Gel polymer electrolyte for lithium battery and lithium battery comprising same

Abstract

Disclosed is a gel polymer electrolyte for a lithium battery comprising a gel polymer and a liquid electrolyte, the liquid electrolyte comprising lithium salt and an organic solvent, and the gel polymer being a cross-linked product of i) a multifunctional acryl-based first polymerizable monomer having at least three polymerizable functional groups and ii) a second polymerizable monomer selected from urethane acryl-based monomers having at least two functional groups.

Description

Gel polymer electrolyte for lithium batteries and lithium batteries containing the same

[0001] The present invention relates to a gel polymer electrolyte for a lithium battery and a lithium battery including the same.

[0002] Currently, liquid electrolytes used in lithium-ion batteries or lithium metal batteries have safety issues, so research is being conducted to use semi-solid or all-solid polymer electrolytes as important alternative materials.

[0003] Gel polymer electrolytes are semi-solid gel-type electrolytes that contain liquid in a polymer solid electrolyte. They can be manufactured in the form of a free-standing film or by being injected together with the electrolyte solution and then cured. Gel polymer electrolytes (GPEs) have increased resistance compared to pure liquid electrolytes (LEs), resulting in a decrease in capacity, but can offer improved stability.

[0004] One aspect is to provide a new gel polymer electrolyte for lithium batteries.

[0005] Another aspect is to provide a lithium battery with improved cell performance by employing the gel polymer electrolyte described above.

[0006] According to one embodiment, a gel polymer electrolyte for a lithium battery comprising a gel polymer and a liquid electrolyte,

[0007] The above liquid electrolyte includes a lithium salt and an organic solvent, and the gel polymer is a crosslinked product of i) a multifunctional acrylic first polymerizable monomer having three or more polymerizable functional groups, and ii) a second polymerizable monomer selected from among urethane acrylic monomers having two or more functional groups. A gel polymer electrolyte for a lithium battery is provided.

[0008] According to another aspect, a lithium battery comprising a positive electrode, a negative electrode current collector, and an electrolyte layer disposed between the positive electrode and the negative electrode current collector,

[0009] The above electrolyte layer provides a lithium battery including the above-described gel polymer electrolyte.

[0010] Gel polymer electrolytes according to one aspect have improved ionic conductivity and physical properties, and their use provides lithium batteries with improved life and high-rate characteristics.

[0011] Figure 1 is a drawing for explaining the laminated structure of a lithium battery according to an embodiment.

[0012] Figure 2 is a drawing for explaining the laminated structure of a lithium battery according to another embodiment.

[0013] Figure 3 is a schematic diagram of a lithium battery according to another embodiment.

[0014] Figure 4 is a schematic diagram of a lithium battery according to another embodiment.

[0015] Figure 5 is a schematic diagram of a lithium battery according to another embodiment.

[0016] Figure 6a shows the life characteristics after 200 cycles in the lithium batteries of Example 1-2 and Comparative Example 1.

[0017] Figure 6b shows the change in capacity characteristics after 200 cycles in the lithium batteries of Example 1-2 and Comparative Example 1.

[0018] Figure 7a shows the ionic conductivity at room temperature for the gel polymer electrolyte in the lithium batteries of Example 2 and Comparative Example 1, and Figure 7b shows the ionic conductivity at high temperature for the gel polymer electrolyte in the lithium batteries of Example 2 and Comparative Example 1.

[0019] [Explanation of symbols]

[0020] 1 lithium battery 2, 20 cathode

[0021] 3, 10 anode 4 separator

[0022] 5 Battery case 6 Cap assembly

[0023] 7 Battery structure 8 Electrode tab

[0024] The present inventive concept described below is capable of various modifications and embodiments. Specific embodiments are illustrated in the drawings and described in detail. However, this is not intended to limit the present inventive concept to specific embodiments, but rather to encompass all modifications, equivalents, or alternatives within the technical scope of the present inventive concept.

[0025] The terminology used below is only used to describe specific embodiments and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. Hereinafter, the terms "comprises" or "has" and the like are intended to indicate the presence of a feature, number, step, operation, component, part, ingredient, material, or combination thereof described in the specification, but should be understood to not preclude the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, ingredients, materials, or combinations thereof. The " / " used below may be interpreted as "and" or "or" depending on the context.

[0026] In order to clearly express various layers and regions in the drawings, the thickness is shown enlarged or reduced. Similar parts are designated by the same drawing reference numerals throughout the specification. When a part such as a layer, film, region, or plate is said to be "on" or "above" another part throughout the specification, this includes not only cases where it is directly above the other part, but also cases where there is another part in between. Terms such as first, second, etc. may be used throughout the specification to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another. In this specification and the drawings, components having substantially the same functional configuration are referred to by the same reference numerals, and redundant descriptions are omitted.

[0027] Unless otherwise specified herein, when a part such as a layer, film, region, or plate is said to be “on top of” another part, this includes not only cases where it is “directly on top of” the other part, but also cases where there are other parts in between.

[0028] Unless otherwise specified herein, the singular may also include the plural. Furthermore, unless otherwise specified, "A or B" may mean "including A, including B, or including A and B."

[0029] As used herein, “combination thereof” may mean mixtures, laminates, composites, copolymers, alloys, blends, and reaction products of the components.

[0030] Unless otherwise defined herein, the particle size may be the average particle size. In addition, the particle size refers to the average particle size (D50), which means the diameter of particles with a cumulative volume of 50% by volume in a particle size distribution. The average particle size (D50) can be measured by a method well known to those skilled in the art, for example, by measuring with a particle size analyzer, or by measuring with a transmission electron microscope (TEM) photograph or a scanning electron microscope (SEM) photograph. Alternatively, the average particle size (D50) value can be obtained by measuring with a measuring device that utilizes dynamic light-scattering, performing data analysis to count the number of particles for each particle size range, and calculating from the counted number. Alternatively, the average particle size (D50) value can be obtained by measuring with a laser diffraction method. When measuring by laser diffraction, more specifically, after the particles to be measured are dispersed in a dispersion medium, they are introduced into a commercially available laser diffraction particle size measuring device (e.g., Microtrac MT 3000) and irradiated with ultrasonic waves of approximately 28 kHz at an output of 60 W, and the average particle size (D50) based on 50% of the particle size distribution in the measuring device can be calculated.

[0031] In the present disclosure, the "particle diameter" of a particle refers to the average diameter when the particle is spherical, and refers to the average major axis length when the particle is non-spherical. The particle diameter of a particle can be measured using a particle size analyzer (PSA). The "particle diameter" of a particle is, for example, the average particle diameter. The average particle diameter is, for example, the median particle diameter (D50). The median particle diameter (D50) is the size of a particle corresponding to 50% of the cumulative volume, calculated from the side of particles having a small particle size in a size distribution of particles measured by, for example, laser diffraction. The average particle diameter and average major axis length of a particle can be measured using a scanning electron microscope. When the particle size is measured using a scanning electron microscope, it is determined as the average value of 30 or more randomly selected particles having a size of 1 μm or more, excluding fine particles.

[0032] In the present disclosure, “metal” includes both metals and metalloids such as silicon and germanium, in their elemental or ionic states, and “alloy” means a mixture of two or more metals.

[0033] In the present disclosure, “positive electrode active material” means a positive electrode material capable of undergoing lithiation and delithiation, and “negative electrode active material” means a negative electrode material capable of undergoing lithiation and delithiation.

[0034] In the present disclosure, “lithiation” and “lithiating” mean a process of adding lithium to a positive electrode active material or a negative electrode active material, and “delithiation” and “delithiating” mean a process of removing lithium from a positive electrode active material or a negative electrode active material.

[0035] In the present disclosure, “charging” and “charging” mean a process of providing electrochemical energy to a battery, and “discharging” and “discharging” mean a process of removing electrochemical energy from a battery.

[0036] In the present disclosure, “positive electrode” and “cathode” mean an electrode where electrochemical reduction and lithiation occur during a discharge process, and “negative electrode” and “anode” mean an electrode where electrochemical oxidation and delithiation occur during a discharge process.

[0037] Hereinafter, a gel polymer electrolyte for a lithium battery, a lithium battery including the same, and a method for manufacturing the same according to exemplary embodiments are described in more detail.

[0038] A gel polymer electrolyte for a lithium battery comprising a gel polymer and a liquid electrolyte according to an embodiment, wherein the liquid electrolyte comprises a lithium salt and an organic solvent, and the gel polymer is a crosslinked product of i) a first polymerizable monomer having three or more polymerizable functional groups and ii) a second polymerizable monomer selected from among urethane acrylic monomers having two or more functional groups.

[0039] In the present disclosure, the terms “first polymerizable monomer” and “second polymerizable monomer” may be referred to as “first cross-linkable monomer” and “second cross-linkable monomer,” respectively.

[0040] When the gel polymer electrolyte is manufactured in the form of a free-standing film, it is difficult to impregnate the positive electrode, and thus the charge-discharge characteristics may deteriorate when a positive electrode with a high actual loading is used.

[0041] In addition, when manufacturing a gel polymer electrolyte by injecting a liquid electrolyte and a crosslinking agent together and curing, the viscosity of the composition for forming a gel polymer electrolyte may increase depending on the crosslinking agent component, and sufficient positive electrode impregnation may not be achieved.

[0042] However, the gel polymer electrolyte described above can be smoothly impregnated into a positive electrode having a high loading content by appropriately controlling the viscosity of the gel polymer electrolyte forming composition for manufacturing the gel polymer electrolyte. The viscosity of the gel polymer electrolyte forming composition according to one embodiment is 2 to 20 cps. Therefore, a composition having such a viscosity can be well impregnated into a positive electrode having a high loading content. In addition, since the gel polymer is a cross-linked product obtained using the first polymerizable monomer and the second polymerizable monomer described above, the lithium cation and anion interactions are strong. As a result, a lithium battery employing such a gel polymer electrolyte has improved ionic conductivity, cycle life characteristics, and high rate characteristics.

[0043] Gel polymer electrolyte refers to a gel-type semi-solid electrolyte in which liquid is contained in a solid polymer electrolyte. Compared to a pure liquid electrolyte, the resistance increases and the capacity decreases, but stability can be improved.

[0044] The above first polymerizable monomer is a multifunctional acrylic monomer having three or more polymerizable functional groups, and has three or more polymerizable functional groups, for example, three to six. In this way, it has an unsaturated functional group, which is a polymerizable functional group capable of participating in a crosslinking reaction with the second polymerizable monomer, and thus can function as a crosslinking agent. When the multifunctional acrylic first polymerizable monomer has three or more polymerizable functional groups, crosslinking with the second polymerizable monomer occurs, thereby obtaining a gel polymer electrolyte with excellent physical properties.

[0045] The first polymerizable monomer is, for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane ethoxylate triacrylate, trimethylolpropane propoxylate triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol ethoxylate tetraacrylate, dipentaerythritol pentaacrylate, Dipentaerythritol hexaacrylate (DPHA), or a combination thereof.

[0046] The above second polymerizable monomer is a urethane-based compound in the form of an oligomer that can impart elasticity to a gel polymer, and since it has high mechanical strength and elasticity by including a urethane moiety, when it is used as a second polymerizable monomer to form a crosslinked product with the first polymerizable monomer, a gel polymer electrolyte that maintains high mechanical strength and has elasticity can be manufactured.

[0047] The ester (COO) group of the first polymerizable monomer can play a role in holding lithium salt and anions. By utilizing this, when lithium ions move from the positive electrode to the negative electrode during the initial charge, the anions can be induced to move together. As a result, it is possible to induce the presence of more anions at the negative electrode, which results in the formation of a robust film by enriching clustered solvation structures. Here, when the film is a lithium salt and a fluorine-containing borate lithium salt is used, a robust film rich in the anions boron and fluorine can be formed.

[0048] The second polymerizable monomer, together with the first polymerizable monomer, has strong Li+ interaction and anion interaction, so that Li+ ions are also transferred through the polymer chain and anions are trapped, thereby significantly increasing the lithium cation transport rate (Li+ transference number). By introducing such a polymerizable monomer, the ion conductivity of the gel polymer electrolyte is improved, and the lifespan of a lithium battery employing such a gel polymer electrolyte can be increased.

[0049] As a second polymerizable monomer, other monomers containing a polyfunctional functional group having a similar structure to the acrylic monomer containing a urethane group may be additionally mixed and used. As the other monomers containing such polyfunctional functional groups, for example, one or more selected from the group consisting of urethane acrylate methacrylate, urethane epoxy methacrylate, and Arkema's product names Satomer N3DE180 and N3DF230 may be used.

[0050] The gel polymer electrolyte made of a crosslinked product obtained from the first polymerizable monomer and the second polymerizable monomer is Li + Cations such as and PF6 -The interaction with anions such as is very strong. This strong interaction can be confirmed to be caused by the difference in electron density distribution in the DFT simulation.

[0051] When a urethane-containing acrylic monomer is used as a polymerizable monomer, it can act as a diluent in the electrolyte, thereby reducing the viscosity of the composition for forming a gel polymer electrolyte. When the first and second polymerizable monomers used in the present disclosure are used, the viscosity of the gel polymer electrolyte composition can be lowered, thereby ensuring processability. The viscosity of the composition for forming a gel polymer electrolyte is 4 to 10 cps. Therefore, using a composition having such a viscosity can facilitate injection into a battery structure.

[0052] In one embodiment, in addition to an organic solvent that helps dissociation and movement of lithium salts during manufacture of a gel polymer electrolyte, a material that simultaneously transfers lithium ions and anions to the polymer chain is added to concentrate the distribution of lithium ions on the polymer chain, and a material that helps movement within the polymer chain to improve the rate characteristics is added, thereby greatly improving the rate characteristics of the gel polymer electrolyte.

[0053] When making a gel polymer electrolyte, a cross-linking agent capable of polymerization and an initiator that induces polymerization at a certain temperature or higher are usually added to a liquid electrolyte, and the gel polymer electrolyte is manufactured by heat-treating the mixture.

[0054] The above initiator is not particularly limited as long as it is commonly used in the relevant technical field. The initiator may be, for example, benzoin ethyl ether, di-tert-butyl peroxide, dibenzoyl peroxide, t-tert-butyl peroxide, azobisdiisobutyronitrile, 2,2'-azodi(isobutyronitrile), 1,1'-azodi(hexahydrobenzoitrile), 2,2'-azodi(2-methylbutyronitrile), or a combination thereof.

