Patent Description:
The present invention relates to a polymer for an electrode protective layer, and a secondary battery using the polymer, and more particularly, to a protective layer capable of enhancing electrochemical stability by suppressing side reactions on an active material surface caused by an electrolyte liquid without inhibiting lithium ion transfer on the active material of a secondary battery electrode, and a secondary battery using the same.

A secondary battery that is representatively known among electrochemical devices refers to a device storing external electrical energy after converting to a form of chemical energy, and generating electricity when needed. A term "rechargeable battery" is also used in that the battery is able to be charged many times. Commonly used secondary batteries may include a lead storage battery, a nickelcadmium (Ni-Cd) battery, a nickel hydrogen (NiMH) storage battery, a lithium ion (Li-ion) battery, and a lithium ion polymer (Li-ion polymer) battery. Secondary batteries offer both economic and environmental advantages over one-time-use primary batteries.

With recent gradual development of wireless communication technologies, weight lightening of portable devices or automobile accessories has been required, and demands for secondary batteries used as an energy source for these devices have increased.

High energy density lithium secondary batteries mainly used in laptops and smart phones currently include a positive electrode formed with lithium oxide, a carbon-based negative electrode, a separator, and a liquid-state or solid-state electrolyte. As application areas for lithium secondary batteries expand to electric vehicles (EV) or energy storage systems (ESS), environments for the battery use become severe such that the driving voltage increases to <NUM> V or higher, and metal lithium is used as a negative electrode. A metal lithium negative electrode has received much attention with very high theoretical specific capacity of <NUM> mAh/g and lowest electrochemical potential of -<NUM> V (vs. standard hydrogen electrode), however, commercialization thereof has been delayed due to problems such as side reactions with an electrolyte liquid or non-uniform deposition/elution of lithium.

Metal lithium continuously forms a solid electrolyte interface (SEI) through a reaction with an organic electrolyte liquid and a lithium salt dissolved therein. The SEI layer continues to undergo destruction and regeneration while a charge and discharge cycle of a battery is repeated, and a newly exposed lithium metal surface reacts again with an electrolyte liquid to induce a decrease in the Coulombic efficiency and a short-circuit through lithium dendrite growth in the battery, which delays commercialization of a secondary battery using a metal lithium electrode.

As a solution to such a problem, attempts to coat a stable artificial SEI layer on an electrode active material surface such as lithium metal, and improve cycle properties therethrough have been made. For example, studies on improving cycle properties through suppressing lithium dendrite formation or side reactions by applying and coating polyacetylene, tetraethoxysilane, lithium phosphorous oxynitride, alumina particles, an ultra-thin alumina film or the like on a lithium film have been actively progressed. However, a phenomenon of reduced electrode protective effect was still observed after continuous battery driving, and this has been analyzed to be due to low lithium ion conductivity of an electrode, low flexibility, and crack occurrences caused by a non-uniform coating film.

Patent Document <NUM> discloses a separator for a battery, a battery, and a method of preparing a graft copolymer for a binder, the separator including a porous substrate; a coating layer on at least one surface of the porous substrate, the coating layer including an inorganic oxide; and a binder between the porous substrate and the inorganic oxide or between adjacent particles of the inorganic oxide, the binder including a graft copolymer, wherein the graft copolymer has a backbone of a polyvinylidene fluoride-based polymer or a polyvinylidene fluoride-based copolymer, and a pendant chain grafted to the backbone, the pendant chain including a hydrophilic repeating unit, and fluorine atoms in the backbone of the graft copolymer are partially substituted with at least one of chlorine, bromine, or iodine.

Patent Document <NUM> pertains to a process for the manufacture of a dense film, said process comprising, preferably consisting of the following steps: a) providing a solid composition comprising, preferably consisting of: at least one vinylidene fluoride (VDF) fluoropolymer comprising one or more carboxylic acid functional end groups, at least one poly(alkylene oxide) (PAO), and optionally, at least one inorganic filler; and b) processing said composition in molten phase thereby providing a dense film having a thickness of from <NUM> to <NUM>. It also pertains to the dense film provided by said process and to use of said dense film as dense separator in electrochemical devices.

Patent Document <NUM> discloses a lithium secondary battery solid electrolyte composition in which an alkylene oxide and a monomer containing a cross-linking functional group are grafted on a fluorine-based polymer; and a secondary battery solid electrolyte formed by thermosetting the composition.

As a result of extensive studies in view of the above, the inventors of the present invention have found out that, when preparing a polymer for an electrode protective layer by graft copolymerizing a monomer including poly(alkylene oxide) having ion conductivity and a monomer including a photocurable functional group on a fluorine-based polymer having a high dielectric constant, and using the same in a secondary battery to protect a lithium metal surface or an active material surface, chemical resistance for an electrolyte liquid is high while having excellent lithium ion conductivity since lithium ion flow is not inhibited in the electrolyte liquid by lithium ion conductivity, and voltage stability of a secondary battery is enhanced by suppressing side reactions with the electrolyte liquid occurring on an electrode active material surface due to properties of a uniform and flexible protective layer, and have completed the present invention.

According to the present invention, there is provided a polymer for an electrode protective layer including a polymer(A) in which a monomer including poly(alkylene oxide) and a monomer including a photocurable functional group are grafted on a fluorine-based polymer, wherein the polymer (A) is defined in the claims.

A polymer for an electrode protective layer according to the present invention is defined in the claims and includes a polymer(A) prepared by grafting a monomer including poly(alkylene oxide) and a monomer including a photocurable functional group on a fluorine-based polymer having a high dielectric constant, and when preparing an electrode by coating an electrode active material layer using the same and thermally curing or photocuring the result, excellent lithium ion conductivity is obtained since lithium ion flow is not inhibited, chemical resistance for an electrolyte liquid is high, and voltage stability of a secondary battery can be enhanced by suppressing side reactions with the electrolyte liquid occurring on an electrode active material surface due to properties of a uniform and flexible protective layer.

