WO2022019642A1 - Solid polymer electrolyte precursor composition, solid polymer electrolyte and all-solid-state battery comprising same - Google Patents

Abstract

The present invention relates to a solid polymer electrolyte precursor composition, and to: a solid polymer electrolyte precursor composition comprising a compound represented by chemical formula 1 (see description of the present invention), a plasticizer and a lithium salt; a solid polymer electrolyte formed therefrom; and an all-solid-state battery comprising same.

Description

Solid polymer electrolyte precursor composition, solid polymer electrolyte, and all-solid battery comprising same

[Citation with related applications]

The present invention claims the benefit of priority based on Korean Patent Application No. 10-2020-0091180 filed on July 22, 2020, and includes all contents disclosed in the literature of the Korean patent application as a part of this specification.

[Technical field]

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

In the secondary battery using lithium ion, conventionally, 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. However, since 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 There is a problem that the negative electrode and the positive electrode may be short-circuited by the , and thus explosion and ignition of the battery may occur.

On the other hand, 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. In addition, since 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. .

In particular, as a solid polymer electrolyte used in an all-solid-state battery, 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.

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.

Accordingly, 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.

In order to solve the above problems, 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.

[Formula 1]

In Formula 1,

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 -, wherein X ¹ At least one or more of to X ^{3 is -NR 7} -, -NR ⁸ - or -NR ⁹ -, and 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.

In addition, 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.

In addition, 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.

When the 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.

1 is a graph showing the discharge capacity according to each current density in the charge/discharge cycle of all-solid-state batteries prepared in Examples 1 to 4 of the present invention.

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.

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.

4 is a graph showing the capacity retention rate according to the cycle life of the all-solid-state batteries prepared in Examples 1 to 4 of the present invention.

Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.

The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

Terms used in the present invention may be defined as follows unless otherwise defined.

The term '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.

The term '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.

In the present invention, 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.

In the present invention, the term 'alkenyl group' may mean a monovalent aliphatic unsaturated hydrocarbon including one or two or more double bonds.

In the present invention, the term 'alkynyl group' may mean a monovalent aliphatic unsaturated hydrocarbon including one or two or more triple bonds.

In the present invention, the term 'cycloalkyl group' may refer to a monovalent aliphatic saturated or unsaturated cyclic hydrocarbon. Here, 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.

In the present invention, 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).

In the present invention, 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. Here, the hetero atom may be an oxygen (O), nitrogen (N), or sulfur (S) atom. Also, the heteroalkyl group may mean including all of an alkoxy group, an amino group, and a sulfide group.

In the present invention, 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. Here, the hetero atom may be an oxygen (O), nitrogen (N), or sulfur (S) atom. In addition, the number of ring atoms of the heterocyclic group may mean the number of atoms forming a ring including carbon and hetero atoms.

As used herein, the term '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. According to an embodiment of the present invention, 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. Hereinafter, each configuration of the all-solid-state battery of the present invention will be described in detail.

solid polymer electrolyte

The present invention provides a solid polymer electrolyte precursor composition for forming a solid polymer electrolyte.

According to an embodiment of the present invention, 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.

[Formula 1]

In Formula 1, X ¹ is -CR ¹ R ² - or -NR ⁷ -, X ² is -CR ³ R ⁴ - or -NR ⁸ -, and 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 -, and R ¹ to R ⁹ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, and 2 carbon atoms. An alkenyl group having to 30, 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. , at least one or more is an alkenyl group having 2 to 30 carbon atoms.

According to an embodiment of the present invention, 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. When 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.

According to an embodiment of the present invention, in the compound represented by Formula 1, 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 An alkyl group or a heterocyclic group having 5 to 30 ring atoms, at least one may be an alkenyl group having 2 to 30 carbon atoms.

According to an embodiment of the present invention, in the compound represented by Formula 1, 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 An alkyl group or a heterocyclic group having 5 to 20 ring atoms, at least one may be an alkenyl group having 2 to 20 carbon atoms.

According to an embodiment of the present invention, in the compound represented by Formula 1, 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 An alkyl group or a heterocyclic group having 5 to 10 ring atoms, at least one may be an alkenyl group having 2 to 10 carbon atoms.

According to an embodiment of the present invention, in the compound represented by Formula 1, 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.

According to an embodiment of the present invention, the compound represented by Formula 1 may be a compound represented by Formula 1-1 below.