[0055] The content of the above initiator may be used in the range of, for example, 1 to 6 parts by weight, or 1 to 3 parts by weight, based on 100 parts by weight of the total content of the first polymerizable monomer and the second polymerizable monomer. Using the gel-type polymer electrolyte formed in this way, the ionic conductivity can be maintained at a value close to that of the liquid electrolyte, and the gel-type polymer electrolyte inside the positive and negative electrodes can play a role in preventing leakage of the liquid electrolyte. The electrolyte can be trapped in the polymer matrix of the gel-type polymer electrolyte and maintained within the polymer matrix, thereby helping the smooth movement of lithium ions. In addition, the excellent electrochemical properties of the polymer can suppress the electrolyte decomposition reaction within the range of -1 V to 5 V.

[0056] Gel polymer electrolytes are created by trapping a liquid within a polymerized polymer matrix, forming a semi-solid. The cycle life of a gel polymer electrolyte is improved when a monomer with a strong affinity for lithium ions or anions is used. This is because lithium ions move more easily through the polymer chain after polymerization.

[0057] In the gel polymer electrolyte according to an embodiment, the gel polymer is a crosslinked product of i) a first polymerizable monomer having three or more polymerizable functional groups, and ii) a second polymerizable monomer selected from among urethane acrylic monomers having two or more functional groups.

[0058] The COO- functional group of the multifunctional acrylic first polymerizable monomer having three or more polymerizable functional groups contributes to the favorable interaction between lithium ions and anions, and since it has three or more polymerizable functional groups, the crosslinking density of the gel polymer formed therefrom can be increased. A gel polymer electrolyte with improved physical properties can be manufactured using the gel polymer having such an increased crosslinking density.

[0059] The second polymerizable monomer is a compound represented by the following chemical formula 1, a compound represented by the following chemical formula 2, or a combination thereof.

[0060] <Chemical Formula 1>

[0061]

[0062] In chemical formula 1, R a and R b are identical or different, and are substituted or unsubstituted C1-

[0063] C10 is an alkylene group, EG is a residue of ethylene glycol, DEG is a residue of diethylene glycol, TMP is a residue of trimethylolpropane, and n is an integer from 1 to 100.

[0064] <Chemical Formula 2>

[0065]

[0066] In chemical formula 2, each R independently represents a hydrogen atom, a C1-C3 alkyl group, or a combination thereof.

[0067] In the above chemical formula 1, n is an integer from 3 to 80, an integer from 5 to 50, or an integer from 5 to 30. And the substituted alkylene may be an alkylene in which at least one hydrogen is substituted with a C1-C3 alkyl.

[0068] The compound represented by the above chemical formula 1 may include, for example, a compound represented by the following chemical formula 3.

[0069] <Chemical Formula 3>

[0070]

[0071] In chemical formula 3, n1 is an integer from 1 to 100, EG is a residue of ethylene glycol, DEG is a residue of diethylene glycol, and trimethylolpropane is a residue.

[0072] In chemical formula 3, n1 is an integer from 3 to 80, an integer from 5 to 50, or an integer from 5 to 30.

[0073] The compound of the above-described chemical formula 1 and the compound of the above-described chemical formula 3 can be manufactured using the manufacturing method disclosed in Korean Patent Publication No. 10-1326629, and Korean Patent Publication No. 10-1326629 is incorporated herein by reference and cited herein.

[0074] The compound of the above-described chemical formula 1 has an isonate group at the terminal, and the method for producing this compound is described as follows.

[0075] A polyester polyol is prepared by mixing C1-C10 aliphatic dicarboxylic acids, diethylene glycol, ethylene glycol, and trimethylolpropane, adding a reaction catalyst, and heat-treating the mixture. Here, the polyester polyol is obtained through an ester reaction between a C1-C10 aliphatic dicarboxylic acid and the alcohols diethylene glycol, ethylene glycol, and trimethylolpropane. Titanium isopropoxide is used as the reaction catalyst.

[0076] By adding isocyanatoethyl methacrylate to the above polyester polyol, a reaction between the polyester polyol and isocyanatoethyl methacrylate occurs to form polyurethane, thereby producing a compound of chemical formula 1 having isocyanate at both ends.

[0077] C1-C10 aliphatic dicarboxylic acids include diadipic acid, succinic acid, sebacic acid, or combinations thereof.

[0078] The reaction of the polyester polyol and isocyanatoethyl methacrylate forms polyurethane by reacting at least a portion of the hydroxyl groups of the polyester polyol with isocyanatoethyl methacrylate. Monomethyl ether hydroquinone as a polymerization inhibitor, butylated hydroxy toluene as an antioxidant, and dibutyl tin dilaulate as a reaction catalyst may be added to the reaction of the polyester polyol and isocyanatoethyl methacrylate.

[0079] The weight average molecular weight of the compound represented by the above chemical formula 1 or 3 may be in the range of 10,000 to 100,000. The range of n in chemical formula 1 and chemical formula 3 may be used to have such a weight average molecular weight.

[0080] Since the polyfunctional acrylic monomer containing a urethane group has high mechanical strength and elasticity by including a urethane moiety, when forming a copolymer structure with a polyfunctional block copolymer, a gel polymer electrolyte having high mechanical strength and elasticity can be manufactured.

[0081] Other monomers containing a multifunctional functional group having a similar structure to the polyfunctional acrylic monomer containing a urethane group may be additionally mixed and used. As the other monomers containing such a multifunctional functional group, for example, one or more selected from the group consisting of urethane acrylate methacrylate, urethane epoxy methacrylate, and Arkema's product names Satomer N3DE180 and N3DF230 may be used.

[0082] The weight ratio of the first polymerizable monomer and the second polymerizable monomer is 10:1 to 1:10, 9:1 to 1:9, 9:1 to 1:1, 7:1 to 1:1, 5:1 to 1:1, or 3:1 to 1:1. When the weight ratio of the first polymerizable monomer and the second polymerizable monomer is within the above range, a lithium battery having excellent effects of improving ion conductivity and increasing lifespan can be manufactured.

[0083] The weight average molecular weight of the first polymerizable monomer is 500 to 50,000, 1000 to 45,000. If the weight average molecular weight of the first polymerizable monomer is less than the above range, the density of crosslinking points within the molecular structure of the polymer after crosslinking may be too high, preventing free movement of the lithium salt. If the weight average molecular weight is greater than the above range, the density of crosslinking points within the molecular structure of the polymer after crosslinking may be too low, reducing the electrolyte blocking ability.

[0084] The weight average molecular weight of the second polymerizable monomer according to one embodiment is 400 to 100,000, or 10,000 to 100,000. The weight average molecular weight of the second polymerizable monomer according to another embodiment is 400 to 40,000. If the weight average molecular weight of the second polymerizable monomer is smaller than the above range, the density of crosslinking points within the molecular structure of the polymer after crosslinking may be too high, so that the movement of the lithium salt may not be free, and if it is larger than the above range, the density of crosslinking points within the molecular structure of the polymer after crosslinking may be too low, so that the electrolyte blocking ability may be reduced. When the weight average molecular weight of the second polymerizable monomer is within the above range, a lithium battery having excellent effects of improving ion conductivity and increasing lifespan can be manufactured.

[0085] The gel polymer electrolyte according to the present invention has excellent ionic conductivity and improved mechanical properties compared to a liquid electrolyte, thereby more effectively suppressing volume changes in a lithium battery during charge and discharge.

[0086] The gel polymer electrolyte can effectively prevent deterioration of a lithium battery by suppressing side reactions with the lithium metal layer during charge and discharge of the lithium battery. For example, when charging and discharging a lithium battery, a solid electrolyte interphase (SEI) layer may be formed between a new gel polymer electrolyte and a precipitated lithium metal layer. By modifying the composition of the SEI layer to have an increased content of lithium salt decomposition products, side reactions between the gel polymer electrolyte and the lithium metal layer can be more effectively suppressed. In addition, the gel polymer electrolyte and / or the modified SEI layer can effectively prevent internal short circuits of the lithium battery by more effectively suppressing the growth of lithium dendrites from the lithium metal layer.

[0087] The content of the liquid electrolyte is 90 to 99 parts by weight, or 90 to 96 parts by weight, based on 100 parts by weight of the total weight of the gel polymer electrolyte, and the content of the gel polymer is 1 to 10 parts by weight, 2 to 10 parts by weight, 3 to 10 parts by weight, or 4 to 10 parts by weight, based on 100 parts by weight of the total weight of the gel polymer electrolyte. When the liquid electrolyte and the gel polymer in the gel polymer electrolyte are within the above ranges, a gel polymer electrolyte with improved ionic conductivity and physical properties can be manufactured, and by using such a gel polymer electrolyte, a lithium battery with improved high-rate characteristics and lifespan can be manufactured.

[0088] The polymer electrolyte according to one embodiment may further include at least one selected from an ionic liquid and a polymer ionic liquid, and the ionic liquid may include at least one selected from the group consisting of diethylmethylammonium trifluoromethanesulfonate ([dema][TfO]), dimethylpropylammonium trifluoromethanesulfonate ([dmpa][TfO]), N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide ([DEMA][TFSI]), N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide ([PP13][TFSI]), N-butyl-N-methyl pyrrolidinium bis(trifluoromethanesulfonyl)imide ([Py14][TFSI]), and methylpropylpiperidinium trifluoromethanesulfonyl imide ([mpp][TFSI]). there is.

[0089] The gel polymer solid electrolyte according to one embodiment may further contain a nitrile compound. The nitrile compound is at least one selected from the group consisting of succinonitrile, adiponitrile, pimelonitrile, suberonitrile, and sebaconitrile, and the content of the nitrile compound is 1 to 5 parts by weight based on 100 parts by weight of the total weight of the gel polymer electrolyte. In addition, the nitrile compound is a compound having a melting point of 30°C or higher, is a solid or solid-like substance at room temperature, has a solid state at room temperature, has excellent stability, and has excellent ionic conductivity. Examples of the nitrile compound include succinonitrile and butyronitrile.

[0090] The liquid electrolyte contains a lithium salt and a non-aqueous organic solvent.

[0091] The above lithium salt is a substance that dissolves in an organic solvent and acts as a source of lithium ions in the battery, enabling the basic operation of a lithium secondary battery and promoting the movement of lithium ions between the positive and negative electrodes. Representative examples of lithium salts include LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiAlO2, LiAlCl4, LiPO2F2, LiCl, LiI, LiN(SO2C2F5)2, Li(FSO2)2N (lithium bis(fluorosulfonyl)imide (LiFSI), Li(SO2CF3) (LiTFSI), LiC4F9SO3, LiN(C x F 2x+1 SO2)(C y F 2y+1 SO2) (wherein x and y are integers from 1 to 20), LiSO3CF3 (lithium trifluoromethane sulfonate), LiSO3C2F5 (lithium tetrafluoroethane sulfonate), LiSO3C2F4 (lithium tetrafluoroethanesulfonate), lithium difluorobis(oxalato)phosphate (LiDFOB), lithium bis(oxalato)borate (LiBOB), or a combination thereof. The concentration of the lithium salt is, for example, 0.01 M to 5.0 M.

[0092] In another embodiment, the lithium salt in the gel polymer electrolyte may include a first lithium salt and a second lithium salt. By including the first lithium salt and the second lithium salt in the gel polymer electrolyte, the ionic conductivity of the gel polymer electrolyte may be improved.

[0093] The first and second lithium salts are borate-based lithium salts. Compared to phosphorus-based lithium salts, borate-based lithium salts exhibit improved high-temperature stability and can suppress the production of hydrofluoric acid (HF). By including borate-based lithium salts in the first and second lithium salts, the high-temperature cycling characteristics of lithium batteries can be improved.

[0094] The first lithium salt and the second lithium salt may, for example, independently be fluorine-containing borate-based lithium salts. By including the fluorine-containing borate-based lithium salt in the first lithium salt and the second lithium salt, the composition of the SEI layer formed during charge and discharge of the lithium battery can be more effectively modified. For example, by increasing the fluorine (F) content of the SEI layer, the structural stability of the SEI layer can be increased, and side reactions with organic solvents can be effectively suppressed.

[0095] The first lithium salt and the second lithium salt may be, for example, a non-cyclic borate lithium salt and a cyclic borate lithium salt. Since the first lithium salt is a non-cyclic lithium salt, the ionic conductivity of the electrolyte can be more effectively increased. Since the second lithium salt is a cyclic lithium salt, the aggregation of anions is increased, so that it can more effectively participate in the composition modification of the SEI layer, and the high-temperature stability of the electrolyte can be improved.

[0096] Fluorine-containing borate lithium salts may include, for example, LiBF4, LiBF3(C2F5), compounds represented by chemical formulae 1-1 to 1-12, or combinations thereof.

[0097] <Chemical Formula 1-1> <Chemical Formula 1-2>

[0098]

[0099] <Chemical Formula 1-3> <Chemical Formula 1-4>

[0100]

[0101] <Chemical Formula 1-5> <Chemical Formula 1-6>

[0102]

[0103] <Chemical Formula 1-7> <Chemical Formula 1-8>

[0104]

[0105] <Chemical Formula 1-9> <Chemical Formula 1-10>

[0106]

[0107] <Chemical Formula 1-11> <Chemical Formula 1-12>

[0108]

[0109] The first lithium salt may include, for example, LiBF4, and the second lithium salt may include a compound selected from compounds represented by chemical formulae 1-1 to 1-12.

[0110] The first lithium salt may include LiBF4, and the second lithium salt may include lithium difluoro(oxalato)borate (LiDFOB) of chemical formula 1-1, for example.

[0111] The content ratio of the first lithium salt and the second lithium salt may be, for example, 1:9 to 9:1, 3:7 to 7:3, or 4:6 to 6:4. When the first lithium salt and the second lithium salt have a content ratio within this range, the gel polymer electrolyte can simultaneously provide excellent ionic conductivity and the formation of a structurally stable SEI layer. The content ratio of the first lithium salt and the second lithium salt may be, for example, a molar ratio.

[0112] According to one embodiment, the mixing weight ratio of lithium difluorodioxalatoborate (LiDFOB) and lithium tetrafluoroborate (LiBF4) is 1:2 to 1:0.3 or 1:1.5 to 1:0.5. When the concentration of the lithium salt and the mixing weight ratio of LiDFOB and LiBF4 are within the above ranges, a lithium battery having improved performance can be manufactured.

[0113] The concentration of the lithium salt in the gel polymer electrolyte is 0.01 to 5.0 M, for example, 0.05 to 5.0 M, for example, 0.1 to 5.0 M, 0.1 to 3 M, 0.1 to 2.4 M, 0.3 to 1.5 M, 0.5 to 1.2 M, or 0.8 to 1.2 M. When the concentration of the lithium salt is within the above range, further improved lithium battery characteristics can be obtained.

