of 5 wt% to 10 wt%, and within this range, the charge/discharge capacity and efficiency of the all-solid-state battery are excellent.
  • the anode active material layer of the anode for an all-solid-state battery may include an electrolyte additive.
  • the electrolyte additive may exist between pores formed by a plurality of negative active material particles in the negative electrode active material layer.
  • the electrolyte additive may be present dispersed in the first solid polymer electrolyte, or may be present in a mixed form with the first solid polymer electrolyte in a three-dimensional network structure formed by the first solid polymer electrolyte. .
  • the electrolyte additive is to further improve the ionic conductivity of the first solid polymer electrolyte, and is at least one selected from the group consisting of a cyclic carbonate-based compound, a cyclic sulfur-based compound, and a nitrile-based compound.
  • the negative electrode for an all-solid-state battery includes an electrolyte additive in the negative electrode active material layer, there is an effect of achieving sufficient charge/discharge capacity and efficiency in an all-solid-state battery while using a carbon-based material as the negative electrode active material.
  • the cyclic carbonate-based compound is vinylene carbonate (Vinylene Carbonate, VC), catechol carbonate (Catechol Carbonate, CC), fluoroethylene carbonate (Fluoro Ethylene Carbonate, FEC), or vinyl It may be ethylene carbonate (Vinyl Ethylene Carbonate, VEC), the cyclic sulfur-based compound may be propane sultone (PS) or glycol sulfite (Glycol Sulfite, GS), and the nitrile-based compound is succinonitrile ( Succinonitrile, SN) or adiponitrile (AN).
  • the electrolyte additive may be vinylene carbonate, fluoroethylene carbonate, or vinyl ethylene carbonate, and in this case, excellent charge/discharge capacity in an all-solid-state battery while using a carbon-based material as an anode active material And there is an effect that can achieve efficiency.
  • the electrolyte additive included in the negative electrode active material layer may be derived from the solid polymer electrolyte precursor composition.
  • the electrolyte additive is not included in the formation of the anode active material layer from the anode active material and the first solid polymer electrolyte precursor composition, and the electrolyte additive included in the solid polymer electrolyte is added to the anode active material layer after manufacturing the all-solid-state battery. It may be impregnated with and finally included in the negative electrode for an all-solid-state battery. Accordingly, the anode active material layer and the electrolyte additive included in the solid polymer electrolyte may be identical to each other.
  • the electrolyte additive is 0.01 parts by weight to 5 parts by weight, 0.01 parts by weight to 1 parts by weight, or 0.01 with respect to 100 parts by weight of the total content of the components of the negative electrode active material layer excluding the electrolyte additive. It may be included in an amount of from 0.1 parts by weight to 0.1 parts by weight, and while maintaining the solid characteristics of the all-solid-state battery within this range, there is an effect of improving the charge/discharge capacity and efficiency.
  • the anode for an all-solid-state battery is an anode used for an all-solid-state battery, it does not contain a liquid such as a solvent, and even if it is included, it may be included in a very small part in order to maintain the solid characteristics of the all-solid-state battery.
  • the negative electrode is impregnated in a liquid such as a solvent derived from a liquid electrolyte
  • a temperature change according to the usage environment of the battery particularly, a problem of evaporating the solvent at a high temperature may occur, and consequently, a liquid electrolyte using the liquid electrolyte
  • a secondary battery there is a problem that may cause the battery to expand due to the evaporated liquid electrolyte.
  • the present invention provides a positive electrode for an all-solid-state battery.
  • the positive electrode for an all-solid-state battery may include a current collector and a positive electrode active material layer formed on at least one surface of the current collector, and the positive electrode active material layer may include a positive electrode active material.
  • the positive electrode for an all-solid-state battery includes a current collector and a positive electrode active material layer formed on at least one surface of the current collector, and the positive electrode active material layer includes a positive electrode active material and a second solid polymer electrolyte. It may be a composite positive electrode for an all-solid-state battery including.
  • the current collector is copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel surface-treated with carbon, nickel, titanium, silver, etc., or aluminum-cadmium It may be an alloy.
  • the current collector may be surface roughened in order to improve the bonding force between the current collector and the positive electrode active material layer through an anchor effect.