Terms or words used in the present specification and the claims are not to be interpreted limitedly to common or dictionary meanings, and shall be interpreted as meanings and concepts corresponding to technological ideas of the present disclosure based on a principle in which the inventors may suitably define the concepts of terms in order to describe the invention in the best possible way.

Terms used in the present invention are for describing specific embodiments only and do not intend to limit the present invention. Singular forms used herein include plural forms as well, unless the context clearly indicates otherwise. In the present invention, terms such as "include" or "have" are to specify the presence of features, numbers, steps, operations, constituents, components, or combinations thereof described in the present specification, and need to be construed as not excluding in advance the possibility of presence or addition of one or more of other features, numbers, steps, operations, constituents, components, or combinations thereof.

A fluorine-based polymer has a very high degree of lithium ion dissociation with a dielectric constant of approximately <NUM> to <NUM>, and, when used in a lithium secondary battery, has an advantage of having electrochemical stability even at a high voltage (<NUM> V), but has a disadvantage of having very low ion conductivity at room temperature due to high crystallinity.

Accordingly, in order to overcome the disadvantage of a fluorine-based polymer, the present invention is defined in the claims and introduces a monomer including poly(alkylene oxide) having a lithium ion chelating property on a fluorine-based polymer having a high dielectric constant through a grafting reaction. In addition, for forming a stable protective layer that is not dissolved by an electrolyte liquid or does not cause side reactions, a polymer for an electrode protective layer including a polymer(A) formed by, in addition to the monomer including poly(alkylene oxide), further graft copolymerizing a monomer including a photocurable functional group is provided.

In the present invention, the fluorine-based polymer may be a polymer including a poly(chlorotrifluoroethylene) (PCTFE) polymerization unit, and the fluorine-based polymer may be a compound represented by the following Chemical Formula <NUM>.

In Chemical Formula <NUM>,
p, q, and r are each independently <NUM>≤p≤<NUM>,<NUM>, <NUM>≤q≤<NUM>,<NUM>, and <NUM>≤r≤<NUM>,<NUM>.

The fluorine-based polymer according to one embodiment may include a dimer of vinylidene fluoride (VdF) and chlorotrifluoroethylene (CTFE), or a trimer of VDF, CTFE, and trifluoroethylene (TrFE), and the polymer may be required to include CTFE.

In order to enhance ion conductivity and electrochemical stability of the fluorine-based polymer, a monomer including poly(alkylene oxide) and a monomer including a photocurable functional group may be graft copolymerized, and one embodiment according to the present invention may be graft copolymerization using atomic transfer radical polymerization (hereinafter, ATRP).

The polymer of the invention includes polymer(A) defined in the claims. Fluorine-based polymers according to the present invention are polymers to which a branched chain can be grafted by the atomic transfer radical polymerization reaction, and any polymer may be used as long as it is such a polymer including a fluorine atom, however, polyvinylidene fluoride (PVdF), polyvinyl fluoride (PVF), polychlorotrifluoroethylene (PCTFE), polytetrafluoroethylene (PTFE), polytrifluoroethylene (PTrFE), poly-<NUM>,<NUM>-difluoroethylene, or a copolymer including two or more thereof is preferably used. Preferably, polychlorotrifluoroethylene (PCTFE), and more preferably, poly(vinylidene fluoride-chlorotrifluoroethylene) (hereinafter, P(VDF-CTFE)), or poly(vinylidene fluoride-chlorotrifluoroethylene-trifluoroethylene) (hereinafter, P(VDF-CTFE-TrFE)) may be used.

One embodiment of the present invention is capable of lowering crystallinity of a fluorine-based polymer electrolyte by introducing a chain including poly(alkylene oxide) having ion conductivity to a chlorine (Cl) group on the CTFE through atomic transfer radical polymerization, and accordingly, has an advantage of enhancing fluidity of the polymer chain. Moreover, by using a fluorine-based polymer having a high dielectric constant, more lithium ions are dissociated, and as a result, higher ion conductivity and electrochemical stability may be obtained compared to existing poly(alkylene oxide)-based polymers.

In addition, in order to secure physical, chemical and electrochemical strength, and stability of an electrode protective layer, the present invention provides a polymer having a monomer including a photocurable functional group further grafted in the polymer. The photocurable functional group may enhance the properties by itself or by being photocured with proper multifunctional vinyl-based functional groups under the presence of a photoinitiator.

In the present invention, a structure copolymerizing the monomer including poly(alkylene oxide), and the monomer including a photocurable functional group on the fluorine-based polymer includes a structure of the following Chemical Formula <NUM>.

In addition, in one specific embodiment of the present invention, the polymer(A) may include a structure of Chemical Formula <NUM>. <CHM>
<IMG>.

The monomer including poly(alkylene oxide) according to one embodiment of the present invention is a material capable of enhancing ion conductivity of a fluorine-based polymer, and the poly(alkylene oxide) is poly(ethylene oxide) or poly(propylene oxide), and may preferably be poly(ethylene oxide). Examples of the monomer including poly(alkylene oxide) include poly(alkylene oxide) (meth)acrylate, poly(alkylene oxide) monoalkyl ether (meth)acrylate, poly(alkylene oxide) monophenyl ether (meth) acrylate.

The polymer of the invention includes polymer(A) having a curable group as defined in the claims. The monomer including a photocurable functional group according to one embodiment of the present invention includes an unsaturated vinyl group, and nonlimiting examples thereof may include vinyl group-containing (meth)acrylates such as vinyl (meth) acrylate, allyl (meth)acrylate, or <NUM>-(vinyloxy)ethyl methacrylate.

The polymer of the invention includes polymer(A) having a curable group as defined in the claims. The polymerization unit including the photocurable functional group may be secondarily induced from (meth)acrylate that does not contain a vinyl group through a polymer reaction (post-polymerization reaction). For example, a hydroxyl group-containing (meth)acrylate is copolymerized with the poly(alkylene oxide) group-containing monomer, and then condensed with <NUM>-isocyanatoethyl (meth)acrylate to introduce a (meth)acrylate group on the side chain, and on the contrary, a (meth)acrylate including an isocyanate group is copolymerized with the poly(alkylene oxide) group-containing monomer, and then condensed with a hydroxyl group-containing (meth)acrylate. Types of the polymer reaction used for introducing a vinyl group on the side chain are not limited, and examples thereof may include an urethane-forming reaction of hydroxyl group-isocyanate group, and ester group-forming reaction of epoxy group-carboxylic acid group, an SN<NUM> reaction of amine group-halogen group, and the like.