[0114] The organic solvent may be at least one selected from a carbonate compound, an ester compound, an ether compound, a nitrile compound, and a ketone compound.

[0115] As carbonate compounds, ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), etc. can be used.

[0116] As ester compounds, methyl propionate, ethyl propionate, ethyl butyrate, methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, gamma butyrolactone, decanolide, gamma valerolactone, mevalonolactone, caprolactone, etc. can be used; as ether compounds, dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, etc. can be used; as ketone compounds, cyclohexanone, etc. can be used; and as nitrile compounds, acetonitrile (AN), succinonitrile (SN), adiponitrile, butyronitrile, etc. can be used.

[0117] Examples of ether compounds that can be used include dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxolane, and other dioxolanes. In addition, examples of ketone compounds that can be used include cyclohexanone. Examples of alcohol solvents that can be used include ethyl alcohol, isopropyl alcohol, and the like. Other solvents that can be used include nitriles such as R-CN (where R is a linear, branched, or cyclic hydrocarbon group having 2 to 20 carbon atoms and may include a double bond, an aromatic ring, or an ether group); amides such as dimethylformamide; and phosphates such as ethylmethoxyethyl sulfolane, ethylmethyl sulfolane, sulfolane, and trimethyl phosphate.

[0118] The above non-aqueous organic solvents can be used alone or in combination of two or more.

[0119] In addition, when using a carbonate compound, a cyclic carbonate and a chain carbonate can be mixed and used, and the cyclic carbonate and the chain carbonate can be mixed in a volume ratio of 1:1 to 1:9.

[0120] Other solvents that can be used in the electrolyte include, but are not limited to, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, tetrahydrofuran, etc., and any organic solvent that can be used in the relevant technical field can be used. For example, the organic solvent may include a mixed solvent of 50 to 95 vol% of a chain carbonate and 5 to 50 vol% of a cyclic carbonate, for example, a mixed solvent of 70 to 95 vol% of a chain carbonate and 5 to 30 vol% of a cyclic carbonate. For example, the organic solvent may be a mixed solvent of three or more organic solvents.

[0121] According to another embodiment, when using a carbonate compound, a cyclic carbonate and a chain carbonate may be mixed and used, and the cyclic carbonate and the chain carbonate may be mixed in a volume ratio of 1:1 to 1:9. And according to one embodiment, the organic solvent includes a carbonate compound, and the carbonate compound includes fluoroethylene carbonate (FEC) and diethyl carbonate (DEC), and the mixing weight ratio of the FEC and DEC is 1:10 to 1:1, 1:8 to 1:1, 1:5 to 1:1, or 1:3 to 1:1. By using such an organic solvent, a gel polymer electrolyte with improved ionic conductivity can be manufactured. Therefore, a lithium battery with improved initial capacity and lifespan characteristics can be manufactured.

[0122] According to one embodiment, the electrolyte includes a nitrile compound, a lithium salt, and a carbonate compound, wherein the lithium salt includes lithium difluorodioxalatoborate (LiDFOB) and lithium tetrafluoroborate (LiBF4).

[0123] The nitrile compound is, for example, butyronitrile, valeronitrile, propionitrile, acetonitrile, or a combination thereof. The content of the nitrile compound is 3 wt% to 45 wt% based on 100 wt% of the total weight of the gel polymer electrolyte.

[0124] A gel polymer electrolyte is a crosslinked product of a precursor composition for forming a gel polymer electrolyte. The precursor composition for forming a gel polymer electrolyte includes, for example, a first polymerizable monomer, a second polymerizable monomer, a lithium salt, and an organic solvent. By crosslinking this precursor composition for forming a gel polymer electrolyte, a gel polymer electrolyte is obtained. By crosslinking the first polymerizable monomer and the second polymerizable monomer, a first polymer including repeating units derived from the first polymerizable monomer and the second polymerizable monomer is obtained. The content of the first polymerizable monomer and the second polymerizable monomer may be, for example, 0.1 to 10 wt%, 0.2 to 8 wt%, 0.5 to 6 wt%, 1 to 5 wt%, or 2 to 4 wt% based on the total weight of the precursor composition for forming a gel polymer electrolyte. A precursor composition for forming a gel polymer electrolyte can form a stable gel polymer electrolyte by including the first cross-linking monomer within this range. If the content of the first polymerizable monomer and the second polymerizable monomer is too low, it may be difficult to form a gel. If the content of the first polymerizable monomer and the second polymerizable monomer is too high, the gel polymer electrolyte may be excessively hardened, which may cause cracks or the like to occur within the gel polymer electrolyte during the charge / discharge process.

[0125] The crosslinking method of the precursor composition for forming a gel polymer electrolyte is not particularly limited, and may be crosslinked, for example, by heat, ultraviolet rays, etc. Thermal crosslinking may be used from the viewpoint of manufacturing efficiency. The precursor composition for forming a gel polymer may include, for example, a thermal initiator. The thermal initiator is not limited to, for example, t-amyl peroxide, azobis, etc., and any thermal initiator used in the art may be used. The content of the thermal initiator may be 0.1 wt% or less or 0.05 wt% or less based on the total weight of the precursor composition for forming a gel polymer electrolyte. The crosslinked product of the precursor composition for forming a gel polymer electrolyte may be, for example, a result of heat treatment at 60 to 90°C for 1 to 3 hours. The heat treatment conditions may be adjusted depending on the type of thermal initiator used.

[0126] The gel polymer electrolyte may be present within the separator and at the interface between the separator and the positive electrode. The gel polymer electrolyte may be contained within a portion of the positive electrode.

[0127] The above gel polymer electrolyte-containing separator can be manufactured separately in the form of a self-supporting membrane, and a lithium battery can be manufactured by positioning the gel polymer electrolyte-containing separator on top of a negative electrode current collector and a protective layer, and placing the positive electrode on top of the separator. Here, the protective layer can be omitted.

[0128] Alternatively, a lithium battery having a separator containing a gel polymer electrolyte can be manufactured by forming a battery structure by positioning a negative electrode current collector and a protective layer and arranging a separator and a positive electrode thereon, injecting a composition for forming a gel polymer electrolyte into the battery structure, and heat-treating the composition.

[0129] According to another aspect, a lithium battery is provided, which includes a positive electrode, a negative electrode current collector, and an electrolyte layer disposed between the positive electrode and the negative electrode current collector, wherein the electrolyte layer includes the gel polymer electrolyte described above.

[0130] The ionic conductivity of the above gel polymer electrolyte at 25°C and 1 atm is 0.44 mS / cm or more, and the ionic conductivity at 45°C and 1 atm is 0.63 mS / cm or more. Using a gel polymer electrolyte having such ionic conductivity can provide a lithium battery with improved cycle characteristics.

[0131] The above lithium battery may further include a separator on the negative electrode current collector. The separator may contain a gel polymer electrolyte.

[0132] A lithium battery may have a structure including a positive electrode; a negative electrode current collector; a separator disposed between the positive electrode and the negative electrode current collector; and a gel-type polymer electrolyte disposed on top of the separator. The gel-type polymer electrolyte may be disposed between the separator and the positive electrode.

[0133] The negative electrode active material layer or protective layer may be disposed between the negative electrode current collector and the separator, or the negative electrode active material layer or protective layer may be absent (free).

[0134] Figure 1 illustrates a laminated structure of a lithium battery according to an embodiment. The lithium battery is, for example, a lithium metal battery.

[0135] A lithium battery (1) comprises a negative electrode (20) including a negative electrode collector (21), and the negative electrode (20) has a structure in which an electrolyte layer (30) is disposed between the negative electrode collector (21) and the positive electrode (10). In the negative electrode (20), a negative electrode active material layer is absent. Although not shown in Fig. 1, a protective layer may be formed on the negative electrode collector (21).

[0136] The electrolyte layer (30) contains a gel polymer electrolyte. The electrolyte layer (30) may further include a separator. The separator may include a porous substrate or the porous substrate and a coating layer formed thereon.

[0137] The positive electrode (10) contains a positive electrode active material layer (12) and a positive electrode current collector (11). The separator (30) contains a gel polymer electrolyte.

[0138] When the electrolyte layer includes a porous substrate, a gel polymer electrolyte may be disposed between the porous substrate and the anode. The porous substrate may contain a gel polymer electrolyte.

[0139] Although not shown in FIGS. 1 and 2, a gel polymer electrolyte may be contained in the positive electrode (10).

[0140] A lithium metal layer (22) may be further disposed between the negative electrode current collector (21) and the electrolyte layer (30), as shown in Fig. 2. The lithium metal layer corresponds to the negative electrode active material layer. The lithium metal layer may include lithium metal or a lithium alloy.

[0141] A protective layer may be positioned between the lithium metal layer and the electrolyte layer. The protective layer is a lithium-ion conductive buffer layer that prevents the separator containing the gel polymer electrolyte from contacting the lithium metal layer as an electrolyte layer. It also inhibits the formation and growth of lithium dendrites positioned on the negative electrode current collector.

[0142] The lithium metal layer can also be placed during battery assembly.

[0143] The binder of the above protective layer may be a vinylidene fluoride-hexafluoropropylene (VDF-HFP) copolymer, polyethylene oxide, polypropylene oxide, polydimethylsiloxane, polyacrylonitrile, polymethyl(meth)acrylate, polyvinyl chloride, polyvinylidene fluoride, polyvinylidene fluoride-co-hexafluoropropylene, polyethyleneimine, polyphenylene terephthalamide, polymethoxypolyethylene glycol(meth)acrylate, poly2-methoxy ethyl glycidyl ether, or a combination thereof.

[0144] The binder of the above protective layer may include a crosslinked polymer of a first polymer and a second polymer, wherein the first polymer containing a hydroxyl group and the second polymer having a crosslinkable functional group are crosslinked reaction products.

[0145] The weight ratio of the first polymer and the second polymer is 50:50 to 99:1, and the second polymer is at least one selected from among fluorinated polyamic acid and fluorinated polyimide having a carboxyl group.

[0146] The protective layer is dense, increasing its density and strength, allowing free lithium ion movement and enhancing lithium ion transport, thereby improving lithium electrodeposition characteristics. Consequently, ionic conductivity is improved, thereby enhancing the high-rate characteristics of lithium batteries. Furthermore, by positioning the protective layer on the negative electrode active material layer, side reactions between the negative electrode active material layer and the electrolyte can be effectively blocked and suppressed.

[0147] The protective layer may further comprise an inorganic material. The inorganic material is selected from the group consisting of silica (SiO2), alumina (Al2O3), titanium oxide (TiO2), lithium titanium oxide (LiTiO2), barium titanium oxide (BaTiO2), lithium alumina (LiAlO2), and zeolite, or a mixture thereof.

[0148] When a protective layer according to an embodiment of the present invention is present on the surface of a negative electrode active material layer including lithium metal, the generation and / or growth of lithium dendrites on the negative electrode current collector can be effectively prevented. In addition, the cycle characteristics and stability of a negative electrode including the above-described protective layer and a lithium battery employing the same are improved.

[0149] The above hydroxyl group-containing first polymer is carboxymethyl cellulose (CMC); polyvinyl alcohol (PVA); Vinyl acetate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 2-hydroxyethylene glycol (meth)acrylate, 2-hydroxypropylene glycol (meth)acrylate, acrylic acid, methacrylic acid, 2-(meth)acryloyloxy acetic acid, 3-(meth)acryloyloxy propyl acid, 4-(meth)acryloyloxy butyric acid, itaconic acid, maleic acid, 2-isocyanatoethyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, A polymerization reaction product of one or more monomers selected from among 4-isocyanatobutyl (meth)acrylate, (meth)acrylamide, ethylene di(meth)acrylate, diethylene glycol (meth)acrylate, triethylene glycol di(meth)acrylate, trimethylene propane tri(meth)acrylate, trimethylene propane triacrylate, 1,3-butanediol (meth)acrylate, 1,6-hexanediol di(meth)acrylate, allyl acrylate, and N-vinyl caprolactam, or a hydrolyzate thereof, may be mentioned.

[0150] The first polymer may be polyvinyl alcohol (PVA). For example, polyvinyl alcohol may be a hydrolyzate obtained by hydrolyzing polyvinyl acetate with an alkali.

[0151] The degree of saponification of polyvinyl alcohol is 60 to 99%, 70 to 95%, 75 to 90% or 80

[0152] The degree of saponification of polyvinyl alcohol may be 85 to 90%. In the above saponification range, the properties of the protective layer may be further improved.

[0153] The weight average molecular weight of the first polymer may be 10,000 to 500,000 Dalton, 10,000 to 500,000 Dalton, 10,000 to 400,000 Dalton, 10,000 to 300,000 Dalton, 10,000 to 200,000 Dalton, 50,000 to 150,000 Dalton, 70,000 to 100,000 Dalton, or 80,000 to 100,000 Dalton. The physical properties of the protective layer may be further improved within the weight average molecular weight range of the first polymer.

[0154] The protective layer may further include a second polymer having a functional group capable of crosslinking with the first polymer containing a hydroxyl group. In this case, the protective layer further includes a crosslinked polymer of the first polymer and the second polymer.

[0155] The second polymer comprises at least one selected from among fluorinated polyamic acid and fluorinated polyimide having a carboxyl group.

[0156] The above polyamic acid is represented by the following chemical formula 4 or 5, and the above polyimide is a polymer represented by the following chemical formula 6 or 7.

[0157] [Chemical Formula 4]

[0158]

[0159] [Chemical Formula 5]

[0160]

[0161] [Chemical Formula 6]

[0162]

[0163] [Chemical Formula 7]

[0164]

[0165] In chemical formulas 4 to 7, n and m are each mole fractions within the repeating unit, and 0 <n≤1, 0≤m<1, n+m=1이다.

[0166] For example, in the second polymer, a repeating unit including a crosslinking group and a crosslinking group

[0167] The mole fraction of repeating units that do not contain each other is 0 <n≤0.5, 0.5≤m<1 및 n+m=1일 수 있다. 예를 들어, 상기 제2 고분자에서 가교기를 포함하는 반복단위와 가교기를 포함하지 않는 반복단위의 몰분율이 각각 0.1≤n≤0.4, 0.6≤m≤0.9 및 n+m=1일 수 있다. 예를 들어, 상기 제2 고분자에서 가교기를 포함하는 반복단위와 가교기를 포함하지 않는 반복단위의 몰분율이 각각 0.15≤n≤0.35, 0.65≤m≤0.85 및 n+m=1일 수 있다. 예를 들어, 상기 제2 고분자에서 가교기를 포함하는 반복단위와 가교기를 포함하지 않는 반복단위의 몰분율이 각각 0.2≤n≤0.3, 0.7≤m≤0.8 및 n+m=1일 수 있다. 상기 몰분율 범위에서 더욱 향상된 물성을 제공할 수 있다.