  • the current collector may be in the form of a film, a sheet, a foil, a net, a porous body, a foam body, or a nonwoven body.
  • the positive active material layer formed on at least one surface of the current collector may exist in a form in which the positive active material is dispersed in the positive electrode active material layer by a binder.
  • the positive active material may be a plurality of positive active material particles.
  • the binder may exist in the form of a continuous phase including a plurality of positive active material particles as a dispersed phase in the positive electrode active material layer.
  • the positive active material layer formed on at least one surface of the current collector may exist in a dispersed form in which the positive active material and the second solid polymer electrolyte are mixed with each other in the positive active material layer.
  • the positive active material may be a plurality of positive active material particles.
  • the second solid polymer electrolyte may exist in the form of a continuous phase including a plurality of positive electrode active material particles as a dispersed phase in the positive electrode active material layer.
  • the second solid polymer electrolyte may be present in the form of covering all or part of the plurality of positive active material particles between pores formed by the plurality of positive active material particles in the positive electrode active material layer.
  • the lithium metal oxide is one selected from the group consisting of LiCoO 2 , LiNi 0.8 Mn 0.1 Co 0.1 O 2 , LiNi 0.6 Mn 0.2 Co 0.2 O 2 , and LiNi 0.8 Co 0.15 Al 0.05 O 2 . or more, and in this case, the all-solid-state battery may exhibit a high voltage.
  • the positive active material is 50% to 90% by weight, 55% to 85% by weight, or 60% to 80% by weight based on the total content of the components of the positive active material layer. It may be included, and within this range, the charge/discharge capacity and efficiency of the all-solid-state battery are excellent.
  • the positive active material layer may include a binder for binding the positive active material to the positive active material layer.
  • the binder is polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HEP), polyvinylidene fluoride (polyvinylidenefluoride), polyacrylonitrile (polyacrylonitrile), polymethyl methacrylate, polyvinyl alcohol, Carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, It may be at least one selected from the group consisting of styrene butyrene rubber (SBR) and fluororubber.
  • SBR styrene butyrene rubber
  • the binder may be included in an amount of 1 wt% to 40 wt%, 10 wt% to 35 wt%, or 15 wt% to 25 wt%, based on the total content of the components of the positive electrode active material layer. And within this range, there is an excellent effect of binding force of the positive electrode active material.
  • the second solid polymer electrolyte may include a binder, a plasticizer, and a lithium salt.
  • the second solid polymer electrolyte may be formed from the second solid polymer electrolyte precursor composition when the cathode active material layer is formed by mixing a second solid polymer electrolyte precursor composition including a binder, a plasticizer and a lithium salt with a cathode active material.
  • the second solid polymer electrolyte is 1 wt% to 40 wt%, 10 wt% to 35 wt%, or 15 wt% to 25 wt% based on the total content of the components of the positive electrode active material layer It may be included in weight %, and within this range, the charge/discharge capacity and efficiency of the all-solid-state battery are excellent.
  • the binder is for binding the positive active material as well as the second solid polymer electrolyte to each other in the positive active material layer, and is a polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co- HEP), polyvinylidenefluoride, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinyl blood It may be at least one selected from the group consisting of rolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, styrene butyrene rubber (SBR), and fluororubber. And, as a specific example, it may be polyvinylidene fluoride.
  • PVDF-co- HEP polyvinylidene fluor
  • the binder is used in an amount of 40 wt% to 80 wt%, 45 wt% to 75 wt%, or 50 wt% to 70 wt%, based on the total content of the second solid polymer electrolyte precursor composition. It may be included, and may be included in the same amount in the second solid polymer electrolyte formed from the second solid polymer electrolyte precursor composition, and within this range, the binding force of the second solid polymer electrolyte and the positive electrode active material is excellent.
  • the plasticizer may be an ion conductive plasticizer, and may be a polyether plasticizer exhibiting ion conductivity as a matrix for a lithium salt in the second solid polymer electrolyte.
  • the plasticizer is polyethylene glycol dimethyl ether, polyethylene glycol diethyl ether, polyethylene glycol dipropyl ether, polyethylene glycol dibutyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol dimethyl ether, polypropylene glycol diglycidyl.