The monomer including the poly(alkylene oxide) and the monomer including a photocurable functional group may have a molar ratio of <NUM>:<NUM> to <NUM>:<NUM>, and specifically, a molar ratio of <NUM>:<NUM> to <NUM>:<NUM>. When the monomer including a photocurable functional group is included in less than the above-mentioned range, a crosslinking reaction between the polymers is not sufficient, and physical, chemical, and electrochemical strength and stability of the electrode protective layer are not sufficient, and the content being greater than the above-mentioned range may significantly decrease ion conductivity due to a small alkylene oxide content and too high polymer network density, and therefore, the content is properly controlled in the above-mentioned range.

The polymer of the invention includes polymer(A) including the structure defined in the claims. In one embodiment of the present invention, the fluorine-based graft polymer(A) may further introduce a unit derived from a third monomer to the graft chain with the purpose of enhancing interfacial adhesion properties and mechanical properties of the electrode active material. Examples of the third monomer may include methyl (meth)acrylate, ethyl (meth) acrylate, n-propyl (meth)acrylate, isopropyl (meth) acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, <NUM>-ethylbutyl (meth)acrylate, <NUM>-ethylhexyl (meth)acrylate, n-octyl.

(meth)acrylate, isooctyl (meth)acrylate, isononyl (meth) acrylate, lauryl (meth)acrylate, styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, (meth)acrylonitrile and the like, but are not limited thereto.

The third monomer according to one embodiment of the present invention may be included in <NUM> part by weight to <NUM> parts by weight with respect to a total <NUM> parts by weight of the fluorine-based graft polymer(A). Improvements in target properties may be insignificant under <NUM> part by weight, and ion conductivity may become too low when including in greater than <NUM> parts by weight.

The fluorine-based polymer according to Chemical Formula <NUM> according to one embodiment of the present invention may be included in <NUM> parts by weight to <NUM> parts by weight, and preferably in <NUM> parts by weight to <NUM> parts by weight with respect to <NUM> parts by weight of the fluorine-based graft polymer(A). When the fluorine-based polymer content is greater than the above-mentioned range, mechanical strength and electrochemical stability of the electrode protective layer may increase, however, crystallinity of the fluorine-based polymer may not be suppressed and the alkylene oxide content excessively decreases reducing ion conductivity. When the fluorine-based polymer content is less than the above-mentioned range, properties of high electrochemical stability and high lithium ion dissociation of the fluorine-based polymer may not be obtained, and therefore, the content is properly selected in the above-mentioned range.

The following polymer compositions are not specified in the claims but are covered by them. The present disclosure provides a polymer composition for an electrode protective layer including the polymer composition for an electrode protective layer and further including a multifunctional vinyl-based crosslinking agent having a functional group capable of reacting with the photocurable functional group included in the fluorine-based graft polymer (A). The fluorine-based graft polymer(A) may be photocured by a vinyl group introduced on the side chain under the presence of a photoinitiator, but may be a polymer composition for photocuring further including a multifunctional vinyl-based crosslinking agent.

The multifunctional vinyl-based crosslinking agent may further react with an unsaturated vinyl functional group included in the graft polymer of Chemical Formula <NUM> to form a crosslinked structure between the polymers. The electrode protective layer formed in a crosslinked structure has high chemical and electrochemical stability, and protects an electrode active material surface from side reactions with an electrolyte liquid, and thereby may overcome problems such as deterioration in the cycle properties and decrease in the Coulombic efficiency of a secondary battery.

In one embodiment of the present disclosure, the multifunctional vinyl-based crosslinking agent is an organic compound having two or more vinyl groups in one molecule, and examples thereof may include one or more types of ethylene glycol di(meth)acrylate, <NUM>,<NUM>-hexanediol di(meth)acrylate, tri(propylene glycol) di(meth)acrylate, tris(<NUM>-(meth)acryloethyl) isocyanate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxylate tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and the like, but are not limited thereto.

The multifunctional vinyl-based crosslinking agent may be included in a ratio of <NUM> parts by weight to <NUM> parts by weight, and preferably <NUM> parts by weight to <NUM> parts by weight with respect to <NUM> parts by weight of the fluorine-based graft polymer(A). By controlling the crosslinking agent content in the above-described range, properties of an electrolyte may be properly obtained at a target level.

In one embodiment of the present disclosure, as the photoinitiator, general initiators capable of initiating photopolymerization by generating radicals through irradiating ultraviolet rays or the like such as acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, oxime-based compounds, benzoin-based compounds, hydroxyketone-based compounds, aminoketone-based compounds, or phosphine oxide-based compounds may be used without limit.