[0168] For example, the second polymer may be a random copolymer. For example, the above

[0169] The second polymer may be a block copolymer.

[0170] The weight average molecular weight of the second polymer may be 10,000 to 1,200,000 Dalton, 10,000 to 1,100,000 Dalton, 10,000 to 1,000,000 Dalton, 10,000 to 500,000 Dalton, 100,000 to 500,000 Dalton, 100,000 to 400,000 Dalton, for example, 100,000 to 300,000 Dalton. The physical properties of the protective layer may be further improved within the weight average molecular weight range of the first polymer.

[0171] In the above protective layer, the weight ratio of the first polymer and the second polymer containing a hydroxyl group included in the third polymer may be 99:1 to 50:50, 95:5 to 55:45, 95:5 to 60:40, 95:5 to 65:35, or 90:10 to 70:30. In the above range of the weight ratio of the first polymer to the second polymer, the physical properties of the protective layer may be further improved.

[0172] The hydroxyl groups of the first polymer and the carboxyl groups of the second polymer react with each other to form an ester bond, thereby forming a third polymer crosslinked with the first and second polymers. The formation of the third polymer enhances the stability of the protective layer, and in the case of halogen groups such as fluorine functional groups, it can improve interfacial stability by reducing the formation of irreversible lithium inclusions.

[0173] The protective layer according to an embodiment includes a crosslinked polymer of polyvinyl alcohol and polyamic acid. The polyamic acid is, for example, a polymer represented by the chemical formula 4 or 5 described above.

[0174] In another embodiment, the crosslinked polymer of the protective layer is a crosslinked polymer of polyvinyl alcohol and fluorinated polyimide (PVA / PI-f). The fluorinated polyimide is a polymer represented by the chemical formula 6 or 7 described above.

[0175] The above protective layer may contain a polar functional group binder and may be free of lithium salt.

[0176] The protective layer may further contain a lithium salt, and when containing a lithium salt, excellent ionic conductivity of the protective layer can be secured. The lithium salt may be one or more of materials such as LiSCN, LiN(CN)2, LiClO4, LiBF4, LiAsF6, LiPF6, LiCF3SO3, LiC(CF3SO2)3, LiC(FSO2)3, LiN(SO2C2F5)2, LiN(SO2CF3)2, LiN(SO2F)2, LiSbF6, LiPF3(CF2CF3)3, LiPF3(CF3)3, and LiB(C2O4)2.

[0177] In the negative electrode according to an embodiment, the lithium metal layer includes a lithium metal foil, a lithium metal powder, a lithium alloy foil, a lithium alloy powder, or a combination thereof, wherein the lithium alloy contains lithium and a first metal.

[0178] The lithium metal of the lithium metal foil and lithium metal powder may include, for example, lithium metal foil, lithium alloy foil, or a combination thereof. The lithium alloy contains lithium and a first metal, wherein the first metal is indium (In), silicon (Si), gallium (Ga), tin (Sn), aluminum (Al), titanium (Ti), zirconium (Zr), niobium (Nb), germanium (Ge), antimony (Sb), bismuth (Bi), gold (Au), platinum (Pt), palladium (Pd), magnesium (Mg), silver (Ag), zinc (Zn), nickel, iron, cobalt, chromium, cesium, sodium, potassium, calcium, yttrium, bismuth, tantalum, hafnium, barium, vanadium, strontium, lanthanum, or a combination thereof.

[0179] Lithium alloys are alloys of lithium and other metals that can be alloyed with lithium, such as lithium-silver alloys, lithium-zinc alloys, lithium-magnesium alloys, and lithium-tin alloys. The negative electrode active material layer including a lithium metal foil may be, for example, a lithium metal layer. The negative electrode active material layer including a lithium alloy foil may be, for example, a lithium alloy layer. The negative electrode active material layer including lithium metal powder and / or lithium alloy powder may be introduced by coating a slurry including lithium powder and a binder onto a negative electrode current collector. The binder may be, for example, a fluorine-based binder such as polyvinylidene fluoride (PVDF). The negative electrode active material layer may not include a carbon-based negative electrode active material. Therefore, the negative electrode active material layer may be formed of a metal-based negative electrode active material.

[0180] The thickness of the lithium metal layer may be, for example, 1 μm to 50 μm, 1 μm to 30 μm, or 10 μm to 30 μm, or 10 μm to 80 μm. When the lithium metal layer has a thickness in this range, the cycle characteristics and life characteristics of the lithium battery can be further improved.

[0181] The thickness of the lithium metal layer (23) may be, for example, smaller than the thickness of the electrolyte layer (30). The thickness of the lithium metal layer (23) may be, for example, 70% or less, 60% or less, 50% or less, 40% or less, or 30% or less of the thickness of the electrolyte layer (30). The thickness of the lithium metal layer (23) may be, for example, 1 to 70%, 1 to 60%, 1 to 50%, 1 to 40%, or 1 to 30% of the thickness of the electrolyte layer (30). Since the thickness of the lithium metal layer (23) is smaller than the thickness of the electrolyte layer (30), volume change during charge and discharge of the lithium battery (1) can be suppressed. As a result, deterioration due to volume change of the lithium battery (1) can be suppressed.

[0182] The thickness of the lithium metal layer (23) may be, for example, smaller than the thickness of the positive electrode active material layer (12). The thickness of the lithium metal layer (23) may be, for example, 70% or less, 60% or less, 50% or less, 40% or less, or 30% or less of the thickness of the positive electrode active material layer (12). The thickness of the lithium metal layer (23) may be, for example, 1 to 70%, 1 to 60%, 1 to 50%, 1 to 40%, or 1 to 30% of the thickness of the positive electrode active material layer (12). Since the thickness of the lithium metal layer (23) is smaller than the thickness of the positive electrode active material layer (30), volume change during charge and discharge of the lithium battery (1) can be suppressed. As a result, deterioration due to volume change of the lithium battery (1) can be suppressed.

[0183] In the XPS analysis of the surface of the lithium metal layer (23), for example, the peak intensity derived from the fluorine (F) element may be greater than the peak intensity derived from the oxygen (O) element. In the XPS analysis of the surface of the lithium metal layer (23), for example, the peak intensity derived from the fluorine (F) element may be more than 100%, 105% or more, 110% or more, or 120% or more of the peak intensity derived from the oxygen (O) element. In the XPS analysis of the surface of the lithium metal layer (23), for example, the peak intensity derived from the fluorine (F) element may be more than 100% to 200%, 105% to 200%, 110% to 200%, or 120% to 200% of the peak intensity derived from the oxygen (O) element. The structural stability of the SEI layer formed on the surface of the lithium metal layer (23) may be improved by mainly including an inorganic compound containing fluorine (F). As a result, the cycle characteristics of the lithium battery (1) can be improved. In contrast, when the SEI layer formed on the surface of the lithium metal layer (23) mainly includes an organic compound containing oxygen (O), the structural stability of the SEI layer can be reduced. The peak derived from the fluorine (F) element can be, for example, a peak derived from the fluorine (F) 1s orbital. The peak derived from the oxygen (O) element can be, for example, a peak derived from the oxygen (O) 1s orbital.

[0184] After assembling the lithium battery (1), a lithium metal layer (23) is deposited by charging, and since the lithium metal layer (23) is not included during the assembly of the lithium battery (1), the energy density of the lithium battery (1) increases. When the lithium metal layer (23) is additionally disposed by charging after assembling the lithium battery (1), the region between the negative electrode (20), i.e., the negative electrode current collector (21), and the electrolyte layer (30) is a Li-free region that does not include lithium (Li), for example, in the initial state of the lithium battery (1) or in the state after complete discharge.

[0185] The particle size of the lithium powder may be, for example, 0.1 ㎛ to 3 ㎛, 0.1 ㎛ to 2 ㎛, or 0.1 ㎛ to 2 ㎛. When the lithium powder has a thickness in this range, the life characteristics of the lithium battery can be further improved.

[0186] The cathode may further include a cathode active material layer.

[0187] The above negative active material layer is a carbon-based compound; a carbon-based material; and a first metal.

[0188] A composition comprising one or more selected mixtures; one or more composites selected from a carbonaceous material and a first metal; or a combination thereof, wherein the carbonaceous material comprises amorphous carbon, and the average particle size of the amorphous carbon is from 10 nm to 100 nm. The carbonaceous material comprises carbon black, carbon nanotubes, carbon nanofibers, fullerenes, activated carbon, carbon fibers, or a combination thereof.

[0189] The first metal is indium (In), silicon (Si), gallium (Ga), tin (Sn), aluminum (Al), titanium (Ti), zirconium (Zr), niobium (Nb), germanium (Ge), antimony (Sb), bismuth (Bi), gold (Au), platinum (Pt), palladium (Pd), magnesium (Mg), silver (Ag), zinc (Zn), nickel, iron, cobalt, chromium, cesium, sodium, potassium, calcium, yttrium, bismuth, tantalum, hafnium, barium, vanadium, strontium, lanthanum, or a combination thereof.

[0190] A lithium metal layer may be further disposed between the negative electrode current collector and one surface of the protective layer.

[0191] There is. A lithium metal layer can be further disposed on the other surface opposite to the one surface of the above protective layer.

[0192] The thickness of the protective layer is 1 to 10 μm, 2 to 8 μm, or 3 to 5 μm.

[0193] When the thickness of the protective layer is within the above range, the internal resistance increases, and the energy density of the lithium battery is improved without decreasing, and the high-rate characteristics and life characteristics are improved.

[0194] In a lithium battery according to one embodiment, the electrolyte layer may further contain an electrolyte. The electrolyte may be a liquid electrolyte, a solid electrolyte, a gel electrolyte, or a combination thereof.

[0195] The above solid electrolyte includes an oxide-based solid electrolyte, a sulfide-based solid electrolyte, a polymer solid electrolyte, or a combination thereof. A gel electrolyte may have a gel state, for example, without including a polymer.

[0196] The above gel electrolyte comprises a polymer gel electrolyte. The positive electrode comprises a positive electrode current collector and a positive electrode active material layer, and at least one of the positive electrode current collector and the negative electrode current collector comprises a base film and a metal layer disposed on one or both sides of the base film, and the base film comprises a polymer, and the polymer comprises polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polybutylene terephthalate (PBT), polyimide (PI), or a combination thereof.

[0197] The above metal layer includes indium (In), copper (Cu), magnesium (Mg), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), lithium (Li), or an alloy thereof.

[0198] The thickness of the negative electrode active material layer may be, for example, 0.1 ㎛ to 500 ㎛, 1 ㎛ to 500 ㎛, or 10 ㎛ to 500 ㎛, but is not necessarily limited to this range and may be adjusted according to the required shape, capacity, etc. of the lithium battery. When the thickness of the negative electrode active material layer is within the above range, the cycle characteristics are improved without lowering the energy density of the lithium battery.

[0199] A lithium battery according to an embodiment does not include a negative electrode active material layer disposed between a negative electrode current collector (21) and a protective layer. An anode not including a negative electrode active material layer may include a negative electrode active material layer by plating lithium metal between a negative electrode current collector (21) and a protective layer by charging after being introduced into a lithium battery together with a positive electrode and an electrolyte. The negative electrode active material layer may be a lithium plating layer (plated lithium layer).

[0200] Lithium batteries may further include a separator.

[0201] The pore diameter of the separator is generally 0.01 to 10 μm, and the thickness can generally be 5 to 20 μm. Examples of such separators include sheets or non-woven fabrics made of olefin-based polymers such as polypropylene, glass fiber, or polyethylene. When a solid polymer electrolyte is used as the electrolyte, the solid polymer electrolyte may also function as the separator.

[0202] Among the above separation membranes, specific examples of olefin-based polymers include polyethylene, polypropylene, or a multilayer membrane of two or more layers thereof, and mixed multilayer membranes such as a polyethylene / polypropylene two-layer separation membrane, a polyethylene / polypropylene / polyethylene three-layer separation membrane, and a polypropylene / polyethylene / polypropylene three-layer separation membrane may be used.

[0203] In a lithium battery according to an embodiment, the liquid electrolyte contains a lithium salt and an organic solvent.

[0204] As the organic solvent, for example, an aprotic organic solvent such as N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyrolactone, 1,2-dimethoxyethane, tetrahydroxy franc, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolan, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, triester phosphate, trimethoxy methane, dioxolane derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ethers, methyl pyropionate, ethyl propionate, etc. can be used. Carbonate solvents such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, and diethyl carbonate can be used.

[0205] The above lithium salt can be any one that is commonly used in lithium secondary batteries, and as a material that is easily dissolved in the non-aqueous solvent, for example, one or more of the following materials can be used: LiSCN, LiN(CN)2, LiClO4, LiBF4, LiAsF6, LiPF6, LiCF3SO3, LiC(CF3SO2)3, LiC(FSO2)3, LiN(SO2C2F5)2, LiN(SO2CF3)2, LiN(SO2F)2, LiSbF6, LiPF3(CF2CF3)3, LiPF3(CF3)3, and LiB(C2O4)2.

[0206] The concentration of the lithium salt may be, for example, 1 to 5 M, for example, 1 to 2.5 M, in the liquid electrolyte. In the above range, a sufficient amount of lithium ions required for charging and discharging a lithium battery can be generated.

[0207] When a gel-type polymer electrolyte exists in the pores of a porous substrate, the interfacial resistance between the positive electrode, negative electrode, and separator is minimized, and lithium movement becomes easier.

[0208] According to one embodiment, the negative electrode active material layer can be arranged during the assembly of the lithium battery. According to another embodiment, the negative electrode active material layer can include a negative electrode active material layer by plating lithium metal after charging. The negative electrode active material layer can be a lithium plating layer (plated lithium layer).

[0209] The above negative electrode active material layer includes lithium metal or a lithium alloy.

[0210] When the negative electrode active material layer is placed at the time of assembly, it may include only a carbon-based material, a carbon-based material, and at least one selected from metals and metalloids.

[0211] The carbon-based material includes amorphous carbon, and the average particle diameter of the amorphous carbon is 10 nm to 100 nm, and the carbon-based material includes carbon black (CB), acetylene black (AB), furnace black (FB), ketjen black (KB), graphene, or a combination thereof.