  • It may be at least one selected from the group consisting of ether, dibutyl ether-terminated polypropylene glycol/polyethylene glycol copolymer, and dibutyl ether-terminated polyethylene glycol/polypropylene glycol/polyethylene glycol block copolymer, and more specifically, polyethylene glycol It may be dimethyl ether.
  • the plasticizer is 15% to 40% by weight, 20% to 35% by weight, or 25% to 35% by weight based on the total content of the second solid polymer electrolyte precursor composition.
  • the lithium salt is a medium for transferring lithium ions in the second solid polymer electrolyte, lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium Hexafluoroantimonate (LiSbF 6 ), lithium hexafluoroacetonate (LiAsF 6 ), lithium difluoromethanesulfonate (LiC 4 F 9 SO 3 ), lithium perchlorate (LiClO 4 ), lithium aluminate (LiAlO) 2 ), lithium tetrachloroaluminate (LiAlCl 4 ), lithium chloride (LiCl), lithium iodide (LiI), lithium bisoxalato borate (LiB(C 2 O 4 ) 2 ), lithium difluoro (oxalato) borate (LiBF 2 (C 2 O 4 )), lithium bis(flufluoro (LiBF 2
  • the lithium salt is 1 wt% to 20 wt%, 3 wt% to 18 wt%, or 5 wt% to 15 wt%, based on the total content of the second solid polymer electrolyte precursor composition and may be included in the same amount in the second solid polymer electrolyte formed from the second solid polymer electrolyte precursor composition, and within this range, the ionic conductivity of the second solid polymer electrolyte is sufficiently secured to provide the charge/discharge capacity of the all-solid-state battery And there is an effect that the efficiency is improved.
  • the positive active material layer may further include a conductive material.
  • the conductive material is to further improve the conductivity of the anode, graphite such as natural graphite, artificial graphite; carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black and the like; conductive fibers such as carbon fibers, metal fibers, and the like; carbon-based conductive materials such as carbon nanotubes and graphene; metal powders such as carbon fluoride, aluminum, nickel powder and the like; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; And it may be at least one selected from the group consisting of polyphenylene derivatives.
  • the conductive material may include carbon black and a carbon-based conductive material at the same time, and in this case, a mixing ratio of the carbon-based conductive material and carbon black may be 1:5 to 1:60 based on weight, In this case, short-distance and long-distance electron paths can be effectively formed in the anode, and low-rate and high-rate discharge capacity are excellent compared to the case of using a single-component conductive material.
  • the conductive material when the conductive material is included in the positive electrode active material layer, the conductive material is 1% to 15% by weight, 1% to 10% by weight based on the total content of the components of the positive electrode active material layer. %, or may be included in an amount of 5 wt% to 10 wt%, and within this range, the charge/discharge capacity and efficiency of the all-solid-state battery are excellent.
  • the positive active material layer including the positive active material and the second solid polymer electrolyte may further include an electrolyte additive.
  • the electrolyte additive may be present between the pores formed by the plurality of positive electrode active material particles in the positive electrode active material layer.
  • the electrolyte additive may be present dispersed in the second solid polymer electrolyte, or may be present in a mixed form with the second solid polymer electrolyte in a three-dimensional network structure formed by the second solid polymer electrolyte. .
  • the electrolyte additive is to further improve the ionic conductivity of the second solid polymer electrolyte, and is at least one selected from the group consisting of a cyclic carbonate-based compound, a cyclic sulfur-based compound, and a nitrile-based compound.
  • the positive electrode for an all-solid-state battery includes an electrolyte additive in the positive electrode active material layer, there is an effect of achieving more excellent charge/discharge capacity and efficiency in the all-solid-state battery.
  • the cyclic carbonate-based compound is vinylene carbonate (Vinylene Carbonate, VC), catechol carbonate (Catechol Carbonate, CC), fluoroethylene carbonate (Fluoro Ethylene Carbonate, FEC), or vinyl It may be ethylene carbonate (Vinyl Ethylene Carbonate, VEC), the cyclic sulfur-based compound may be propane sultone (PS) or glycol sulfite (Glycol Sulfite, GS), and the nitrile-based compound is succinonitrile ( Succinonitrile, SN) or adiponitrile (AN).