The acetophenone-based compound usable as the photoinitiator is selected from the group consisting of <NUM>-hydroxy-<NUM>-methyl-<NUM>-phenylpropan-<NUM>-one, <NUM>-(<NUM>-isopropylphenyl)-<NUM>-hydroxy-<NUM>-methylpropan-<NUM>-one, <NUM>-(<NUM>-hydroxyethoxy)-phenyl-(<NUM>-hydroxy-<NUM>-propyl) ketone, <NUM>-hydroxycyclohexylphenylketone, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin butyl ether, <NUM>,<NUM>-dimethoxy-<NUM>-phenylacetophenone, <NUM>-methyl-(<NUM>-methylthio)phenyl-<NUM>-morpholino-<NUM>-propan-<NUM>-one, <NUM>-benzyl-<NUM>-dimethylamino-<NUM>-(<NUM>-morpholinophenyl)-butan-<NUM>-one, <NUM>-(<NUM>-bromo-benzyl-<NUM>-dimethylamino-<NUM>-(<NUM>-morpholinophenyl)-butan-<NUM>-one, and <NUM>-methyl-<NUM>-[<NUM>-(methylthio)phenyl]-<NUM>-morpholinopropan-<NUM>-one, the biimidazole-based compound is selected from the group consisting of <NUM>,<NUM>-bis(<NUM>-chlorophenyl)-<NUM>,<NUM>',<NUM>,<NUM>'-tetraphenyl biimidazole, <NUM>,<NUM>'-bis(o-chlorophenyl)-<NUM>,<NUM>',<NUM>,<NUM>'-tetrakis(<NUM>,<NUM>,<NUM>-trimethoxyphenyl)-<NUM>,<NUM>'-biimidazole, <NUM>,<NUM>'-bis(<NUM>,<NUM>-dichlorophenyl)-<NUM>,<NUM>',<NUM>,<NUM>'-tetraphenyl biimidazole, and <NUM>,<NUM>'-bis(o-chlorophenyl)-<NUM>,<NUM>,<NUM>,<NUM>'-tetraphenyl-<NUM>,<NUM>'-biimidazole, the triazine-based compound is selected from the group consisting of <NUM>-{<NUM>-[<NUM>,<NUM>-bis(trichloromethyl)-s-triazin-<NUM>-yl]phenylthio}propionic acid, <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoroisopropyl-<NUM>-{<NUM>-[<NUM>,<NUM>-bis(trichloromethyl)-s-triazin-<NUM>-yl]phenylthio}propionate, ethyl-<NUM>-{<NUM>-[<NUM>,<NUM>-bis(trichloromethyl)-s-triazin-<NUM>-yl]phenylthio}acetate, <NUM>-epoxyethyl-<NUM>-{<NUM>-[<NUM>,<NUM>-bis(trichloromethyl)-s-triazin-<NUM>-yl]phenylthio}acetate, cyclohexyl-<NUM>-{<NUM>-[<NUM>,<NUM>-bis(trichloromethyl)-s-triazin-<NUM>-yl]phenylthio}acetate, benzyl-<NUM>-{<NUM>-[<NUM>,<NUM>-bis(trichloromethyl)-s-triazin-<NUM>-yl]phenylthio}acetate, <NUM>-{chloro-<NUM>-[<NUM>,<NUM>-bis(trichloromethyl)-s-triazin-<NUM>-yl]phenylthio}propionic acid, <NUM>-{<NUM>-[<NUM>,<NUM>-bis(trichloromethyl)-s-triazin-<NUM>-yl]phenylthio}propionamide, <NUM>,<NUM>-bis(trichloromethyl)-<NUM>-p-methoxystyryl-s-triazine, <NUM>,<NUM>-bis(trichloromethyl)-<NUM>-(<NUM>-p-dimethylaminophenyl)-<NUM>,<NUM>,-butadienyl-s-triazine, and <NUM>-trichloromethyl-<NUM>-amino-<NUM>-p-methoxystyryl-s-triazine, and examples of the oxime-based compound may include <NUM>,<NUM>-octadione-<NUM>-(<NUM>-phenylthio)phenyl-<NUM>-(o-benzoyloxime) (Ciba Geigy Ltd. , CGI <NUM>), and ethanone-<NUM>-(<NUM>-ethyl)-<NUM>-(<NUM>-methylbenzoyl-<NUM>-yl)-<NUM>-(o-acetyloxime) (CGI <NUM>), oxime OX-<NUM> (Ciba Geigy Ltd. ), NCI-<NUM> (Adeka Corporation), PI-<NUM> (LG Chem. ), PBG <NUM>, PBG <NUM>, PBG <NUM> (Tronly) and the like.

In addition, α-hydroxyketone-based compounds (ex. IRGACURE <NUM>, IRGACURE <NUM>, IRGACURE <NUM>, DAROCUR <NUM>; manufactured by Ciba Specialty Chemicals); phenyl glyoxylate-based compounds (ex. IRGACURE <NUM>, DAROCUR MBF; manufactured by Ciba Specialty Chemicals); benzyl dimethyl ketal-based compounds (ex. IRGACURE <NUM>; manufactured by Ciba Specialty Chemicals); α-aminoketone-based compounds (ex. IRGACURE <NUM>, IRGACURE <NUM>, IRGACURE <NUM>; manufactured by Ciba Specialty Chemicals); monoacylphosphine-based compounds (MAPO) (ex. DAROCUR TPO; manufactured by Ciba Specialty Chemicals); bisacylphosphine-based compounds (BAPO) (ex. IRGACURE <NUM>, IRGACURE 819DW; manufactured by Ciba Specialty Chemicals); phosphine oxide-based compounds (ex. IRGACURE <NUM>; manufactured by Ciba Specialty Chemicals); metallocene-based compounds (ex. IRGACURE <NUM>; manufactured by Ciba Specialty Chemicals); iodonium salts (ex. IRGACURE <NUM>; manufactured by Ciba Specialty Chemicals); and a mixture of two or more thereof may be included as an example, however, the photoinitiator is not limited thereto.

The photoinitiator content may be from <NUM> parts by weight to <NUM> parts by weight and preferably from <NUM> parts by weight to <NUM> part by weight with respect to <NUM> parts by weight of the fluorine-based graft polymer(A), but is not limited thereto. When the photoinitiator content is <NUM> or less, curing may not be sufficiently obtained, and an electrode protective layer having target properties may not be obtained, and therefore, the content is properly controlled in the above-mentioned range.

A method for preparing a polymer for an electrode protective layer according to the present invention may include mixing, polymerizing, and, selectively, polymer reacting.

In the method, the mixing may be forming a mixture by mixing a raw material for preparing a polymer in which a monomer including poly(alkylene oxide) and a monomer including a photocurable functional group or a monomer including a functional group capable of introducing a photocurable functional group in the polymer reacting are grafted, and the mixing, which is one example, may be mixing a fluorine-based polymer, the monomer to polymerize, and a solvent. After that, mixing a catalyst and a ligand with the solvent may be further included.