[0212] The above negative active material layer includes a lithium metal foil, a lithium metal powder, a lithium alloy foil, a lithium alloy powder, or a combination thereof, wherein the lithium alloy contains lithium and a first metal.

[0213] The first metal is indium (In), silicon (Si), gallium (Ga), tin (Sn), aluminum (Al), titanium (Ti), zirconium (Zr), niobium (Nb), germanium (Ge), antimony (Sb), bismuth (Bi), gold (Au), platinum (Pt), palladium (Pd), magnesium (Mg), silver (Ag), zinc (Zn), nickel, iron, cobalt, chromium, cesium, sodium, potassium, calcium, yttrium, bismuth, tantalum, hafnium, barium, vanadium, strontium, lanthanum, or a combination thereof.

[0214] The negative electrode active material layer (22) may include, for example, lithium foil, lithium powder, or a combination thereof. The lithium foil may include, for example, lithium metal foil, lithium alloy foil, or a combination thereof. The lithium powder may include lithium metal powder, lithium alloy powder, or a combination thereof. A lithium alloy is an alloy of lithium and another metal that can be alloyed with lithium, such as a lithium-silver alloy, a lithium-zinc alloy, a lithium-magnesium alloy, or a lithium-tin alloy. The negative electrode active material layer including a lithium metal foil may be, for example, a lithium metal layer. The negative electrode active material layer including a lithium alloy foil may be, for example, a lithium alloy layer. The negative electrode active material layer including a lithium metal powder and / or a lithium alloy powder may be introduced by coating a slurry including lithium powder and a binder, etc., on a negative electrode current collector. The binder may be, for example, a fluorine-based binder such as polyvinylidene fluoride (PVDF). The negative electrode active material layer may not include a carbon-based negative electrode active material. Therefore, the negative electrode active material layer can be made of a metal-based negative electrode active material.

[0215] The negative electrode current collector is composed of a material that does not react with lithium, i.e., does not form an alloy or compound. The material constituting the negative electrode current collector includes, but is not limited to, copper (Cu), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), and nickel (Ni), and any material that is used as an electrode current collector in the relevant technical field may be used. The negative electrode current collector may be composed of one of the above-mentioned metals, or may be composed of an alloy or a coating material of two or more metals. The negative electrode current collector is, for example, in the form of a plate or foil.

[0216] In one embodiment of the present invention, the positive electrode collector uses a plate or foil made of, for example, indium (In), copper (Cu), magnesium (Mg), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), lithium (Li), or an alloy thereof. The thickness of the positive electrode collector is, for example, 1 µm to 100 µm, 1 µm to 50 µm, 5 µm to 25 µm, or 10 µm to 20 µm.

[0217] The negative electrode active material layer may contain a negative electrode active material and a binder.

[0218] The negative active material has, for example, a particle form. The average particle diameter of the negative active material having a particle form is, for example, 10 nm to 4 ㎛, 10 nm to 1 ㎛, 10 nm to 500 nm, 10 nm to 100 nm, or 20 nm to 80 nm. When the negative active material has an average particle diameter in this range, reversible plating and / or dissolution of lithium can be facilitated during charge and discharge. The average particle diameter of the negative active material is, for example, a median diameter (D50) measured using a laser particle size distribution analyzer.

[0219] The negative electrode active material may include, for example, at least one selected from a carbon-based negative electrode active material and a metal or metalloid negative electrode active material. The carbon-based negative electrode active material may be, for example, amorphous carbon. Examples of the carbon-based negative electrode active material include, but are not limited to, carbon black (CB), acetylene black (AB), furnace black (FB), ketjen black (KB), graphene, etc., and any material classified as amorphous carbon in the relevant technical field may be used. Amorphous carbon is carbon that has no crystallinity or very low crystallinity, and is distinguished from crystalline carbon or graphite-based carbon. The metal or metalloid negative electrode active material includes, but is not limited to, one or more selected from the group consisting of gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), and zinc (Zn), and any metal or metalloid negative electrode active material that forms an alloy or compound with lithium in the relevant technical field may be used. For example, nickel (Ni) does not form an alloy with lithium, and therefore is not a metal negative electrode active material in the present specification. The negative electrode active material layer includes a type of negative electrode active material among these negative electrode active materials, or includes a mixture of a plurality of different negative electrode active materials. For example, the negative electrode active material layer may include a mixture of amorphous carbon and one or more selected from the group consisting of gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), and zinc (Zn). The mixing ratio of the mixture may be, for example, 10:1 to 1:2, 10:1 to 1:1, 7:1 to 1:1, 5:1 to 1:1, or 4:1 to 2:1 by weight.The negative electrode active material included in the negative electrode active material layer may include a mixture of first particles made of, for example, amorphous carbon and second particles made of a metal or a metalloid. The metal includes, for example, gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), and zinc (Zn). The content of the second particles is 8 to 60 wt%, 10 to 50 wt%, 15 to 40 wt%, or 20 to 30 wt% based on the total weight of the mixture. When the second particles have a content in this range, the cycle characteristics of, for example, a lithium battery are further improved.

[0220] The binder included in the negative electrode active material layer may be, for example, styrene-butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, vinylidene fluoride / hexafluoropropylene copolymer, polyacrylonitrile, polymethyl methacrylate, etc., but is not necessarily limited thereto, and any binder used in the relevant technical field may be used. The binder may be composed of a single binder or a plurality of different binders. When the negative electrode active material layer does not include a binder, the negative electrode active material layer can be easily separated from the ceramic coating layer (21) or the negative electrode current collector (21). The content of the binder included in the negative electrode active material layer may be, for example, 1 to 20 wt% based on the total weight of the negative electrode active material layer.

[0221] The thickness of the negative electrode active material layer may be, for example, 0.1 ㎛ to 500 ㎛, or 100 ㎛ to 50 ㎛. The thickness of the negative electrode active material layer may be, for example, 1% to 50%, 1% to 30%, 1% to 10%, or 1% to 5% of the thickness of the positive electrode active material layer. If the thickness of the negative electrode active material layer is too thin, lithium dendrites formed between the negative electrode active material layer and the negative electrode current collector may collapse the negative electrode active material layer, making it difficult to improve the cycle characteristics of the lithium battery. If the thickness of the negative electrode active material layer increases excessively, the energy density of the lithium battery employing the negative electrode (20) may decrease, and it may be difficult to improve the cycle characteristics.

[0222] If the thickness of the negative electrode active material layer decreases, for example, the charge capacity of the negative electrode active material layer also decreases. The charge capacity of the negative electrode active material layer may be, for example, 0.1% to 50%, 1% to 30%, 1% to 10%, 1% to 5%, or 1% to 2% of the charge capacity. If the charge capacity of the negative electrode active material layer is too small, lithium dendrites formed between the negative electrode active material layer and the negative electrode current collector may collapse the negative electrode active material layer, making it difficult to improve the cycle characteristics of the lithium battery. If the charge capacity of the negative electrode active material layer increases excessively, the energy density of the lithium battery using the negative electrode (20) may decrease, and it may be difficult to improve the cycle characteristics. The charge capacity of the positive electrode active material layer is obtained by multiplying the charge capacity density (mAh / g) of the positive electrode active material by the mass of the positive electrode active material in the positive electrode active material layer. When multiple types of positive electrode active materials are used, the charge capacity density × mass value is calculated for each positive electrode active material, and the sum of these values ​​is the charge capacity of the positive electrode active material layer. The charge capacity of the negative electrode active material layer is calculated in the same way. That is, the charge capacity of the negative electrode active material layer is obtained by multiplying the charge capacity density (mAh / g) of the negative electrode active material by the mass of the negative electrode active material in the negative electrode active material layer. When multiple types of negative electrode active materials are used, the charge capacity density × mass value is calculated for each negative electrode active material, and the sum of these values ​​is the capacity of the negative electrode active material layer. Here, the charge capacity density of the positive electrode active material and the negative electrode active material is the capacity estimated using an all-solid-state half-cell using lithium metal as a counter electrode. The charge capacity of the positive electrode active material layer and the negative electrode active material layer are directly measured by measuring the charge capacity using an all-solid-state half-cell. The charge capacity density is obtained by dividing the measured charge capacity by the mass of each active material. Alternatively, the charge capacity of the positive electrode active material layer and the negative electrode active material layer may be the initial charge capacity measured at the first charge cycle.

[0223] [Lithium battery]

[0224] According to one embodiment, a lithium battery includes a positive electrode; a negative electrode current collector; and an electrolyte layer disposed between the positive electrode and the negative electrode current collector. The lithium battery may further include a separator. A lithium metal layer may further be included between the negative electrode current collector and the electrolyte layer. And, a negative electrode active material layer may further be included between the negative electrode current collector and the electrolyte layer. Such a lithium battery can simultaneously provide excellent life characteristics. The lithium battery may be, for example, a lithium primary battery, a lithium battery, a lithium-sulfur battery, a lithium-air battery, etc., but is not limited thereto, and any lithium battery used in the art may be used.

[0225] Lithium batteries are manufactured by, for example, the following exemplary methods, but are not necessarily limited to these methods and are adjusted according to required conditions.

[0226] (anode)

[0227] First, a positive electrode active material composition is prepared by mixing a positive electrode active material, a conductive agent, a binder, and a solvent. The prepared positive electrode active material composition is directly coated on an aluminum current collector and dried to produce a positive electrode plate having a positive electrode active material layer formed thereon. Alternatively, the positive electrode active material composition is cast on a separate support, and then the film obtained by peeling from the support is laminated on the aluminum current collector to produce a positive electrode plate having a positive electrode active material layer formed thereon.

[0228] A compound capable of reversible intercalation and deintercalation of lithium (a lithiated intercalation compound) can be used as a cathode active material. Specifically, one or more of a composite oxide of lithium and a metal selected from cobalt, manganese, nickel, and combinations thereof can be used.

[0229] The above composite oxide may be a lithium transition metal composite oxide, and specific examples thereof include lithium nickel-based oxide, lithium cobalt-based oxide, lithium manganese-based oxide, lithium iron phosphate-based compound, cobalt-free nickel-manganese-based oxide, or a combination thereof.

[0230] As an example, a compound represented by any one of the following chemical formulas may be used: Li a A 1-b X b O 2-c D c (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05); Li a Mn 2-b X b O 4-c D c (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05); Li a Ni 1-b-c Co b X c O 2-α D α (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5, 0<α<2); Li a Ni 1-b-c Mn b X c O 2-α D α (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5, 0<α<2); Li a Ni b Co c L 1 d G e O2(0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5, 0≤e≤0.1); Li a NiG b O2(0.90≤a≤1.8, 0.001≤b≤0.1); Li a CoG b O2(0.90≤a≤1.8, 0.001≤b≤0.1); Li a Mn 1-b G b O2(0.90≤a≤1.8, 0.001≤b≤0.1); Lia Mn2G b O4(0.90≤a≤1.8, 0.001≤b≤0.1); Li a Mn 1-g G g PO4(0.90≤a≤1.8, 0≤g≤0.5); Li (3-f) Fe2(PO4)3(0≤f≤2); Li a FePO4(0.90≤a≤1.8).

[0231] In the above chemical formula, A is Ni, Co, Mn, or a combination thereof; X is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof; D is O, F, S, P, or a combination thereof; G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof; L 1 is Mn, Al or a combination thereof.

[0232] For example, the cathode active material may be a high-nickel cathode active material in which the nickel content is 80 mol% or more, 85 mol% or more, 90 mol% or more, 91 mol% or more, or 94 mol% or more and 99 mol% or less, based on 100 mol% of metals excluding lithium in the lithium transition metal composite oxide. The high-nickel cathode active material can realize high capacity and thus can be applied to high-capacity, high-density lithium secondary batteries.

[0233] The cathode active material is, for example, Li a Ni x Co y M z O 2-b A b(1.0≤a≤1.2, 0≤b≤0.2, 0.8≤x<1, 0 <y≤0.3, 0<z≤0.3, 및 x+y+z=1이고, M은 망간(Mn), 니오븀(Nb), 바나듐(V), 마그네슘(Mg), 갈륨(Ga), 실리콘(Si), 텅스텐(W), 몰리브덴(Mo), 철(Fe), 크롬(Cr), 구리(Cu), 아연(Zn), 티타늄(Ti), 알루미늄(Al), 보론(B) 또는 이들의 조합이고, A는 F, S, Cl, Br 또는 이들의 조합), LiNi x Co y Mn z O2(0.8≤x≤0.95, 0≤y≤0.2, 0 <z≤0.2 및 x+y+z=1), LiNi x Co y Al z O2(0.8≤x≤0.95, 0≤y≤0.2, 0 <z≤0.2 및 x+y+z=1), LiNi x Co y Mn z Al w O2(0.8≤x≤0.95, 0≤y≤0.2, 0 <z≤0.2, 0<w≤0.2, 및 x+y+z+w=1), Li a Co x M y O 2-b A b (1.0≤a≤1.2, 0≤b≤0.2, 0.9≤x≤1, 0≤y≤0.1, and x+y=1, M is manganese (Mn), niobium (Nb), vanadium (V), magnesium (Mg), gallium (Ga), silicon (Si), tungsten (W), molybdenum (Mo), iron (Fe), chromium (Cr), copper (Cu), zinc (Zn), titanium (Ti), aluminum (Al), boron (B) or a combination thereof, and A is F, S, Cl, Br or a combination thereof), Li a Ni x Mn y M' z O 2-b A b(1.0≤a≤1.2, 0≤b≤0.2, 0 <x≤0.3, 0.5≤y<1, 0<z≤0.3, 및 x+y+z=1이고, M'는 코발트(Co), 니오븀(Nb), 바나듐(V), 마그네슘(Mg), 갈륨(Ga), 실리콘(Si), 텅스텐(W), 몰리브덴(Mo), 철(Fe), 크롬(Cr), 구리(Cu), 아연(Zn), 티타늄(Ti), 알루미늄(Al), 보론(B) 또는 이들의 조합이고, A는 F, S, Cl, Br 또는 이들의 조합), Li a M1 x M2 y PO 4-b X b (Here, 0.90≤a≤1.1, 0≤x≤0.9, 0≤y≤0.5, 0.9 <x+y<1.1, 0≤b≤2 이며, M1이 크롬(Cr), 망간(Mn), 철(Fe), 코발트(Co), 니켈(Ni), 구리(Cu), 지르코늄(Zr) 또는 이들의 조합이며, M2가 마그네슘(Mg), 칼슘(Ca), 스트론튬(Sr), 바륨(Ba), 티탄(Ti), 아연(Zn), 보론(B), 니오븀(Nb), 갈륨(Ga), 인듐(In), 몰리브덴(Mo), 텅스텐(W), 알루미늄(Al), 실리콘(Si), 크롬(Cr), 바나듐(V), 스칸듐(Sc), 이트륨(Y) 또는 이들의 조합이며, X가 O, F, S, P 또는 이들의 조합), Li a M3 z PO4 (0.90≤a≤1.1, 0.9≤z≤1.1, and M3 is chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zirconium (Zr), or a combination thereof).