[Formula 1-1]

According to an embodiment of the present invention, the solid polymer electrolyte precursor composition may include a thiol-based crosslinking agent. 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. As a specific example, 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.

According to an embodiment of the present invention, when the solid polymer electrolyte precursor composition includes a thiol-based crosslinking agent, when the compound represented by Formula 1 forms a polymer forming a semi-interpenetrating network together with a plasticizer, the By the crosslinking reaction, 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. In the case of forming a solid polymer electrolyte including the compound represented by Formula 1 and the thiol-based crosslinking agent according to the present invention, 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

According to an embodiment of the present invention, 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).

In addition, according to an embodiment of the present invention, the thiol-based crosslinking agent may be a thiol compound represented by the following formula (2).

[Formula 2]

In 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, and Y is a single bond or a carbon number 1 to 7 may be an alkylene group.

As a specific example, in Formula 2, R ¹⁰ is an alkyl group having 1 to 3 carbon atoms, n is an integer selected from 2 to 7, and Y may be a single bond or an alkylene group having 1 to 3 carbon atoms.

According to an embodiment of the present invention, 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. In the case of preparing a solid polymer electrolyte from the polymer electrolyte precursor composition, there is an advantage of excellent ionic conductivity. Due to the advantages of such ionic conductivity, it is possible to form an ultra-thin film, but there is no leakage of leakage, and there is an advantage of commercializing a solid polymer electrolyte through high ionic conductivity.

According to an embodiment of the present invention, the thiol compound represented by Formula 2 may be a compound represented by Formula 2-1 or Formula 2-2.

[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 and 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.

As a specific example, in Formulas 2-1 and 2-2, n is an integer selected from 2 to 10, and Y may be a single bond or an alkylene group having 1 to 3 carbon atoms.

As a more specific example, in Formulas 2-1 and 2-2, n may be an integer selected from 2 to 7, and Y may be a single bond or an alkylene group having 1 to 3 carbon atoms.

According to an embodiment of the present invention, 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. When the molar ratio of the compound represented by Formula 1 and the thiol-based crosslinking agent is within the above range, it is possible to simplify the polymerization reaction while preventing shrinkage when forming a solid polymer electrolyte, and to form a structurally homogeneous polymer network. .

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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. As a specific example, 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.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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(fluorosulfonyl)imide (LiN(FSO ₂ ) ₂ , LiFSI), and lithium bis(trifluoromethanesulfonyl)imide (LiN(CF ₃ SO ₂ ) ₂ , LiTFSI) may be at least one selected from the group consisting of, and a specific example may be lithium bis(trifluoromethanesulfonyl)imide (LiN(CF ₃ SO ₂ ) ₂ , LiTFSI).

According to an embodiment of the present invention, 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. .

According to an embodiment of the present invention, 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. According to the present invention, when the electrolyte additive is included in the solid polymer electrolyte precursor composition, 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.

According to an embodiment of the present invention, 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).

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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. Specifically, 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-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, 1,1-di-(t-amylper oxy) cyclohexane, 1,1-di-(t-butylperoxy) 3,3,5-trimethyl cyclohexane, 1,1-di-(t-butylperoxy) cyclohexane, t-butyl peroxyacetate , t-butyl peroxybenzoate, t-amyl peroxybenzoate, ethyl 3,3-di-(t-amylperoxy) butyrate and ethyl 3,3-di-(t-butylperoxy) butyrate and diQ peroxide-based initiators such as wheat peroxide; or 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2-methylpropionamidine) dihydrochloride and 4,4'-azobis(4-cyanovaleric acid), etc. It may be at least one selected from the group consisting of azo-based initiators, and a more specific example may be t-butyl peroxypivalate (t-BPP).

According to an embodiment of the present invention, 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.

In addition, the present invention provides a solid polymer electrolyte formed from the solid polymer electrolyte precursor composition.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, when the solid polymer electrolyte precursor composition includes a thiol-based crosslinking agent, the crosslinkable polymer may include a thiol-based crosslinking agent unit.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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. In this case, it is possible to apply a high voltage cathode material, thereby improving the cycle life and capacity characteristics of the all-solid-state battery.

Anode for all-solid-state battery

The present invention provides an anode for an all-solid-state battery.

According to an embodiment of the present invention, 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.