The fluorine-based polymer is a part becoming a main chain of the grafted polymer(A), and specific examples thereof may be the same as described above, and, as one embodiment according to the present invention, may include poly(vinylidene-co-chlorotrifluoroethylene) (hereinafter, P(VDF-co-CTFE)). In one embodiment of the present invention, the monomer including poly(alkylene oxide), and the monomer having a photocurable functional group may be poly(ethylene glycol) monomethyl ether methacrylate (hereinafter, mPEGMA) and <NUM>-hydroxyethyl methacrylate (hereinafter, HEMA).

As the solvent, various solvents known in the art may be used, and for example, N-methyl-<NUM>-pyrrolidone (NMP), gamma-butyrolactone (GBL), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), acetonitrile (AcCN), tetrahydrofuran (THF) or the like may be used, however, the solvent is not limited thereto.

To the mixture solution, a catalyst and a ligand may be further mixed with the solvent.

Examples of the catalyst may include Cu(I)Cl, Cu(II)Cl<NUM>, Cu(I)Br, Cu(II)Br<NUM>, Fe(II)Cl<NUM>, Fe(III)Cl<NUM> or mixtures thereof, and preferably, Cu(I) Cl, Cu(II)Cl<NUM>, Cu(I)Br, Cu(II)Br<NUM> or mixtures thereof may be included as an example.

In addition, the catalyst content may be from <NUM> parts by weight to <NUM> part by weight, <NUM> parts by weight to <NUM> parts by weight, or <NUM> parts by weight to <NUM> parts by weight with respect to <NUM> parts by weight of the monomer mixture. When the catalyst content is less than <NUM> parts by weight, the reaction rate is very delayed, and when greater than <NUM> part by weight, problems such as gelation before producing the polymerized graft polymer or very difficult catalyst removal occur, and therefore, the content is properly selected in the above-mentioned range.

The ligand is not particularly limited as long as it is usable in a polymerization reaction by bonding to the catalyst.

As one example, the ligand may include ligands having one or more nitrogen, oxygen, phosphorous, and sulfur atoms that may coordinate to the catalyst through σ-bonds or ligands having two or more carbon atoms that may coordinate to the catalyst through n-bonds, but is not limited thereto. Specifically, one or more types selected from the group consisting of N,N,N',N"",N""-pentamethyldiethylenetriamine (PMDETA), <NUM>,<NUM>'-bipyridine (bpy), <NUM>,<NUM>'-di-<NUM>-nonyl-<NUM>,<NUM>'-bipyridine (dNbpy), tris(<NUM>-pyridylmethyl)amine (TPMA), and tris(<NUM>-dimethylaminoethyl)amine (Me6TREN) may be used, however, the ligand is not limited thereto.

The ligand content may be from <NUM> parts by weight to <NUM> parts by weight, <NUM> parts by weight to <NUM> parts by weight, or <NUM> parts by weight to <NUM> parts by weight with respect to <NUM> parts by weight of the catalyst. When the ligand content is less than <NUM> parts by weight, metal complex formation obtained by bonding with the catalyst is too little resulting in very slow or no reaction, and the ligand content being greater than <NUM> parts by weight may increase manufacturing costs and cause concern of side reactions caused by an excessive ligand use.

The ATRP reaction may use a catalyst reducing agent as necessary. Examples of the reducing agent may include an organic reducing agent, an inorganic reducing agent, a radical generator and the like, but are not limited thereto.

When the catalyst, the ligand, and, as necessary, the catalyst reducing agent of the ATRP reaction are mixed and stirred at <NUM> to <NUM>, the ATRP reaction occurs, and a grafted polymer may be obtained.

The polymer reacting is a step required when using a monomer including a functional group capable of introducing a photocurable functional group in the mixing, and may be included when the photocurable vinyl-based monomer has a high risk of producing a gelation reaction in the polymerizing. In the polymer reacting, a proper condensation reaction condition may be selected depending on the grafted polymer prepared in the ATRP reacting and the types of the functional group as a condensation reaction of the monomer compound. As a specific example, when the monomer used in the mixing is an alcohol group-containing monomer such as <NUM>-hydroxyethyl methacrylate, a (meth)acrylate group may be introduced in the polymer reacting through condensation with an isocyanate-containing (meth)acrylate compound. Herein, the reaction temperature may be selected in a range of <NUM> to <NUM>, and selectively, the reaction may be facilitated using a catalyst such as dibutyltin dilaurate.

In addition, the polymer according to one embodiment of the present invention may be PVDF-co-(PCTFE-g-(mPEGMA-co-HEMA-AOI)), a compound obtained by preparing PVDF-co-(PCTFE-g- (mPEGMA-co-HEMA)) using the ATRP method, and then introducing a (meth)acrylate group on the side chain through a polymer reaction between the graft polymer and <NUM>-isocyanatoethyl acrylate or <NUM>-(acryloyloxy)ethyl isocyanate (AOI).

After the grafting polymerization reaction, removing the unreacted monomer by precipitating the produced polymer in a proper nonsolvent may be further included. After that, the polymer is dried under a vacuum condition to obtain the fluorine-based graft polymer(A) according to the present invention.

This method is not specified in the claims but is covered by them when the method uses the polymer defined in the claims. The electrode protective layer according to the present disclosure specifically means an electrode protective layer for resolving the above-described problems by being coated on at least one surface of an electrode active material or metal lithium, and the forming method of the electrode protective layer may include the following steps: introducing a multifunctional crosslinking agent to the fluorine-based graft polymer (A) or the fluorine-based graft polymer (A) -dissolved solution in a ratio of <NUM> parts by weight to <NUM> parts by weight or <NUM> parts by weight to <NUM> parts by weight with respect to <NUM> parts by weight of the whole fluorine-based graft polymer(A), properly diluting the result in a solvent, and stirring the result for <NUM> hour to <NUM> hours. After that, the solution is mixed with an active material to coat to prepare a paste or coated on a foil-type electrode surface, heat treated for <NUM> minute to <NUM> hours at <NUM> to <NUM>, and then cured and dried to be prepared. On the coating film-formed active material, a vacuum drying process or a heating process may be further conducted to remove the residual solvent.