[0234] The conductive material may include, but is not limited to, carbon black, graphite particles, natural graphite, artificial graphite, acetylene black, Ketjen black, carbon fibers; carbon nanotubes; metal powders or metal fibers or metal tubes such as copper, nickel, aluminum, and silver; and conductive polymers such as polyphenylene derivatives. Any conductive material used in the relevant technical field may be used. Alternatively, the anode may not include a separate conductive material, for example.

[0235] As binders, vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene (PTFE), mixtures of the above-mentioned polymers, styrene butadiene rubber-based polymers, etc. are used, and as solvents, N-methylpyrrolidone (NMP), acetone, water, etc. are used, but are not necessarily limited to these, and any solvent used in the relevant technical field may be used.

[0236] A positive electrode for a lithium secondary battery may include a current collector and a positive electrode active material layer formed on the current collector. The positive electrode active material layer includes a positive electrode active material and may further include a binder and / or a conductive material.

[0237] For example, the anode may further include an additive that can act as a sacrificial anode.

[0238] The content of the positive electrode active material may be 90 wt% to 99.5 wt% with respect to 100 wt% of the positive electrode active material layer, and the contents of the binder and conductive material may be 0.5 wt% to 5 wt%, respectively, with respect to 100 wt% of the positive electrode active material layer.

[0239] The above binder serves to adhere the positive electrode active material particles well to each other and also to adhere the positive electrode active material well to the current collector. Representative examples of the binder include, but are not limited to, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, (meth)acrylated styrene-butadiene rubber, epoxy resin, (meth)acrylic resin, polyester resin, nylon, etc.

[0240] The conductive material is used to provide conductivity to the electrode, and any material that does not cause chemical changes and is electronically conductive can be used in the battery. Examples of the conductive material include carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, carbon nanofiber, and carbon nanotube; metal-based materials containing copper, nickel, aluminum, silver, etc. in the form of metal powder or metal fiber; conductive polymers such as polyphenylene derivatives; or mixtures thereof.

[0241] The positive electrode collector uses a plate or foil made of, for example, indium (In), copper (Cu), magnesium (Mg), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), lithium (Li), or an alloy thereof. The thickness of the positive electrode collector is, for example, 1 ㎛ to 100 ㎛, 1 ㎛ to 50 ㎛, 5 ㎛ to 25 ㎛, or 10 ㎛ to 20 ㎛.

[0242] The cathode current collector may include, for example, a base film and a metal layer disposed on one or both sides of the base film. The base film may include, for example, a polymer. The polymer may be, for example, a thermoplastic polymer. The polymer may include, for example, polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polybutylene terephthalate (PBT), polyimide (PI), or a combination thereof. The base film may be, for example, an insulator. Since the base film includes an insulating thermoplastic polymer, when a short circuit occurs, the base film may soften or liquefy, thereby blocking battery operation and suppressing a sudden increase in current. The metal layer may include, for example, indium (In), copper (Cu), magnesium (Mg), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), or an alloy thereof. The metal layer can act as an electrochemical fuse and cut off in case of overcurrent to prevent short circuits. The limit current and maximum current can be controlled by adjusting the thickness of the metal layer. The metal layer can be plated or deposited on the base film. As the thickness of the metal layer decreases, the limit current and / or maximum current of the positive electrode current collector decreases, thereby improving the stability of the lithium battery in case of a short circuit. A lead tab can be added to the metal layer for external connection. The lead tab can be welded to the metal layer or the metal layer / base film laminate by ultrasonic welding, laser welding, spot welding, etc. During welding, the base film and / or the metal layer melt, so that the metal layer can be electrically connected to the lead tab. To strengthen the welding between the metal layer and the lead tab, a metal chip can be added between the metal layer and the lead tab.The metal piece may be a thin piece of the same material as the metal of the metal layer. The metal piece may be, for example, a metal foil, a metal mesh, etc. The metal piece may be, for example, aluminum foil, copper foil, SUS foil, etc. After the metal piece is placed on the metal layer, the lead tab may be welded to the metal piece / metal layer laminate or the metal piece / metal layer / base film laminate. During welding, the base film, the metal layer, and / or the metal piece may melt, so that the metal layer or the metal layer / metal piece laminate may be electrically connected to the lead tab. A metal chip and / or a lead tab may be added to a portion of the metal layer. The base film may have a thickness of, for example, 1 to 50 μm, 1.5 to 50 μm, 1.5 to 40 μm, or 1 to 30 μm. When the base film has a thickness in this range, the weight of the electrode assembly can be more effectively reduced. The melting point of the base film may be, for example, 100 to 300°C, 100 to 250°C or less, or 100 to 200°C. Since the base film has a melting point within this range, the base film can be melted and easily bonded to the lead tab during the welding process of the lead tab. To improve the adhesion between the base film and the metal layer, a surface treatment such as corona treatment may be performed on the base film. The thickness of the metal layer may be, for example, 0.01 to 3 μm, 0.1 to 3 μm, 0.1 to 2 μm, or 0.1 to μm. Since the metal layer has a thickness within this range, conductivity can be maintained while ensuring the stability of the electrode assembly. The thickness of the metal piece may be, for example, 2 to 10 μm, 2 to 7 μm, or 4 to 6 μm. Since the metal piece has a thickness within this range, the connection between the metal layer and the lead tab can be performed more easily. By having this structure as the cathode current collector, the weight of the cathode can be reduced, and as a result, the energy density of the cathode and lithium battery can be improved.

[0243] (electrolyte layer)

[0244] Next, an electrolyte layer is prepared. The electrolyte layer contains a gel polymer electrolyte according to an embodiment.

[0245] The electrolyte layer may further include a separator.

[0246] Any separator commonly used in lithium batteries can be used.

[0247] As such a separator, a multilayer membrane of two or more layers of polyethylene, polypropylene, polyvinylidene fluoride, or these may be used, and of course, a mixed multilayer membrane such as a polyethylene / polypropylene two-layer separator, a polyethylene / polypropylene / polyethylene three-layer separator, or a polypropylene / polyethylene / polypropylene three-layer separator may be used.

[0248] The above separator may include a porous substrate and a coating layer including an organic material, an inorganic material, or a combination thereof located on one or both sides of the porous substrate.

[0249] The above porous substrate is a porous membrane, and the porous membrane is a woven fabric or a non-woven fabric,

[0250] The porous substrate includes an olefin resin, a fluorine resin, an ester resin, an imide resin, an acrylic resin, a cellulose resin, or a combination thereof, and the olefin resin includes polyethylene, polypropylene, or a combination thereof.

[0251] The fluorine-based resin includes polyvinylidene fluoride, polytetrafluoroethylene, or a combination thereof, the ester-based resin includes polyethylene terephthalate, polybutylene terephthalate, or a combination thereof, the imide-based resin includes polyamideimide, polyetherimide, or a combination thereof, the acrylic-based resin includes polyacrylonitrile, polyacrylate, or a combination thereof, and the cellulose-based resin includes carboxymethyl cellulose, microbial cellulose, plant cellulose, animal cellulose, or a combination thereof.

[0252] The above porous substrate may be a polymer film formed of any one polymer selected from polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyacetal, polyamide, polyimide, polycarbonate, polyether ketone, polyarylether ketone, polyetherimide, polyamideimide, polybenzimidazole, polyethersulfone, polyphenylene oxide, cyclic olefin copolymer, polyphenylene sulfide, polyethylene naphthalate, glass fiber, Teflon, and polytetrafluoroethylene, or a copolymer or mixture of two or more thereof.

[0253] The organic material may include a polyvinylidene fluoride polymer or a (meth)acrylic polymer.

[0254] The above inorganic materials are Al2O3, SiO2, TiO2, SnO2, CeO2, MgO, NiO, CaO, GaO, ZnO, ZrO2, Y2O3, It may include inorganic particles selected from, but not limited to, SrTiO3, BaTiO3, Mg(OH)2, boehmite, and combinations thereof.

[0255] The organic and inorganic substances may be mixed and present in one coating layer, or a coating layer including an organic substance and a coating layer including an inorganic substance may be present in a laminated form.

[0256] A lithium battery according to an embodiment may further include a solid electrolyte. The solid electrolyte is, for example, an oxide-based solid electrolyte, a sulfide-based solid electrolyte, or a combination thereof.

[0257] Solid electrolytes are, for example, oxide-based solid electrolytes. Oxide-based solid electrolytes are Li 1+x+y Al x Ti 2-x Si y P 3-y O 12 (0 <x<2, 0≤y<3), Li3PO4, Li x Ti y (PO4)3(0 <x<2, 0<y<3), Li x Al y Ti z (PO4)3(0 <x<2, 0<y<1, 0<z<3), Li 1+x+y (Al, Ga) x (Ti, Ge) 2-x Si y P 3-y O 12 (0≤x≤1 0≤y≤1), Li x La y TiO3(0 <x<2, 0<y<3), Li2O, LiOH, Li2CO3, LiAlO2, Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2, Li 3+x La3M2O 12 (M = Te, Nb, or Zr, x is an integer from 1 to 10) is one or more selected from. The solid electrolyte is manufactured by a sintering method, etc. For example, the oxide-based solid electrolyte is Li7La3Zr2O 12 (LLZO) and Li 3+x La3Zr 2-a M a O 12 A garnet-type solid electrolyte selected from (M doped LLZO, M=Ga, W, Nb, Ta, or Al, x is an integer from 1 to 10).

[0258] The sulfide-based solid electrolyte may include, for example, lithium sulfide, silicon sulfide, phosphorus sulfide, boron sulfide, or a combination thereof. The sulfide-based solid electrolyte particles may include Li2S, P2S5, SiS2, GeS2, B2S3, or a combination thereof. The sulfide-based solid electrolyte particles may be Li2S or P2S5. Sulfide-based solid electrolyte particles are known to have high lithium ion conductivity compared to other inorganic compounds. For example, the sulfide-based solid electrolyte includes Li2S and P2S5. When the sulfide solid electrolyte material constituting the sulfide-based solid electrolyte includes Li2S-P2S5, the mixing molar ratio of Li2S to P2S5 may be, for example, in a range of about 50:50 to about 90:10. In addition, Li3PO4, halogen, halogen compound, Li 2+2x Zn 1??x GeO4("LISICON", 0≤x<1), Li 3+y PO 4-x N x( "LIPON", 0 <x<4, 0<y<3), Li 3.25 Ge 0.25 P 0.75 S4("ThioLISICON"), Li2O-Al2O3-TiO2-P2O 5( An inorganic solid electrolyte prepared by adding "LATP") etc. to an inorganic solid electrolyte of Li2S-P2S5, SiS2, GeS2, B2S3, or a combination thereof can be used as a sulfide solid electrolyte. Non-limiting examples of sulfide solid electrolyte materials include Li2S-P2S5; Li2S-P2S5-LiX (X=halogen element); Li2S-P2S5-Li2O; Li2S-P2S5-Li2O-LiI; Li2S-SiS2; Li2S-SiS2-LiI; Li2S-SiS2-LiBr; Li2S-SiS2-LiCl; Li2S-SiS2-B2S3-LiI; Li2S-SiS2-P2S5-LiI; Li2S-B2S3; Li2S -P2S5-Z m S n(0 <m<10, 0<n<10, Z=Ge, Zn 또는 Ga); Li2S-GeS2; Li2S-SiS2-Li3PO4; 및 Li2S-SiS2-Li p MO q (0 <p<10, 0<q<10, M=P, Si, Ge, B, Al, Ga 또는 In)을 포함한다. 이와 관련하여, 황화물계 고체전해질 재료는 황화물계 고체전해질 물질의 원료 시작 물질(예를 들면, Li2S, P2S5, 등)을 용융 담금질법(melt quenching method), 기계적 밀링법 등에 의해 처리함으로써 제조될 수 있다. 또한, 소성(calcinations) 공정이 상기 처리 후에 수행될 수 있다. 황화물계 고체전해질은 비정질이거나, 결정질이거나, 이들이 혼합된 상태일 수 있다.

[0259] (cathode)

[0260] The cathode contains a cathode current collector.

[0261] Although not shown in the drawing, the negative electrode current collector (21) may include, for example, a base film and a metal layer disposed on one or both sides of the base film. The base film may include, for example, a polymer. The polymer may be, for example, a thermoplastic polymer. The polymer may include, for example, polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polybutylene terephthalate (PBT), polyimide (PI), or a combination thereof. The polymer may be an insulating polymer. Since the base film includes an insulating thermoplastic polymer, when a short circuit occurs, the base film may soften or liquefy, thereby blocking battery operation and suppressing a rapid increase in current. The metal layer may include, for example, copper (Cu), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), or an alloy thereof. The metal layer may correspond to, for example, the first metal substrate. The metal layer may additionally include a coating layer including a second metal. The negative electrode current collector (21) may additionally include a metal piece and / or a lead tab. For more specific details on the base film, metal layer, metal chip, and lead tab of the negative electrode current collector (21), refer to the positive electrode current collector. By having such a structure, the negative electrode current collector (21) can reduce the weight of the negative electrode, thereby improving the energy density of the negative electrode and the lithium battery.

[0262] The negative electrode collector may contain, for example, copper (Cu), nickel (Ni), nickel-coated copper, stainless steel (SUS), iron (Fe), cobalt (Co), or an alloy thereof.

[0263] A negative electrode active material layer may be formed on the negative electrode current collector. The negative electrode active material layer may be formed as a lithium deposition layer after charging. Alternatively, the negative electrode active material layer may be formed using a negative electrode active material during battery assembly.

[0264] The method of forming a negative electrode active material layer using a negative electrode active material can be manufactured in the same manner as described above, except that the negative electrode active material is used instead of the positive electrode active material when forming the positive electrode active material layer.