In addition, according to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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. In addition, 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. In addition, 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.

According to an embodiment of the present invention, 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. In this case, the negative active material may be a plurality of negative active material particles. As a specific example, 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.

In addition, according to an embodiment of the present invention, 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. In this case, the negative active material may be a plurality of negative active material particles. As a specific example, 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. As another specific example, 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.

According to an embodiment of the present invention, the negative active material may be a carbon-based material, and as a specific example, the carbon-based material is crystalline carbon, amorphous carbon, or a mixture thereof capable of intercalation and deintercalation with lithium. it could be As a more specific example, the crystalline carbon may be amorphous, plate-like, scale-like, spherical or fibrous natural graphite or artificial graphite, and the amorphous carbon may be soft carbon, hard carbon, mesophase pitch-based carbon fiber, or calcined coke. can

Here, 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. According to the present invention, since 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.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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.

Also, according to an embodiment of the present invention, the first solid polymer electrolyte may include a binder, a plasticizer, and a lithium salt. As a specific example, 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. can

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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. As a specific example, 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.

According to an embodiment of the present invention, 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. 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 ionic conductivity of the first solid polymer electrolyte is sufficiently secured to determine the charge/discharge capacity of the all-solid-state battery and It has the effect of improving the efficiency.

According to an embodiment of the present invention, 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(fluorosulfonyl)imide (LiN(FSO ₂ ) ₂ , LiFSI) and lithium bis(trifluoromethanesulfonyl)imide (LiN(CF ₃ SO) ₂ ) ₂ , LiTFSI), and the like may be at least one selected from the group consisting of, and a specific example may be lithium bis(trifluoromethanesulfonyl)imide (LiN(CF ₃ SO ₂ ) ₂ , LiTFSI).

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, the anode active material layer of the anode for an all-solid-state battery may include an electrolyte additive. As a specific example, the electrolyte additive may exist between pores formed by a plurality of negative active material particles in the negative electrode active material layer. As another specific example, 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. .

According to an embodiment of the present invention, 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. can According to the present invention, when 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.

According to an embodiment of the present invention, 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).

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, the electrolyte additive included in the negative electrode active material layer may be derived from the solid polymer electrolyte precursor composition. As a specific example, 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.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, since 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. can If 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 As in a secondary battery, there is a problem that may cause the battery to expand due to the evaporated liquid electrolyte.

Positive electrode for all-solid-state battery

The present invention provides a positive electrode for an all-solid-state battery.

According to an embodiment of the present invention, 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.

In addition, according to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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. In addition, 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. In addition, 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.

According to an embodiment of the present invention, 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. In this case, the positive active material may be a plurality of positive active material particles. As a specific example, 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.

In addition, according to an embodiment of the present invention, 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. In this case, the positive active material may be a plurality of positive active material particles. As a specific example, 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. As another specific example, 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.

According to an embodiment of the present invention, the positive active material may be a lithium metal oxide capable of intercalation and deintercalation with lithium, and as a specific example, the lithium metal oxide is selected from the group consisting of cobalt, manganese, nickel and aluminum. It may be a lithium metal oxide including one or more selected metals, and as a more specific example, the lithium metal oxide is LiCo _a M1 _b M2 _c O ₂ capable of exhibiting a high voltage of 4V class (M1 and M2 are each independently Ni, Mn or Al, but different from each other, and 0.05≤a≤1.0, 0≤b≤0.95, 0≤c≤0.95, a+b+c=1).

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, the second solid polymer electrolyte may include a binder, a plasticizer, and a lithium salt. As a specific example, 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. can

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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. As a specific example, 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.

According to an embodiment of the present invention, 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. 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 ionic conductivity of the second solid polymer electrolyte is sufficiently secured to determine the charge/discharge capacity of the all-solid-state battery and It has the effect of improving the efficiency.

According to an embodiment of the present invention, 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(fluorosulfonyl)imide (LiN(FSO ₂ ) ₂ , LiFSI) and lithium bis(trifluoromethanesulfonyl)imide (LiN(CF ₃ SO) ₂ ) ₂ , and may be at least one selected from the group consisting of LiTFSI), and a specific example thereof may be lithium bis(trifluoromethanesulfonyl)imide (LiN(CF ₃ SO ₂ ) ₂ , LiTFSI).

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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. As a specific example, 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.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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. As another specific example, 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. .