Alternatively, the forming method of the electrode protective layer may include the following steps: introducing a multifunctional vinyl-based crosslinking agent to the fluorine-based graft polymer(A) or the fluorine-based graft polymer (A) -dissolved solution in a ratio of <NUM> parts by weight to <NUM> parts by weight with respect to <NUM> parts by weight of the whole fluorine-based graft polymer(A), introducing a photoinitiator in a ratio of <NUM> parts by weight to <NUM> parts by weight with respect to a total <NUM> parts by weight of the fluorine-based graft polymer(A) and the multifunctional vinyl-based crosslinking agent, properly diluting the result in a solvent, and stirring the result for <NUM> hour to <NUM> hours. After that, the solution is mixed with an active material to coat to prepare a paste or coated on a foil-type electrode surface, photocured by irradiating ultraviolet (UV) rays thereon, and then a vacuum drying process or a heating process may be further conducted to remove the residual solvent.

According to one embodiment of the present disclosure, the protective layer-formed electrode may include an electrode active material, and the electrode active material may be any one selected from the group consisting of metal lithium, a positive electrode active material, and a negative electrode active material.

However, the examples according to the present invention may be modified to various other forms, and the scope of the present invention is not to be construed as being limited to the examples described below. Examples of the present invention are provided in order to more fully describe the present invention to those having average knowledge in the art.

In a <NUM> flask, <NUM> of P(VDF-co-CTFE) having a weight average molecular weight (hereinafter, Mw) of <NUM>,<NUM> as a fluorine-based polymer, and <NUM> of poly(ethylene glycol) monomethyl ether methacrylate (mPEGMA, ethylene oxide repeating number=<NUM>), and <NUM> of <NUM>-hydroxyethyl methacrylate (HEMA), as monomers to polymerize, were introduced to <NUM> of a dimethyl sulfoxide (DMSO) solvent, and were stirred for <NUM> hour under the nitrogen condition.

After that, <NUM> of CuCl<NUM> as an ATRP reaction catalyst, <NUM> of TPMA as a ligand, and <NUM> of tin(II) <NUM>-ethylhexanoate (Sn(EH)<NUM>) as a reducing agent were introduced to the flask, and the ATRP reaction was proceeded for <NUM> hours at <NUM> under the nitrogen condition with stirring. Herein, the monomer conversion was <NUM>%.

After the reaction was completed, a produced polymer was reprecipitated in a diethyl ether solvent to remove the unreacted monomers. The finally obtained polymer was dried for <NUM> hours under the vacuum condition to obtain a PVDF-co-(PCTFE-g-(mPEGMA-co-HEMA)) polymer (A1-<NUM>) having a fluorine-based chain content of <NUM>%.

In a <NUM> flask, <NUM> of P(VDF-co-CTFE) having a weight average molecular weight (hereinafter, Mw) of <NUM>,<NUM> as a fluorine-based polymer, and <NUM> of poly(ethylene glycol)monomethyl ether acrylate (mPEGA, ethylene oxide repeating number=<NUM>), and <NUM> of <NUM>-hydroxybutyl acrylate (HBA), as monomers to polymerize, were introduced to <NUM> of a DMSO solvent, and were stirred for <NUM> hour under the nitrogen condition.

After that, <NUM> of CuCl<NUM> as an ATRP reaction catalyst, <NUM> of TPMA as a ligand, and <NUM> of azobisisobutyronitrile (AIBN) as a reducing agent were introduced to the flask, and the ATRP reaction was proceeded for <NUM> hours at <NUM> under the nitrogen conditionwith stirring. Herein, the monomer conversion was <NUM>%.

After the reaction was completed, a produced polymer was reprecipitated in an ether solvent to remove the unreacted monomers. The finally obtained polymer was vacuum dried for <NUM> hours at room temperature to obtain a PVDF-co-(PCTFE-g-(mPEGA-co-HBA) )-polymer (A1-<NUM>) having a fluorine-based chain content of <NUM>%.

In a <NUM> flask, <NUM> of P(VDF-co-CTFE-co-TrFE) having a weight average molecular weight (Mw) of <NUM>,<NUM> as a fluorine-based polymer, and <NUM> of mPEGMA (ethylene oxide repeating number=<NUM>), and <NUM> of <NUM>-(trimethoxysilyl)propyl methacrylate (TMSPMA), as monomers to polymerize, were introduced to <NUM> of a dimethylformamide (DMF) solvent, and were stirred for <NUM> hour under the nitrogen condition.

After the reaction was completed, a produced polymer was reprecipitated in a diethyl ether solvent to remove the unreacted monomers. The finally obtained polymer was vacuum dried for <NUM> hours at room temperature to obtain a PVDF-co-(PCTFE-g-(mPEGMA-co-TMSPMA))-co-PTrFE polymer (A1-<NUM>) having a fluorine-based chain content of <NUM>%.

In a <NUM> flask, <NUM> of mPEGMA (ethylene oxide repeating number=<NUM>) and <NUM> of HEMA were introduced to <NUM> of a DMSO solvent, and were stirred for <NUM> hour under the nitrogen condition. <NUM> of AIBN was introduced thereto as a radical initiator, and the polymerization reaction was proceeded for <NUM> hours at <NUM> under the nitrogen atmospherewith stirring.

After the reaction was completed, a produced polymer was reprecipitated in a diethyl ether solvent to remove the unreacted monomers. The finally obtained polymer was vacuum dried for <NUM> hours at room temperature to obtain a P(mPEGMA-co-HEMA) polymer (B1-<NUM>) that does not contain a fluorine-based chain.

Preparation Examples <NUM>-<NUM> to <NUM>-<NUM> and Comparative Preparation Example <NUM>-<NUM> are shown in the following Table <NUM>.

After that, <NUM> of CuCl<NUM> as an ATRP reaction catalyst, <NUM> of TPMA as a ligand, and <NUM> of azobisisobutyronitrile (AIBN) as a reducing agent were introduced to the flask, and the ATRP reaction was proceeded for <NUM> hours at <NUM> under the nitrogen conditionwith stirring. Herein, the monomer conversion rate was <NUM>%.