  • the electrolyte additive may be vinylene carbonate, fluoroethylene carbonate, or vinyl ethylene carbonate, and in this case, the effect of achieving better charge/discharge capacity and efficiency in an all-solid-state battery there is
  • the electrolyte additive included in the positive electrode active material layer may be derived from the solid polymer electrolyte precursor composition.
  • the electrolyte additive is not included in the formation of the positive electrode active material layer from the positive electrode active material and the second solid polymer electrolyte precursor composition, and the electrolyte additive included in the solid polymer electrolyte is added to the positive electrode active material layer after the all-solid-state battery is manufactured. It may be impregnated with and finally included in the positive electrode for an all-solid-state battery. Accordingly, the electrolyte additives included in the positive electrode active material layer and the second solid polymer electrolyte may be identical to each other.
  • the electrolyte additive is 0.01 parts by weight to 5 parts by weight, 0.01 parts by weight to 1 parts by weight, or 0.01 with respect to 100 parts by weight of the total content of the components of the positive electrode active material layer excluding the electrolyte additive. It may be included in an amount of from 0.1 parts by weight to 0.1 parts by weight, and while maintaining the solid characteristics of the all-solid-state battery within this range, there is an effect of improving the charge/discharge capacity and efficiency.
  • the positive electrode for an all-solid-state battery is a positive electrode used in an all-solid-state battery, it does not contain a liquid such as a solvent, and even if it is included, it may be included in a very small part in order to maintain the solid characteristics of the all-solid-state battery.
  • the all-solid-state battery according to the present invention may include a negative electrode, a positive electrode, and a solid polymer electrolyte interposed between the negative electrode and the positive electrode, wherein the solid polymer electrolyte is a solid polymer electrolyte formed from the solid polymer electrolyte precursor composition described above.
  • the all-solid-state battery can exist in an all-solid state by including the solid polymer electrolyte, and the solid polymer electrolyte is an electrolyte in the all-solid-state battery and a separator for separating the anode and the cathode. roles can be performed at the same time.
  • the negative electrode and the positive electrode may be the negative electrode and the positive electrode for an all-solid-state battery described above.
  • the all-solid-state battery according to the present invention includes the solid polymer electrolyte, it is possible to use a positive electrode using a high-voltage positive electrode material by preventing a decrease in oxidation voltage stability while including a plasticizer.
  • the all-solid-state battery includes a negative electrode, a positive electrode, and a solid polymer electrolyte interposed between the negative electrode and the positive electrode, and the negative electrode includes a current collector and at least one surface of the current collector.
  • the negative active material layer includes a negative active material
  • the negative active material is a carbon-based material
  • the positive electrode includes a current collector, and a positive electrode active material layer formed on at least one surface of the current collector
  • the positive active material layer includes a positive active material
  • the solid polymer electrolyte may include a cross-linkable polymer including a compound unit represented by Formula 1; It may include a plasticizer and a lithium salt, and in this case, the cycle life and capacity characteristics of the all-solid-state battery are excellent.
  • the present invention provides a method for manufacturing an all-solid-state battery.
  • the all-solid-state battery manufacturing method includes the steps of preparing a negative electrode (S1); applying a solid polymer electrolyte precursor composition on the negative electrode (S2); Laminating a positive electrode on the applied solid polymer electrolyte precursor composition (S3); and thermally curing the electrode assembly on which the positive electrode is stacked (S4).
  • the step of preparing the negative electrode (S1) includes preparing a negative electrode slurry by mixing the negative electrode active material, the first solid polymer electrolyte and the solvent (S10); and coating the negative electrode slurry on the current collector and drying it to form a negative electrode active material layer (S20).
  • step (S10) is a step of preparing a negative electrode slurry for forming the negative electrode active material layer, and may be performed by mixing the negative electrode active material, the first solid polymer electrolyte, and the solvent.
  • the negative active material and the first solid polymer electrolyte may be the same as the negative active material and the first solid polymer electrolyte described in the negative electrode for an all-solid-state battery.
  • the first solid polymer electrolyte may be mixed into the negative electrode slurry in the form of the first solid polymer electrolyte precursor composition as described above.