According to an embodiment of the present invention, 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. can According to the present invention, when 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.

According to an embodiment of the present invention, 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).

According to an embodiment of the present invention, 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

According to an embodiment of the present invention, the electrolyte additive included in the positive electrode active material layer may be derived from the solid polymer electrolyte precursor composition. As a specific example, 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.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, since 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. can

All-solid-state battery and manufacturing method thereof

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. can be

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, the negative electrode and the positive electrode may be the negative electrode and the positive electrode for an all-solid-state battery described above. In particular, since 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.

That is, according to an embodiment of the present invention, 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. a negative active material layer formed, wherein 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, and the positive active material is LiCo _a M1 _b M2 _c O ₂ (M1 and M2 are each independently Ni, Mn, or Al, but are different from each other, and 0.05≤a≤1.0, 0≤ b≤0.95, 0≤c≤0.95, and a+b+c=1), and 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.

In addition, the present invention provides a method for manufacturing an all-solid-state battery.

According to an embodiment of the present invention, 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).

According to an embodiment of the present invention, 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).

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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. Here, 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.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, when preparing the negative electrode slurry, the loading density of the negative electrode active material 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.

According to an embodiment of the present invention, 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. Here, the current collector may be the same as the current collector described in the negative electrode for an all-solid-state battery.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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).

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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. Specific examples of 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-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, 1,1-di-(t-amyl) peroxy) cyclohexane, 1,1-di-(t-butylperoxy) 3,3,5-trimethyl cyclohexane, 1,1-di-(t-butylperoxy) cyclohexane, t-butyl peroxy acetate, t-butyl peroxybenzoate, t-amyl peroxybenzoate, ethyl 3,3-di-(t-amylperoxy) butyrate and ethyl 3,3-di-(t-butylperoxy) butyrate and peroxide-based initiators such as dicumyl peroxide; or 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2-methylpropionamidine) dihydrochloride and 4,4'-azobis(4-cyanovaleric acid), etc. It may be at least one selected from the group consisting of azo-based initiators, and a more specific example may be t-butyl peroxypivalate (t-BPP).

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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). As a specific example, 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. As a more specific example, 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.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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. Here, 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.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, when preparing the positive electrode slurry, 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.

According to an embodiment of the present invention, 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. Here, the current collector may be the same as the current collector described in the positive electrode for an all-solid-state battery.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, in the all-solid-state battery manufacturing method, before the step (S4) is performed, 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.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, the step (S4) is a step of thermally curing the electrode assembly on which the positive electrode is stacked. In this case, the solid polymer electrolyte precursor composition is a solid polymer through a direct crosslinking reaction by thermal curing. electrolytes can be formed.

According to an embodiment of the present invention, 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

According to an embodiment of the present invention, 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

In the case of manufacturing an all-solid-state battery according to the all-solid-state battery manufacturing method of the present invention, 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 .

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.

Example

Example 1

<Production of solid polymer electrolyte>

5.9 wt% of a compound represented by the following formula 1-1, pentaerythritol tetrakis (3-mercaptopropionate) 8.7 as a thiol-based crosslinking agent Weight %, as a plasticizer, polyethylene glycol dimethyl ether (poly(ethylene glycol) dimethyl ether, PEGDME, number average molecular weight: 500 g/mol) 58.4 wt%, lithium salt as lithium bis(trifluoromethanesulfonyl)imide (LiTFSI ) 23.0 wt%, 0.3 wt% of t-butyl peroxypivalate (t-BPP) as a thermal curing initiator and 3.7 wt% of Fluoro Ethylene Carbonate (FEC) as an electrolyte additive A solid polymer electrolyte precursor composition was prepared.

At this time, 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.

[Formula 1-1]

<Production of composite negative electrode for all-solid-state battery>

22 wt% of a polymer electrolyte, 70 wt% of artificial graphite, and 8 wt% of conductive carbon (super P) were dissolved in 2.4 ml NMP (N-Methyl-2-pyrrolidone) and stirred for 10 minutes to prepare a slurry. Next, the prepared slurry was applied on a copper foil and dried in a vacuum oven at 80° C. for 24 hours to prepare a composite negative electrode.

Here, 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).