After the polymerization was completed, the reaction material was cooled to room temperature, and air was bubbled into the reaction vessel for <NUM> hours. <NUM> of <NUM>,<NUM>-bis(<NUM>,<NUM>-dimethylethyl)-<NUM>-methylphenol (BHT) was introduced thereto as a thermal polymerization inhibitor, and after heating the reaction material to <NUM>, <NUM> of <NUM>-isocyanatoethyl acrylate (AOI), and <NUM> of dibutyltin dilaurate (DBTDL) as a condensation catalyst were introduced thereto. The result was reacted for <NUM> hours under the presence of oxygen, and then the reaction was terminated. Using the above-described method, a mixture solution of a PVDF-co- (PCTFE-g-(mPEGMA-co-(HEMA-AOI))) polymer having a fluorine-based chain content of <NUM>% and the monomers was obtained. The unreacted residual monomer was included in a polymer network in a photopolymerization process afterward.

In a <NUM> flask, <NUM> of P(VDF-co-CTFE) having a weight average molecular weight (hereinafter, Mw) of <NUM>,<NUM> as a fluorine-based polymer, and <NUM> of polyethylene glycol monomethyl ether acrylate (mPEGA, ethylene oxide repeating number=<NUM>), and <NUM> of <NUM>-hydroxybutyl acrylate (HBA), as monomers to polymerize, were introduced to <NUM> of a DMSO solvent, and were stirred for <NUM> hour under the nitrogen condition.

After that, <NUM> of CuCl<NUM> as an ATRP reaction catalyst, <NUM> of TPMA as a ligand, and <NUM> of AIBN as a reducing agent were introduced to the flask, and the ATRP reaction was proceeded for <NUM> hours at <NUM> under the nitrogen conditionwith stirring. Herein, the monomer conversion rate was <NUM>%.

After the polymerization was completed, the reaction material was cooled to room temperature, and air was bubbled into the reaction vessel for <NUM> hours. <NUM> of <NUM>,<NUM>-bis(<NUM>,<NUM>-dimethylethyl)-<NUM>-methylphenol (BHT) was introduced thereto as a thermal polymerization inhibitor, and after heating the reaction material to <NUM>, <NUM> of <NUM>-isocyanatoethyl acrylate (AOI), and <NUM> of dibutyltin dilaurate (DBTDL) as a condensation catalyst were introduced thereto. The result was reacted for <NUM> hours under the presence of oxygen, and then the reaction was terminated. Using the above-described method, a mixture solution of a PVDF-co-(PCTFE-g-(mPEGA-co-(HBA-AOI))) polymer having a fluorine-based chain content of <NUM>% and the monomers was obtained. The unreacted residual monomer was included in a polymer network in a photopolymerization process afterward.

In a <NUM> flask, <NUM> of P(VDF-co-CTFE-co-TrFE) having a weight average molecular weight (Mw) of <NUM>,<NUM> as a fluorine-based polymer, and <NUM> of mPEGMA (ethylene oxide repeating number=<NUM>), and <NUM> of HEMA, as monomers to polymerize, were introduced to <NUM> of a dimethylformamide (DMF) solvent, and were stirred for <NUM> hour under the nitrogen condition.

After the polymerization was completed, the reaction material was cooled to room temperature, and air was bubbled into the reaction vessel for <NUM> hours. <NUM> of <NUM>,<NUM>-bis(<NUM>,<NUM>-dimethylethyl)-<NUM>-methylphenol (BHT) was introduced thereto as a thermal polymerization inhibitor, and after heating the reaction material to <NUM>, <NUM> of <NUM>-isocyanatoethyl acrylate (AOI), and <NUM> of dibutyltin dilaurate (DBTDL) as a condensation catalyst were introduced thereto. The result was reacted for <NUM> hours under the presence of oxygen, and then the reaction was terminated. Using the above-described method, a mixture solution of a PVDF-co-(PCTFE-g-(mPEGMA-co-(HHEMA-AOI)))-co-PTrFE polymer having a fluorine-based chain content of <NUM>% and the monomers was obtained. The unreacted residual monomer was included in a polymer network in a photopolymerization process afterward.

In a <NUM> flask, <NUM> of mPEGMA (ethylene oxide repeating number=<NUM>) and <NUM> of HEMA were introduced to <NUM> of a DMSO solvent, and were stirred for <NUM> hour under the nitrogen condition. <NUM> of AIBN was introduced thereto as a radical initiator, and the polymerization reaction was proceeded for <NUM> hours at <NUM> under the nitrogen atmospherewith stirring. After that, the process was conducted in the same manner as in Preparation Example <NUM> to obtain a mixture solution of a P(mPEGMA-co-(HEMA-AOI))) polymer and the monomers (B2-<NUM>).

A graft polymerization was conducted in the same manner as in Preparation Example <NUM> using <NUM> of P(VDF-co-CTFE) having a weight average molecular weight (hereinafter, Mw) of <NUM>,<NUM> as a fluorine-based polymer, and <NUM> of mPEGMA (ethylene oxide repeating number=<NUM>) and <NUM> of HEMA, as monomers to polymerize, with <NUM> of a DMSO solvent, and, without a polymer reaction introducing a vinyl group on the side chain, a mixture solution of a PCTFE-g-P(mPEGMA-co-HEMA) and the unreacted monomers (B2-<NUM>) was obtained.

Preparation Examples <NUM>-<NUM> to <NUM>-<NUM> and Comparative Preparation Examples <NUM>-<NUM> and <NUM>-<NUM> are shown in the following Table <NUM>.