  • the solvent is ethanol, methanol, propanol, butanol, isopropyl alcohol, dimethylformamide (DMF), acetone, tetrahydrofuran (Tetrahydrofuran, THF), toluene, dimethylacetamide and It may be at least one organic solvent selected from the group consisting of N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP), and a specific example may be N-methyl-2-pyrrolidone.
  • N-methyl-2-pyrrolidone N-methyl-2-pyrrolidone
  • NMP N-methyl-2-pyrrolidone
  • the loading density of the negative electrode active material when preparing the negative electrode slurry, may be 1.0 mg/cm 2 to 10.0 mg/cm 2 , and within this range, sufficient charge/discharge capacity of the solid-state battery and It has the effect of securing efficiency.
  • the step (S20) is a step of forming the negative electrode active material layer by applying the negative electrode slurry prepared in the step (S10) on the current collector and drying it, and does not include an electrolyte additive. It may be a step of preparing a preliminary negative electrode for an all-solid-state battery.
  • the current collector may be the same as the current collector described in the negative electrode for an all-solid-state battery.
  • the negative electrode active material layer is formed through the step of applying and drying the negative electrode slurry on the current collector, and at the same time, the first solid polymer electrolyte mixed with the negative electrode slurry in the step (S10).
  • a first solid polymer electrolyte may be formed from the precursor composition.
  • the step (S2) is a step of applying a second solid polymer electrolyte precursor composition on the negative electrode prepared in the step (S1), specifically, the negative electrode active material layer formed in the step (S20). and the solid polymer electrolyte may not be formed from the solid polymer electrolyte precursor composition in step (S2).
  • the solid polymer electrolyte precursor composition may include an electrolyte additive in the same manner as described in the solid polymer electrolyte precursor composition, and the second solid polymer electrolyte precursor composition comprises: A thermal curing initiator for initiating a direct crosslinking reaction of the crosslinking agent by thermal curing in step (S4) performed later may be further included.
  • the thermal curing initiator may be a peroxide-based initiator or an azo-based initiator capable of providing radicals for initiating a crosslinking reaction from a crosslinkable functional group of the crosslinking agent.
  • the thermal curing initiator include benzoyl peroxide, di-tert-butyl peroxide, di-tert-amyl peroxide, a-cumyl peroxyneodecanoate, a-cumyl peroxyneopeptanoate, t-amyl Peroxyneodecanoate, di-(2-ethylhexyl) peroxy-dicarbonate, t-amyl peroxypivalate, t-butyl peroxypivalate, 2,5-dimethyl-2,5 bis(2- Ethyl-hexanoylperoxy) hexane, dibenzoyl peroxide, t-amyl peroxy-2-ethylhe
  • the step (S3) is a step of laminating a positive electrode on the solid polymer electrolyte precursor composition applied in the step (S2), and the 'cathode/solid polymer electrolyte An electrode assembly having a stacked structure of precursor composition/anode' may be formed.
  • the positive electrode may be a positive electrode manufactured independently of the time before or after the step (S1), specifically, the steps (S10) and (S20).
  • the positive electrode may be prepared by coating a positive electrode slurry containing a positive electrode active material on a current collector and drying the positive electrode active material layer to form a positive electrode active material layer.
  • the positive electrode is prepared by mixing a positive electrode active material, a second solid polymer electrolyte, and a solvent to prepare a positive electrode slurry (S100) and applying the positive electrode slurry on a current collector and drying to form a positive electrode active material layer It may be the one prepared in step S200.
  • step (S100) is a step of preparing a cathode slurry for forming a cathode active material layer, and may be performed by mixing a cathode active material, a second solid polymer electrolyte, and a solvent.
  • the positive active material and the second solid polymer electrolyte may be the same as the positive active material and the second solid polymer electrolyte described in the positive electrode for an all-solid-state battery.
  • the second solid polymer electrolyte may be mixed into the positive electrode slurry in the form of a second solid polymer electrolyte precursor composition as described above.
  • the solvent is ethanol, methanol, propanol, butanol, isopropyl alcohol, dimethylformamide (DMF), acetone, tetrahydrofuran (Tetrahydrofuran, THF), toluene, dimethylacetamide and It may be at least one organic solvent selected from the group consisting of N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP), and a specific example may be N-methyl-2-pyrrolidone.