[0265] A lithium battery may further include, for example, a thin film comprising an element capable of forming an alloy with lithium on one surface of an anode current collector. The thin film is disposed between the anode current collector and the anode active material layer. The thin film includes, for example, an element capable of forming an alloy with lithium. The element capable of forming an alloy with lithium includes, but is not limited to, gold, silver, zinc, tin, indium, silicon, aluminum, bismuth, etc., and any element capable of forming an alloy with lithium in the art may be used. The thin film may be composed of one of these metals or an alloy of several types of metals. By disposing the thin film on one surface of the anode current collector, for example, the deposition shape of the first anode active material layer deposited between the thin film and the anode active material layer becomes flatter, and the cycle characteristics of the lithium battery may be further improved.

[0266] Let us look at a lithium battery according to another embodiment with reference to FIGS. 3 to 5.

[0267] Referring to FIG. 3, a lithium battery (1) according to one embodiment includes a positive electrode (3), a negative electrode (2), and a separator (4). The separator is contained in an electrolyte layer according to one embodiment.

[0268] The separator may contain a gel-type polymer electrolyte disposed on the upper portion thereof, and the separator may contain a gel-type polymer electrolyte.

[0269] A gel polymer electrolyte (not shown) may be placed between the separator and the positive electrode. The positive electrode (3), the negative electrode (2), and the separator (4) are wound or folded to form a battery structure (7). The formed battery structure (7) is accommodated in a battery case (5). An organic electrolyte is injected into the battery case (5) and sealed with a cap assembly (6), thereby completing the lithium battery (1). The battery case (5) is cylindrical, but is not necessarily limited to this shape, and may be, for example, square, thin-film, etc.

[0270] Referring to Fig. 4, a lithium battery (1) according to one embodiment includes a positive electrode (3), a negative electrode (2), and a separator (4). The separator is contained in an electrolyte layer according to one embodiment.

[0271] The separator may contain a gel-type polymer electrolyte disposed on the upper portion thereof, and the separator may contain a gel-type polymer electrolyte.

[0272] A separator (4) is placed between the positive electrode (3) and the negative electrode (2), and the positive electrode (3), the negative electrode (2), and the separator (4) are wound or folded to form a battery structure (7). The formed battery structure (7) is accommodated in a battery case (5). An electrode tab (8) that serves as an electrical path for guiding the current formed in the battery structure (7) to the outside may be included. An organic electrolyte is injected into the battery case (5) and sealed to complete the lithium battery (1). The battery case (5) is square, but is not necessarily limited to this shape, and may have, for example, a cylindrical shape, a thin film shape, etc.

[0273] Referring to FIG. 5, a lithium battery (1) according to one embodiment includes a positive electrode (3), a negative electrode (2), and a separator (4). The separator is contained in the electrolyte layer according to one embodiment. In addition, a gel-type polymer electrolyte disposed on the upper portion of the separator may be contained, and the gel-type polymer electrolyte may be contained in the separator. A separator (4) is disposed between the positive electrode (3) and the negative electrode (2) to form a battery structure. The gel-type polymer electrolyte between the separator and the positive electrode is not shown. The battery structure (7) is stacked in a bi-cell structure and then accommodated in a battery case (5). An electrode tab (8) that serves as an electrical path for inducing a current formed in the battery structure (7) to the outside may be included. An organic electrolyte is injected into the battery case (5) and sealed to complete the lithium battery (1). The battery case (5) is not necessarily limited to a square shape, but may be, for example, a cylindrical shape, a thin film shape, etc.

[0274] A pouch-type lithium battery corresponds to the lithium batteries of FIGS. 4 and 5, each of which uses a pouch as a battery case. The pouch-type lithium battery includes one or more battery structures. An electrolyte is disposed between a positive electrode and a negative electrode, or an electrolyte and a separator are disposed to form a battery structure. The battery structures are laminated in a bi-cell structure, then impregnated with a liquid electrolyte, and accommodated and sealed in a pouch to complete the pouch-type lithium battery. For example, although not shown in the drawings, the above-described positive electrode, negative electrode, and separator may be simply laminated and accommodated in a pouch in the form of an electrode assembly, or may be wound or folded into a jelly-roll-shaped electrode assembly and then accommodated in a pouch. Subsequently, an organic electrolyte is injected into the pouch and sealed to complete the lithium battery.

[0275] The lithium battery of the present disclosure has excellent discharge capacity and lifespan characteristics, as well as high energy density, and is therefore used in, for example, electric vehicles (EVs). For example, it is used in hybrid vehicles such as plug-in hybrid electric vehicles (PHEVs). It is also used in applications requiring large amounts of power storage, such as electric bicycles and power tools.

[0276] Lithium batteries are stacked in multiple layers to form a battery module, and the multiple battery modules form a battery pack. Such a battery pack can be used in any device requiring high capacity and high output. For example, it can be used in laptops, smartphones, electric vehicles, etc. The battery module includes, for example, multiple batteries and a frame that holds them. The battery pack includes, for example, multiple battery modules and a bus bar that connects them. The battery module and / or the battery pack may further include a cooling device. The multiple battery packs are controlled by a battery management system. The battery management system includes a battery pack and a battery control device connected to the battery pack.

[0277] [Method for manufacturing lithium batteries]

[0278] According to one embodiment, a lithium battery can be manufactured by the steps of: preparing a negative electrode current collector; preparing a separator; preparing a positive electrode; preparing a battery assembly by laminating the negative electrode current collector, the separator, and the positive electrode; injecting a composition for forming a gel polymer electrolyte, which includes a first polymerizable monomer and a second polymerizable monomer as polymerizable monomers for forming a gel polymer, a lithium salt as a liquid electrolyte, and an organic solvent, into the battery assembly; and performing crosslinking to form a gel polymer electrolyte.

[0279] In a lithium battery according to an embodiment, a separator containing a gel polymer electrolyte can be formed in situ by injecting a composition for forming a gel polymer electrolyte into a battery assembly and crosslinking the composition, as described above. Alternatively, a separator containing a gel polymer electrolyte can be manufactured separately to form a self-supporting film, which is then placed on a negative electrode current collector and a positive electrode placed on top of the self-supporting film, thereby manufacturing a lithium battery.

[0280] In the composition for forming the gel polymer electrolyte, the total content of the first polymerizable monomer and the second polymerizable monomer may be, for example, 0.1 to 10 wt%, 0.2 to 8 wt%, 0.5 to 6 wt%, 1 to 5 wt%, or 2 to 4 wt% based on the total weight of the composition for forming the gel polymer electrolyte. When the content is within this range, a stable gel polymer electrolyte can be formed.

[0281] The separator may further include a liquid electrolyte and / or a gel polymer electrolyte.

[0282] The crosslinking method of the composition for forming a gel polymer electrolyte is not particularly limited, and crosslinking may be performed, for example, by heat, ultraviolet rays, etc. From the viewpoint of manufacturing efficiency, thermal crosslinking using heat treatment may be used. The composition for forming a gel polymer may include, for example, a thermal initiator. The thermal initiator is not limited to, for example, t-amyl peroxide, azobis, etc., and any thermal initiator used in the relevant technical field may be used. The content of the thermal initiator may be 0.1 wt% or less or 0.05 wt% or less of the total weight of the composition for forming a gel polymer electrolyte.

[0283] Crosslinking can be performed, for example, by heat treatment. The heat treatment varies depending on the types of the first polymerizable monomer and the second polymerizable monomer constituting the composition for forming a gel polymer, and although it varies depending on the types, it is performed, for example, at 40 to 120°C, 60 to 110°C, or 70 to 100°C.

[0284] The crosslinked product of the composition for forming a gel polymer electrolyte may be, for example, the result of heat treatment at 40 to 120°C, 60 to 110°C, or 70 to 100°C for 1 to 3 hours. The heat treatment conditions may be adjusted depending on the type of thermal initiator used.

[0285] The above lithium battery may further include a separator. The separator may further include a liquid electrolyte and / or a gel-type polymer electrolyte.

[0286] A step of forming a protective layer on the negative electrode current collector may be further included.

[0287] The step of forming the above protective layer can be performed by coating and heat treating a composition for forming a protective layer comprising at least one binder precursor and a binder selected from boron nitride on a negative electrode current collector. Here, the binder precursor may include, for example, the first polymer and the second polymer, and the binder refers to the binder mentioned in the above-described protective layer.

[0288] A solvent such as N-methylpyrrolidone or dimethylformamide may be added to the composition for forming the protective layer. The content of the solvent may be 0.05 to 5 parts by weight based on 100 parts by weight of the total weight of boron nitride and binder.

[0289] The above protective layer may further include a lithium salt. The content of the lithium salt is 30 to 80 parts by weight, 40 to 60 parts by weight, or 45 to 55 parts by weight based on 100 parts by weight of the total weight of the binder and the lithium salt.

[0290] The composition for forming the protective layer may further include a second polymer having a crosslinkable functional group with the first polymer containing a hydroxyl group. The protective layer formed from the composition for forming the protective layer further includes a crosslinked polymer of the first polymer and the second polymer. Here, the mixing weight ratio of the first polymer containing a hydroxyl group and the second polymer is adjusted to be in the range of 50:50 to 99:1, 50:50 to 99:1, or 60:40 to 90:10.

[0291] The above second polymer is at least one selected from among fluorinated polyamic acid and fluorinated polyimide having a carboxyl group.

[0292] When the second polymer is a fluorinated polyamic acid having a carboxyl group, a composition for forming a protective layer containing the same may be coated on a negative electrode current collector, dried, and then further heat-treated to cause a crosslinking reaction between the first polymer and the second polymer, thereby forming a protective layer containing a crosslinked polymer. The heat-treatment may vary depending on the composition of the first polymer and the second polymer, but may be performed at, for example, 80 to 200°C, 100 to 200°C, 150 to 200°C, or 150 to 190°C. When the heat-treatment temperature is within the above range, the protective layer formed on the electrode surface can minimize exposure of the electrolyte at the electrode surface and create a uniform lithium ion flow throughout the electrode, thereby effectively suppressing lithium dendrite growth.

[0293] The present invention is explained in more detail through the following examples and comparative examples. However, the examples are intended to illustrate the present invention and are not intended to limit the scope of the present invention.

[0294] (Preparation of urethane acrylic monomer having two or more functional groups)

[0295] Manufacturing Example 1: Manufacturing of compound DRIC of the following chemical formula 3

[0296] <Chemical Formula 3>

[0297]

[0298] In chemical formula 3, EG represents a residue of ethylene glycol, DEG represents a residue of diethylene glycol, TMP represents a residue of trimethylolpropane, and n1 is 10.

[0299] Adipic acid (AA) 150.6 g, diethylene glycol (DG) 115.14 g, ethylene glycol (EG) 81.05 g, and trimethylolpropane (TMP) 21.32 g were added to a reaction vessel at room temperature (25°C) and the temperature was increased to 220°C. Titanium isopropoxide (TIP) was added to the reaction vessel. After the mixture reached full vacuum, it was subjected to a primary reaction at 220°C for 10 hours to obtain a polyester polyol. The polyol was first cooled to 130°C, vacuum-treated at 130°C for 2 hours, and then cooled to 75°C for a second time. 18.24 g of isocyanato ethyl methacrylate (ICEMA), 0.54 g of monomethyl ether hydroquinone (MEHQ), 0.566 g of butylated hydroxy toluene (BHT), and 0.526 g of dibutyl-tin-dilaulate (DBTDL) were added to the polyester polyol, and a secondary reaction was performed at 70 to 80°C for 3 hours to obtain compound DRIC of the chemical formula 3.

[0300] (Manufacturing of lithium batteries)

[0301] Example 1: Gel polymer formed using GPE (DPHA + DRIC 2:2 weight ratio + LE (0.6 M LiDFOB + 0.6 M LiBF4 in FEC:DEC (1:2 v / v))

[0302] A polyethylene single film having a thickness of 20 μm was laminated as a separator on top of a copper foil having a thickness of 10 μm, which is a negative current collector, and a positive electrode was laminated on the other side of the separator to manufacture a laminate. A composition for forming a gel polymer electrolyte (GPE) was injected into the prepared laminate and heat-treated at 70°C for 120 minutes to manufacture a lithium battery in which a gel polymer electrolyte was formed in the pores of the separator. The lithium battery had a structure of positive electrode / gel polymer electrolyte (separator) / protective layer / negative current collector.

[0303] The composition for forming the above gel polymer electrolyte was prepared by mixing dipentaerythritol hexaacrylate (DPHA) as a first polymerizable monomer, a compound represented by the chemical formula 3 (DRIC) as a second polymerizable monomer, and benzoin ethyl ether (Sigma-Aldrich, 240.30 g / mol) as a liquid electrolyte and initiator. The mixing weight ratio of DPHA and DRIC is 2:2.

[0304] <Chemical Formula 3>

[0305]

[0306] In chemical formula 3, EG represents a residue of ethylene glycol, DEG represents a residue of diethylene glycol, TMP represents a residue of trimethylolpropane, and n1 is 10.

[0307] As the liquid electrolyte, a 2:1 volume ratio mixed solvent of diethyl carbonate (DEC) and fluoroethylene carbonate (FEC) was used, in which 0.6 M LiBF4 and 0.6 M LiDFOB (lithium difluoro(oxalate)borate) were added.

[0308] The composition for forming the above gel polymer electrolyte contained 2 parts by weight of DPHA, 2 parts by weight of DRIC, 96 parts by weight of a liquid electrolyte, and an initiator based on 100 parts by weight of the total weight of the composition. The initiator was used in an amount of 5 parts by weight based on 100 parts by weight of the total weight of DPHA and DRIC, which are crosslinking monomers.

[0309] The above anode was manufactured according to the following method.

[0310] Li 1.04 Ni 0.88 Co 0.1 Al 0.02 O2 powder and carbon conductive material (Super-P; Timcal Ltd.) were uniformly mixed at a weight ratio of 90:5, and then a PVDF (polyvinylidene fluoride) binder solution was added to prepare a positive electrode active material slurry with a weight ratio of active material:carbon conductive material:binder = 90:5:5.

[0311] The positive electrode active material slurry manufactured according to the above process was coated on an aluminum substrate having a thickness of 15 μm using a doctor blade, dried under reduced pressure at 120°C, and then rolled using a roll press to form a sheet to manufacture a positive electrode.

[0312] Example 2: Gel polymer formed using GPE (DPHA + DRIC 3:1 weight ratio + LE (0.6 M LiDFOB + 0.6 M LiBF4 in FEC:DEC (1:2 v / v))

[0313] A lithium battery was manufactured in the same manner as in Example 1, except that the mixing weight ratio of DPHA and DRIC, which are crosslinking monomers, was changed to 3:1 when manufacturing a composition for forming a gel polymer electrolyte.