Each of the fluorine-based graft polymers prepared in Preparation Examples <NUM>-<NUM> to <NUM>-<NUM> (these examples do not form part of the invention and are provided for information purposes only) was mixed in a weight ratio (pt) as written in Table <NUM>, and stirred for <NUM> hours to prepare a thermocurable polymer solution. The solution was coated on a <NUM><NUM> × <NUM> circular SUS substrate in a dry room, heated for <NUM> hours at a temperature of <NUM> for drying, and further thermally cured for <NUM> hours at <NUM>. After that, the result was vacuum dried for <NUM> hours at <NUM> to prepare a completely dried polymer electrode protective layer. The amount of the coated polymer solution was adjusted so that a thickness of the final electrode protective layer becomes approximately <NUM>.

The polymer prepared in Comparative Preparation Example <NUM>-<NUM> and a P(VDF-CTFE) copolymer was mixed in a composition as in Table <NUM>, and stirred for <NUM> hours to prepare a homogeneous solution. After that, the same cured film preparation method as the example was used to prepare a polymer cured film.

Examples <NUM>-<NUM> to <NUM>-<NUM> (these examples do not form part of the invention and are provided for information purposes only) and Comparative Examples <NUM>-<NUM> to <NUM>-<NUM> are shown in the following Table <NUM>.

Each of the fluorine-based graft polymers prepared in Preparation Examples <NUM>-<NUM> to <NUM>-<NUM> was mixed in a weight ratio (pt) as in Table <NUM>, and stirred for <NUM> hours to prepare a photocurable polymer solution. The solution was coated on a <NUM><NUM>×<NUM> circular SUS substrate in a dry room, and then exposed to a metal halide lamp for <NUM> minutes. After that, the result was vacuum dried for <NUM> hours at <NUM> to prepare a completely dried polymer electrode protective layer. The amount of the coated polymer solution was adjusted so that a thickness of the final electrode protective layer becomes approximately <NUM>.

Each of the polymers prepared in Comparative Preparation Examples <NUM>-<NUM> and <NUM>-<NUM> was mixed in a composition as in Table <NUM>, and stirred for <NUM> hours to prepare a homogeneous solution. After that, the same cured film preparation method as the example was used to prepare a polymer cured film.

Examples <NUM>-<NUM> to <NUM>-<NUM> and Comparative Examples <NUM>-<NUM> to <NUM>-<NUM> are shown in the following Table <NUM>.

Ion conductivity of each of the electrode protective layers prepared in Examples <NUM>-<NUM> to <NUM>-<NUM> (these examples do not form part of the invention and are provided for information purposes only), Examples <NUM>-<NUM> to <NUM>-<NUM>, Comparative Examples <NUM>-<NUM> to <NUM>-<NUM> and Comparative Examples <NUM>-<NUM> to <NUM>-<NUM> was obtained using the following Mathematical Formula <NUM> after measuring the impedance.

After bringing a lithium salt-containing electrode protective layer coated on a circular SUS (stainless steel) substrate into contact with a lithium metal electrode having the same surface area, an alternating current voltage was applied through electrodes on both surfaces of the sample at room temperature. Herein, an amplitude range of a measuring frequency of <NUM> to <NUM> was set as the applied condition, and impedance was measured using VMP3 manufactured by Bio-Logic. Resistance of the bulk electrolyte was obtained from an intersection (Rb) where a semicircle or straight line of the measured impedance trajectory meets the real-number axis, and ion conductivity of the polymer electrode protective layer was calculated from the width and the thickness of the sample, and the results are shown in the following Table <NUM>.

A cell having a lithium-salt containing polymer electrode protective layer sandwiched between SUS and lithium metal was manufactured in the same manner as in the experimental example. A cyclic voltammetry (IVIUM Technologies) was performed by applying a voltage of <NUM> V to <NUM> V at a rate of <NUM> mV/sec at <NUM> to evaluate oxidation potential stability by an off-set voltage. The results are shown in Table <NUM>.

Each of the polymer electrode protective layers, the electrode protective layer prepared in each of Examples <NUM>-<NUM> to <NUM>-<NUM> (these examples do not form part of the invention and are provided for information purposes only), Examples <NUM>-<NUM> to <NUM>-<NUM>, Comparative Examples <NUM>-<NUM> to <NUM>-<NUM> and Comparative Examples <NUM>-<NUM> to <NUM>-<NUM>, was coated on a SUS (stainless steel) substrate, and the result was dipped in a <NUM> diethyl carbonate solution including <NUM> LiPF<NUM>. After that, the result was deposited for <NUM> hours at room temperature, and the film shape was visually observed. The results are shown in Table <NUM>.

Claim 1:
A polymer for an electrode protective layer comprising a polymer(A) in which a monomer including poly(alkylene oxide) and a monomer including a curable functional group are grafted on a fluorine-based polymer, wherein the polymer(A) includes a structure of the following Chemical Formula <NUM>:
<CHM>
in Chemical Formula <NUM>,
p, q, r, and s are each independently <NUM>≤p≤<NUM>,<NUM>, <NUM><q≤<NUM>,<NUM>, <NUM>≤r≤<NUM>,<NUM> and <NUM>≤s<<NUM>,<NUM>;
R<NUM>, R<NUM>, and R<NUM> are each independently hydrogen or methyl;
R<NUM> is any one selected from among hydrogen, an alkyl group having <NUM> to <NUM> carbon atoms, and a phenyl group unsubstituted or substituted with an alkyl group having <NUM> to <NUM> carbon atoms;
Z is a curable functional group represented by the following Chemical Formula <NUM>;
l, m and n are each independently <NUM>≤<NUM>≤<NUM>, <NUM>≤m≤<NUM> and <NUM>≤n≤<NUM>; and
R<NUM> is any one selected from among hydrogen, chlorine or bromine,
<CHM>
in Chemical Formula <NUM>,
X is a single bond, or any one selected from among alkylene having <NUM> to <NUM> carbon atoms, alkyleneoxycarbonyl having <NUM> to <NUM> carbon atoms (.
<CHM>
), urethane group-containing alkyleneoxycarbonyl having <NUM> to <NUM> carbon atoms, poly(ethylene oxide)carbonyl having an ethylene oxide repeating number of <NUM> to <NUM> and phenylene; and
* represents a bonding site directly bonding to O in Chemical Formula <NUM>.