<Manufacture of composite positive electrode for all-solid-state battery>

Polyelectrolyte 22 wt%, positive electrode active material LiNi _0.8 Mn _0.1 Co _0.1 O ₂ 70 wt%, conductive carbon (super P) 7.85 wt%, carbon-based conductive material carbon nanotube 0.15 wt%, 2.4 ml of N-methyl- 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 μm on an aluminum foil and dried at a temperature of 120° C. for 1 hour to prepare a positive electrode.

Here, 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).

<All-solid-state battery manufacturing>

On the composite negative electrode prepared above, 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 2

In 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 3

In 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 4

In 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.

Experimental example

Experimental Example 1: Evaluation of charge/discharge characteristics of a full cell according to the charge/discharge rate (coin cell)

In order to evaluate the charge/discharge characteristics according to the charge/discharge rate of the all-solid-state batteries prepared in Examples 1 to 4, the following experiment was performed. At this time, the ratio of the negative electrode capacity to the positive electrode capacity of the all-solid-state battery prepared in Example 1 (N/P ratio) was 1.02, and the ratio of the negative electrode capacity to the positive electrode capacity of the all-solid-state battery prepared in Example 2 ( N/P ratio) was 1.09, and the ratio of the negative electrode capacity to the positive electrode capacity of the all-solid-state battery prepared in Example 3 (N/P ratio) was 1.05, compared to the positive electrode capacity of the all-solid-state battery prepared in Example 4 The capacity ratio of the negative electrode (N/P ratio) was 1.07.

Specifically, in order to confirm the rate capability of the all-solid-state battery, it was divided into current densities of 0.1 C, 0.2 C, 0.5 C, 1.0 C, 2.0 C, and 0.1 C, and charging and discharging cycles were performed twice or three times. , The first cycle discharge capacity for each current density is shown in Tables 1 and 2 below, and the discharge capacity according to each current density in the charge/discharge cycle is shown in FIG. 1 .

In addition, the charge-discharge characteristic curve according to the charge-discharge rate of the all-solid-state battery is shown in FIG. 2 .

division	0.1 C	0.2 C	0.5 C	1.0 C	2.0 C	0.1 C
	1 cycle	3 cycle	5 cycle	7 cycle	9 cycle	11 cycle
Example 1	137.2 mAh/g	126.2 mAh/g	57.4 mAh/g	20.7 mAh/g	10.5 mAh/g	140.1 mAh/g
Example 2	128.7 mAh/g	116.5 mAh/g	59.7 mAh/g	22.2 mAh/g	9.3 mAh/g	121.6 mAh/g
Example 4	107.5 mAh/g	101.5 mAh/g	30.6 mAh/g	14.9 mAh/g	4.9 mAh/g	123.7 mAh/g

division	0.1 C	0.2 C	0.5 C	1.0 C	2.0 C	0.2 C
	1 cycle	2 cycle	5 cycle	8 cycle	11 cycle	14 cycle
Example 3	107.4 mAh/g	90.0 mAh/g	27.1 mAh/g	9.1 mAh/g	2.7 mAh/g	76.1 mAh/g

As shown in Tables 1, 2 and 1, 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. In addition, when the charge/discharge rate was returned to 0.1 C, the capacity of 140.1 mAh/g was recovered.

In addition, 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.

In addition, 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.

In addition, 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.

That is, it was confirmed that 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.

Experimental Example 2: Capacity retention rate according to rate

In order to evaluate the capacity retention rate characteristics according to the rate of the all-solid-state batteries prepared in Examples 1 to 4, the following experiment was performed.

Specifically, in order to confirm the capacity retention of the all-solid-state battery, charge and discharge cycles were performed at current densities of 0.1 C, 0.2 C, 0.5 C, 1.0 C, and 2.0 C, and the capacity retention rate according to the rate was 0.1 C The percentage of the capacity when the discharge rate was increased compared to the capacity in the was calculated and shown in Table 3 and FIG. 3 .

division	0.1 C	0.2 C	0.5 C	1.0 C	2.0 C
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%

As shown in FIG. 3 , it was confirmed that 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.

Experimental Example 3: Cycle life characteristic evaluation

In order to evaluate the cycle life characteristics of the all-solid-state batteries prepared in Examples 1 to 4, the following experiment was performed.