  • N-methyl-2-pyrrolidone N-methyl-2-pyrrolidone
  • NMP N-methyl-2-pyrrolidone
  • the loading density of the positive electrode active material is 1.0 mg/cm 2 to 10.0 mg/cm 2 , 3.0 mg/cm 2 to 8.0 mg/cm 2 , or 5.0 to 6.0 It may be mg/cm 2 , and within this range, there is an effect of securing sufficient charge/discharge capacity and efficiency of the all-solid-state battery.
  • the step (S200) is a step of applying the positive electrode slurry prepared in the step (S100) on the current collector and drying it to form a positive electrode active material layer, and does not include an electrolyte additive. It may be a step of preparing a preliminary positive electrode for an all-solid-state battery that is not used.
  • the current collector may be the same as the current collector described in the positive electrode for an all-solid-state battery.
  • the cathode active material layer is formed through the step of applying and drying the cathode slurry on the current collector, and at the same time, the second solid polymer electrolyte mixed with the cathode slurry in the step (S100).
  • a second solid polymer electrolyte may be formed from the precursor composition.
  • the 'cathode/solid polymer electrolyte precursor composition/anode' in which the stacking from the step (S3) to the positive electrode is completed. It may further include the step of sealing the electrode assembly having a stacked structure (S3-1). In this case, when the subsequent thermal curing of step (S4) is performed, even if the electrolyte additive included in the solid polymer electrolyte precursor composition is volatilized, it remains as a gas phase in the sealed electrode assembly, so that the electrolyte additive in the all-solid battery There is an effect that the content can be constantly controlled.
  • the sealing in step (S3-1) may be performed by accommodating the electrode assembly in the outer case of the all-solid-state battery and then sealing the outer case, in which case the outer case is cylindrical. , a square shape, a pouch type, etc. may be appropriately selected according to the type of use of the battery.
  • the step (S4) is a step of thermally curing the electrode assembly on which the positive electrode is stacked.
  • the solid polymer electrolyte precursor composition is a solid polymer through a direct crosslinking reaction by thermal curing. electrolytes can be formed.
  • the thermal curing in step (S4) is at a temperature of 50 °C to 150 °C, 60 °C to 140 °C, 70 °C to 130 °C, 80 °C to 120 °C, or 80 °C to 110 °C. can be carried out in
  • the thermal curing in step (S4) is a time of 10 minutes to 100 minutes, 10 minutes to 80 minutes, 10 minutes to 60 minutes, 10 minutes to 50 minutes, or 20 minutes to 40 minutes. can be carried out during
  • the solid polymer electrolyte corresponding to the all-solid-state battery electrolyte, the negative electrode active material layer of the negative electrode for an all-solid-state battery and/or the positive electrode active material layer of the positive electrode for an all-solid-state battery It is possible to effectively include the electrolyte additive, and by forming a solid polymer electrolyte between the negative electrode and the positive electrode by direct crosslinking, the interfacial resistance between the negative electrode and the positive electrode and the solid polymer electrolyte can be lowered, resulting in uniform performance of the all-solid-state battery It becomes possible to improve the charging/discharging capacity and efficiency while securing the .
  • the molar ratio of the compound represented by Formula 1-1 to the thiol-based crosslinking agent was 4:3, and the weight ratio of the plasticizer to the crosslinking agent composition including the compound represented by Formula 1-1 and the thiol-based crosslinking agent was 8:2,
  • the electrolyte additive was 5 parts by weight based on 100 parts by weight of the total amount of the crosslinking agent and the plasticizer, and the [EO]/[Li + ] ratio was 15.
  • the [EO]/[Li + ] ratio is for indicating the content of lithium salt in the solid polymer electrolyte precursor composition, and is a ratio of the number of repeating units of ethylene oxide to lithium ions.
  • a slurry was prepared by dissolving in 2-pyrrolidone (NMP) and stirring for 10 minutes. Next, the prepared slurry was applied to a thickness of 60 ⁇ m on an aluminum foil and dried at a temperature of 120° C. for 1 hour to prepare a positive electrode.
  • the polymer electrolyte contains 60.7 wt% of polyvinylidenefluoride (PVdF) as a polymer binder, poly(ethylene glycol) dimethyl ether as a plasticizer, PEGDME, number average molecular weight 500 g/mol) 30.34 and 8.96% by weight of lithium salt lithium bis(trifluoromethanesulfonyl)imide (LiTFSI).