Specifically, one cycle formation charge/discharge at 0.1 C and a charge/discharge test for 100 cycles at 0.2 C were performed, and the discharge capacity for each cycle was converted into a percentage compared to the initial cycle. it was

As shown in FIG. 4 , in the case of the all-solid-state batteries prepared in Examples 1 and 2, a capacity retention rate of about 80% was exhibited after 100 cycles of charging and discharging, and in the case of the all-solid-state batteries prepared in Example 3, 100 After charging and discharging cycles, a capacity retention rate of about 60% was exhibited, and in the case of the all-solid-state battery prepared in Example 3, a capacity retention rate of about 90% was exhibited after 100 cycles of charging and discharging.

From these results, when the 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, it is possible to apply a high-voltage cathode material, thereby improving the cycle life and capacity characteristics of the all-solid-state battery. was able to confirm

Claims (16)

1. a compound represented by the following formula (1); A solid polymer electrolyte precursor composition comprising a plasticizer and a lithium salt:

   [Formula 1]

   

   In Formula 1,

   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 -, wherein X ¹ At least one 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, 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, at least one or more is an alkenyl group having 2 to 30 carbon atoms.
2. According to claim 1,

   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 solid polymer electrolyte precursor composition which is a heteroalkyl group having 1 to 30 carbon atoms or a heterocyclic group having 5 to 30 ring atoms, wherein at least one is an alkenyl group having 2 to 30 carbon atoms.
3. According to claim 1,

   X ¹ is -NR ⁷ -, X ² is -NR ⁸ -, X ³ is -NR ⁹ -, and R ⁷ to R ⁹ are each independently an alkenyl group having 2 to 30 carbon atoms.
4. According to claim 1,

   A solid polymer electrolyte precursor composition comprising a thiol-based crosslinking agent.
5. 5. The method of claim 4,

   The thiol-based crosslinking agent is 1,3-propanedithiol, 2,3-butanedithiol, 2-mercaptopropionic acid, 3-mercaptopropionic acid, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane A solid polymer electrolyte precursor composition of at least one selected from the group consisting of tris(3-mercaptopropionate) and 2,2'-(ethylenedioxy)diethanethiol.
6. 5. The method of claim 4,

   The thiol-based crosslinking agent is a solid polymer electrolyte precursor composition, which is a thiol compound represented by the following Chemical Formula 2:

   [Formula 2]

   

   In Formula 2,

   X is each 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 an alkylene group having 1 to 7 carbon atoms .
7. 5. The method of claim 4,

   A solid polymer electrolyte precursor composition in which the compound represented by Formula 1 and the thiol-based crosslinking agent have a molar ratio of 10:1 to 1:10.
8. According to claim 1,

   The plasticizer is a solid polymer electrolyte precursor composition that is a polyether-based plasticizer.
9. According to claim 1,

   A solid polyelectrolyte precursor composition comprising an electrolyte additive.
10. 10. The method of claim 9,

    The electrolyte additive is at least one solid polymer electrolyte precursor composition selected from the group consisting of a cyclic carbonate-based compound, a cyclic sulfur-based compound, and a nitrile-based compound.
11. According to claim 1,

    A solid polymer electrolyte precursor composition comprising a curable initiator.
12. A cross-linkable polymer comprising a compound unit represented by the following formula (1); A solid polymer electrolyte comprising a plasticizer and a lithium salt:

    [Formula 1]

    

    In Formula 1,

    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 -, wherein X ¹ At least one 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, 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, at least one or more is an alkenyl group having 2 to 30 carbon atoms.
13. 13. The method of claim 12,

    The crosslinkable polymer is a solid polymer electrolyte comprising a thiol-based crosslinking agent unit.
14. 13. The method of claim 12,

    the crosslinkable polymer forms a semi-interpenetrating network with the plasticizer,

    The lithium salt is a solid polymer electrolyte dispersed in the network.
15. cathode; anode; and a solid polymer electrolyte interposed between the negative electrode and the positive electrode,

    The solid polymer electrolyte is an all-solid-state battery comprising the solid polymer electrolyte according to any one of claims 12 to 14.
16. 16. The method of claim 15,

    The positive electrode includes a positive electrode 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 positive active material is LiCo _a M1 _b M2 _c O ₂ (M1 and M2 are each independently Ni, Mn or Al, but are different from each other, and 0.05≤a≤1.0, 0≤b≤0.95, 0≤c≤0.95, a +b + c = 1.) all-solid-state battery.

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