  • PVdF polyvinylidenefluoride
  • PEGDME poly(ethylene glycol) dimethyl ether
  • the solid polymer electrolyte precursor composition prepared above was applied, and the composite positive electrode prepared above was laminated thereon to construct a battery. Thereafter, the battery was sealed so that oxygen did not come into contact with it, and then cured at a temperature of 90° C. for 30 minutes, and the solid polymer electrolyte precursor composition was converted into a solid polymer electrolyte to prepare an all-solid-state battery.
  • Example 1 it was carried out in the same manner as in Example 1, except that the same amount of LiNi 0.6 Mn 0.2 Co 0.2 O 2 instead of LiNi 0.8 Mn 0.1 Co 0.1 O 2 as the positive electrode active material was added.
  • Example 1 it was carried out in the same manner as in Example 1, except that the same amount of LiCoO 2 instead of LiNi 0.8 Mn 0.1 Co 0.1 O 2 as the positive electrode active material was input.
  • Example 1 it was carried out in the same manner as in Example 1, except that the same amount of LiNi 0.8 Co 0.15 Al 0.05 O 2 instead of LiNi 0.8 Mn 0.1 Co 0.1 O 2 as the positive electrode active material was added.
  • the ratio of the negative electrode capacity to the positive electrode capacity of the all-solid-state battery prepared in Example 1 was 1.02
  • the ratio of the negative electrode capacity to the positive electrode capacity of the all-solid-state battery prepared in Example 2 was 1.09
  • the ratio of the negative electrode capacity to the positive electrode capacity of the all-solid-state battery prepared in Example 3 was 1.05
  • the capacity ratio of the negative electrode (N/P ratio) was 1.07.
  • the all-solid-state battery prepared in Example 1 had a first cycle capacity of 137.2 mAh/g at 0.1 C, 0.2 C, 0.5 C, 1.0 C and 2.0 C showed capacities of 126.2 mAh/g, 57.4 mAh/g, 20.7 mAh/g and 10.5 mAh/g, respectively.
  • the capacity of 140.1 mAh/g was recovered.
  • the all-solid-state battery prepared in Example 2 exhibited a first cycle capacity of 128.7 mAh/g at 0.1 C, and 116.5 mAh/g and 59.7 mAh/g at 0.2 C, 0.5 C, 1.0 C and 2.0 C, respectively. , 22.2 mAh/g and 9.3 mAh/g capacities were shown. In addition, when the charge/discharge rate was returned to 0.1 C, the capacity of 121.6 mAh/g was recovered.
  • the all-solid-state battery prepared in Example 3 exhibited a first cycle capacity of 107.4 mAh/g at 0.1 C, and 90.0 mAh/g and 27.1 mAh/g at 0.2 C, 0.5 C, 1.0 C and 2.0 C, respectively. , 9.1 mAh/g and 2.7 mAh/g capacities were shown. In addition, when the charge/discharge rate was returned to 0.2 C, the capacity of 76.1 mAh/g was recovered.
  • the all-solid-state battery prepared in Example 4 exhibited a first cycle capacity of 107.5 mAh/g at 0.1 C, and 101.5 mAh/g and 30.6 mAh/g at 0.2 C, 0.5 C, 1.0 C and 2.0 C, respectively. , 14.9 mAh/g and 4.9 mAh/g capacities were shown. In addition, when the charge/discharge rate was returned to 0.1 C, the capacity of 123.7 mAh/g was recovered.
  • the all-solid-state battery according to the present invention exhibits excellent electrochemical reversibility with respect to charging and discharging when a high voltage cathode material is applied, and at the same time, it is possible to secure a discharge capacity.
  • Example 1 100.0% 92.0% 41.8% 15.0% 7.7%
  • Example 2 100.0% 90.5% 46.4% 17.3% 7.3%
  • Example 3 100.0% 83.7% 25.2% 8.5% 2.5%
  • Example 4 100.0% 94.4% 28.5% 13.9% 4.6%
  • the all-solid-state battery according to the present invention can implement a capacity retention rate of 80% or more even at 0.2 C when a high voltage cathode material is applied.

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Abstract

La présente invention concerne une composition de précurseur d'électrolyte polymère solide, et : une composition de précurseur d'électrolyte polymère solide comprenant un composé représenté par la formule chimique 1 (voir description de la présente invention), un plastifiant et un sel de lithium ; un électrolyte polymère solide formé à partir de celle-ci ; et une batterie tout solide le comprenant.
PCT/KR2021/009404 2020-07-22 2021-07-21 Composition de précurseur d'électrolyte polymère solide, électrolyte polymère solide et batterie tout solide le comprenant Ceased WO2022019642A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114914539A (zh) * 2022-06-28 2022-08-16 肇庆小鹏汽车有限公司 固态/半固体电解质及其制备方法和应用
CN114976486A (zh) * 2022-06-13 2022-08-30 吉林省东驰新能源科技有限公司 电解质隔膜、凝胶态电解质膜及其制备方法和半固态锂硫电池
CN115548432A (zh) * 2022-10-09 2022-12-30 中国科学院苏州纳米技术与纳米仿生研究所 一种固态电解质、固态电池极片及其制备方法与应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102756695B1 (ko) * 2023-08-25 2025-01-21 한국화학연구원 고체 고분자 전해질의 함침에 사용되는 다공성 지지체, 이를 포함하는 이차전지 및 이의 제조방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20120074952A (ko) * 2010-12-28 2012-07-06 호남석유화학 주식회사 화학 가교 구조의 플라스틱 결정 전해질 조성물
KR101826496B1 (ko) * 2016-11-04 2018-02-07 한국화학연구원 신규한 트리아진계 화합물, 이를 가교제로 포함하는 전고상 고분자 전해질 조성물 및 이의 응용
KR101840335B1 (ko) * 2017-06-19 2018-03-20 한국화학연구원 신규한 화합물 및 이의 용도
JP2020076024A (ja) * 2018-11-09 2020-05-21 公立大学法人首都大学東京 ２次電池用の電解質。
KR20200055176A (ko) * 2018-11-12 2020-05-21 한국화학연구원 활물질을 포함하는 양극과 그라파이트를 포함하는 음극 및 기능성 첨가제를 포함하는 고분자 전해질로 구비된 전고상 리튬-폴리머 이차전지 및 이의 제조방법

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100722834B1 (ko) 2005-09-16 2007-05-30 한국화학연구원 고체 고분자 전해질 복합재료의 제조방법 및 그로 제조된 고체 고분자 전해질 복합재료를 구비한 리튬 고분자 전지

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20120074952A (ko) * 2010-12-28 2012-07-06 호남석유화학 주식회사 화학 가교 구조의 플라스틱 결정 전해질 조성물
KR101826496B1 (ko) * 2016-11-04 2018-02-07 한국화학연구원 신규한 트리아진계 화합물, 이를 가교제로 포함하는 전고상 고분자 전해질 조성물 및 이의 응용
KR101840335B1 (ko) * 2017-06-19 2018-03-20 한국화학연구원 신규한 화합물 및 이의 용도
JP2020076024A (ja) * 2018-11-09 2020-05-21 公立大学法人首都大学東京 ２次電池用の電解質。
KR20200055176A (ko) * 2018-11-12 2020-05-21 한국화학연구원 활물질을 포함하는 양극과 그라파이트를 포함하는 음극 및 기능성 첨가제를 포함하는 고분자 전해질로 구비된 전고상 리튬-폴리머 이차전지 및 이의 제조방법

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114976486A (zh) * 2022-06-13 2022-08-30 吉林省东驰新能源科技有限公司 电解质隔膜、凝胶态电解质膜及其制备方法和半固态锂硫电池
CN114976486B (zh) * 2022-06-13 2023-11-17 吉林省东驰新能源科技有限公司 电解质隔膜、凝胶态电解质膜及其制备方法和半固态锂硫电池
CN114914539A (zh) * 2022-06-28 2022-08-16 肇庆小鹏汽车有限公司 固态/半固体电解质及其制备方法和应用
CN115548432A (zh) * 2022-10-09 2022-12-30 中国科学院苏州纳米技术与纳米仿生研究所 一种固态电解质、固态电池极片及其制备方法与应用

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