[0314] Example 3: Gel polymer formed using GPE (DPHA + DRIC 5:1) + LE (0.6 M LiDFOB + 0.6 M LiBF4 in FEC:DEC (1:2 v / v))

[0315] A lithium battery was manufactured in the same manner as in Example 1, except that the mixing weight ratio of DPHA and DRIC was changed to 5:1 when manufacturing a composition for forming a gel polymer electrolyte.

[0316] Example 4: Gel polymer formed using GPE (DPHA + DUDMA 3:1 weight ratio + LE (0.6 M LiDFOB + 0.6 M LiBF4 in FEC:DEC (1:2 v / v))

[0317] A lithium battery was manufactured in the same manner as in Example 2, except that the compound of Chemical Formula 2 (DUDMA) (Sigma-Aldrich, 470.56 / mol) was used instead of DRIC of Chemical Formula 6 when manufacturing a composition for forming a gel polymer electrolyte.

[0318] <Chemical Formula 2>

[0319]

[0320] In chemical formula 2, R is H, CH3 or a combination thereof, H and CH3 are 1:1, and are an isomer mixture.

[0321] Example 5: Gel polymer formed using GPE (TMPTMA+DRIC 3:1 weight ratio) + LE (0.6 M LiDFOB + 0.6 M LiBF4 in FEC:DEC (1:2 v / v)

[0322] A lithium battery was manufactured in the same manner as in Example 2, except that trimethylolpropane triacrylate (TMPTMA) was used instead of DPHA when manufacturing a composition for forming a gel polymer electrolyte.

[0323] Comparative Example 1: Use of gel polymer formed using DPHA

[0324] A lithium battery was manufactured in the same manner as in Example 2, except that DPHA was used as a polymerizable monomer in the preparation of a composition for forming a gel polymer electrolyte.

[0325] Comparative Example 2: Use of a gel polymer formed using a bifunctional monomer (PEO-DMA) + DRIC

[0326] A lithium battery was manufactured in the same manner as in Example 2, except that a bifunctional monomer, polyethylene glycol dimethacrylate (PEO-DMA), was used instead of DPHA as a polymerizable monomer when manufacturing a composition for forming a gel polymer electrolyte. PEO-DMA is poly(ethylene glycol) dimethacrylate disclosed in Example 2C of WO2017 / 153310A.

[0327] Comparative Example 3

[0328] A lithium battery was manufactured in the same manner as in Example 2, except that only DRIC was used as a polymerizable monomer in the preparation of a composition for forming a gel polymer electrolyte.

[0329] Evaluation Example 1: High Temperature (45℃) Lifespan

[0330] The charge / discharge characteristics of the lithium batteries of Example 1-5 and Comparative Example 1-3 were evaluated under the following conditions.

[0331] The battery was charged at a constant current of 0.1 C rate at 45°C until the voltage reached 4.3 V (vs. Li), and then cut-off at a current of 0.05 C rate while maintaining 4.3 V in constant voltage mode. Subsequently, the battery was discharged at a constant current of 0.1 C rate until the voltage reached 3.6 V (vs. Li) during discharge (formation cycle).

[0332] The lithium battery, which had undergone a Mars cycle, was charged at a constant current of 0.2 C rate at 25°C until the voltage reached 4.3 V (vs. Li), and then cut-off at a current of 0.05 C rate while maintaining 4.3 V in constant voltage mode. Subsequently, the battery was discharged at a constant current of 0.5 C rate until the voltage reached 3.6 V (vs. Li) (1 st cycle). These cycles are 300 th The cycle was repeated under the same conditions.

[0333] In all charge / discharge cycles, a 10-minute pause was placed after each charge / discharge cycle. Some of the results of the high-temperature charge / discharge experiments are shown in Table 1 and Figures 6a and 6b below. Figure 7a shows the life characteristics after 200 cycles for the lithium batteries of Examples 1-2 and Comparative Example 1, and Figure 7b shows the change in capacity characteristics after 200 cycles for the lithium batteries of Examples 1-2 and Comparative Example 1.

[0334] In addition, the life characteristics were evaluated according to the following equation 1 and are shown in Table 1 below.

[0335] <Formula 1>

[0336] Lifespan (%) = (300 discharge capacity / 2 discharge capacity) X 100

[0337] In Table 1 below, the cycle number refers to the number of cycles required for the discharge capacity to decrease to 80% of the standard capacity after the second cycle. As the cycle number increases, it is considered that the battery has better life characteristics.

[0338] Classification Condition Initial Efficiency (%) Cycle Count (%) Lifespan (%) Example 1 Gel polymer formed using GPE (DPHA + DRIC 2:2 weight ratio + LE (0.6 M LiDFOB + 0.6 M LiBF4 in FEC:DEC (1:2 v / v) 76.41 15 24 1.31 Example 2 Gel polymer formed using GPE (DPHA + DRIC 3:1 weight ratio + LE (0.6 M LiDFOB + 0.6 M LiBF4 in FEC:DEC (1:2 v / v) 76.75 18 6 5 8.71 Example 3 Gel polymer formed using GPE (DPHA + DRIC 5:1 weight ratio + LE (0.6 M LiDFOB + 0.6 M LiBF4 in FEC:DEC (1:2 v / v) 76.59 17 7 5 2.3 Example 4GPE(DPHA+DUDMA Gel polymer formed using 3:1 weight ratio+LE(0.6M LiDFOB + 0.6M LiBF4 in FEC:DEC(1:2 v / v)76.7717253.4Example 5GPE(TMPTMA+DRIC Gel polymer formed using 3:1 weight ratio+LE(0.6M LiDFOB + 0.6M LiBF4 in FEC:DEC(1:2 v / v)77.0213739.3Comparative Example 1GPE: DPHA76.8157-Comparative Example 2GPE: PEO-DMA+DRIC76.5537-Comparative Example 3GPE: DRIC73.1789-

[0339] In Table 1 above, “-“ indicates that the battery was not operating and thus measurement was not possible. As shown in Table 1, it was found that the lithium battery of Example 1-5 had improved high-temperature life characteristics compared to Comparative Example 1-3.

[0340] The lithium battery of Comparative Example 1 showed a similar initial efficiency to the lithium metal batteries of Examples 1 and 2, but the room temperature life was significantly reduced compared to the lithium batteries of Examples 1-5.

[0341] Evaluation Example 2: Ionic Conductivity

[0342] The ionic conductivity of the gel polymer electrolyte used in the lithium battery of Example 2-4 at room temperature (25°C) and high temperature (45°C) was investigated and is shown in Table 2 below and Figures 7a and 7b. The ionic conductivity was measured by applying a voltage bias of 10 mV to the gel polymer electrolyte in the frequency range of 1 Hz to 1 MHz, scanning the temperature, and measuring the resistance.

[0343] Figure 7a shows the ionic conductivity at room temperature for the gel polymer electrolyte in the lithium batteries of Example 2 and Comparative Example 1, and Figure 7b shows the ionic conductivity at high temperature for the gel polymer electrolyte in the lithium batteries of Example 2 and Comparative Example 1.

[0344] ClassificationRoom temperature ionic conductivity (mS / cm)High temperature ionic conductivity (mS / cm)Example 20.470.71Example 30.450.63Example 40.440.70Comparative example 10.430.61

[0345] As shown in Table 2, the gel polymer electrolyte used in the lithium battery of Example 2-4 showed an ionic conductivity of 0.44 mS / cm or more at 25 ℃ and 1 atm, and an ionic conductivity of 0.63 mS / cm or more at 45 ℃ and 1 atm.

[0346] Among them, it was found that the gel polymer electrolyte of the lithium battery of Example 2 had improved ionic conductivity at room temperature and high temperature compared to the gel polymer electrolyte of Comparative Example 1, as shown in FIGS. 7a and 7b.

[0347] Evaluation Example 3: High-rate characteristics

[0348] The lithium batteries manufactured in Example 1-5 and Comparative Example 1-3 were charged at a constant current of 0.1 C rate at 25°C until the voltage reached 4.3 V (vs. Li), and then cut-off at a current of 0.05 C rate while maintaining 4.3 V in constant voltage mode. Subsequently, the batteries were discharged at a constant current of 0.1 C rate until the voltage reached 3.6 V (vs. Li) during discharge (formation cycle).

[0349] The lithium battery that had undergone the Mars cycle was charged at a constant current of 0.2 C rate at 25°C until the voltage reached 4.3 V (vs. Li), and then cut-off at a current of 0.05 C rate while maintaining 4.3 V in constant voltage mode. Subsequently, the battery was discharged at a constant current of 0.2 C rate until the voltage reached 3.6 V (vs. Li) (4 st cycle).

[0350] 1 st The cycled lithium battery was charged at a constant current of 0.2 C at 25°C until the voltage reached 4.3 V (vs. Li), and then cut off at a current of 0.05 C while maintaining 4.3 V in constant voltage mode. Subsequently, the battery was discharged at a constant current of 0.5 C until the voltage reached 2.8 V (vs. Li) (5 st cycle).

[0351] 5 nd Cycle 9 th The cycle was repeated under the same conditions.

[0352] 7 thThe cycled lithium battery was charged at a constant current of 0.33 C at 25°C until the voltage reached 4.35 V (vs. Li), and then cut off at a current of 0.05 C while maintaining 4.35 V in constant voltage mode. Subsequently, the battery was discharged at a constant current of 3 C until the voltage reached 2.8 V (vs. Li) (13 st cycle).

[0353] 8th cycle 18 th The cycle was repeated under the same conditions.

[0354] 17 th The cycled lithium battery was charged at a constant current of 0.33 C at 25°C until the voltage reached 4.35 V (vs. Li), and then cut off at a current of 0.05 C while maintaining 4.35 V in constant voltage mode. Subsequently, the battery was discharged at a constant current of 3 C until the voltage reached 2.8 V (vs. Li) (19 th cycle).

[0355] 19 th Cycle 23 th The cycle was repeated under the same conditions.

[0356] 23 st The cycled lithium battery was charged at a constant current of 0.33 C at 25°C until the voltage reached 4.35 V (vs. Li), and then cut off at a current of 0.05 C while maintaining 4.35 V in constant voltage mode. Subsequently, the battery was discharged at a constant current of 0.2 C until the voltage reached 2.8 V (vs. Li) (24 th cycle).

[0357] 24 stThe cycled lithium battery was charged at a constant current of 0.33 C at 25°C until the voltage reached 4.35 V (vs. Li), and then cut off at a current of 0.05 C while maintaining 4.35 V in constant voltage mode. Subsequently, the battery was discharged at a constant current of 0.5 C until the voltage reached 2.8 V (vs. Li) (25 th cycle). 25 th Cycle 30 th The cycle was repeated under the same conditions.

[0358] In all the above charge / discharge cycles, a pause of 10 minutes was allowed after each charge / discharge cycle.

[0359] Some of the results of the above charge-discharge experiment are shown in Table 3 below.

[0360] The high-rate characteristic is defined by Equation 2 below.

[0361] <Formula 2>

[0362] High rate characteristic [%] = [23 st Discharge capacity in cycle (3C rate) / 2 nd Discharge capacity in cycle (0.2C rate)] × 100

[0363] Distinction Condition High Rate Characteristics (%) Example 1 Gel polymer formed using GPE (DPHA + DRIC 2:2 weight ratio + LE (0.6 M LiDFOB + 0.6 M LiBF4 in FEC:DEC (1:2 v / v) 40.4 Example 2 Gel polymer formed using GPE (DPHA + DRIC 3:1 weight ratio + LE (0.6 M LiDFOB + 0.6 M LiBF4 in FEC:DEC (1:2 v / v) 43.2 Example 3 Gel polymer formed using GPE (DPHA + DRIC 5:1 weight ratio + LE (0.6 M LiDFOB + 0.6 M LiBF4 in FEC:DEC (1:2 v / v) 42.1 Example 4 Gel polymer formed using GPE (DPHA + DUDMA 3:1 weight ratio + LE (0.6 M LiDFOB + 0.6 M LiBF4 in FEC:DEC LiBF4 in FEC:DEC(1:2 v / v)44.5Example 5GPE(Gel polymer formed using PETA+DRIC 3:1 weight ratio+LE(0.6M LiDFOB + 0.6M LiBF4 in FEC:DEC(1:2 v / v)41.5Comparative Example 1GPE: DPHA38.3Comparative Example 2GPE: PEO-DMA+DRIC19.7Comparative Example 3GPE: DRIC22.5

[0364] As shown in Table 3, the lithium battery of Examples 1-5 showed improved high-rate characteristics compared to Comparative Examples 1-2. While exemplary embodiments have been described in detail with reference to the attached drawings, the present invention is not limited to these examples. It is obvious that a person skilled in the art to which the present invention pertains can devise various modifications or variations within the scope of the technical concepts described in the claims, and these also naturally fall within the technical scope of the present invention.

Claims

1. A gel polymer electrolyte for a lithium battery comprising a gel polymer and a liquid electrolyte. The above liquid electrolyte contains a lithium salt and an organic solvent, A gel polymer electrolyte for a lithium battery, wherein the above gel polymer is a crosslinked product of i) a first polymerizable monomer having three or more polymerizable functional groups, and ii) a second polymerizable monomer selected from among urethane acrylic monomers having two or more functional groups.

2. In the first paragraph, the first polymerizable monomer is trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane ethoxylate triacrylate, trimethylolpropane propoxylate triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol ethoxylate tetraacrylate, dipentaerythritol pentaacrylate. A gel polymer electrolyte for a lithium battery, comprising: dipentaerythritol pentaacrylate (DPHA), dipentaerythritol hexaacrylate (DPHA), or a combination thereof.

3. A gel polymer electrolyte for a lithium battery in the first paragraph, wherein the second polymerizable monomer is a compound represented by the following chemical formula 1, a compound represented by the following chemical formula 2, or a combination thereof: <Chemical Formula 1> In chemical formula 1, R a and R b are identical or different from each other, and are substituted or unsubstituted C1- C10 is an alkylene group, EG is a residue of ethylene glycol, DEG is a residue of diethylene glycol, TMP is a residue of trimethylolpropane, and n is an integer from 1 to 100. <Chemical Formula 2> In chemical formula 2, each R independently represents a hydrogen atom, a C1-C3 alkyl group, or a combination thereof.

4. In the third paragraph, a gel polymer electrolyte for a lithium battery, wherein the compound represented by the chemical formula 1 is a compound represented by the following chemical formula 3: <Chemical Formula 3> In chemical formula 3, EG is a residue of ethylene glycol, DEG is a residue of diethylene glycol, TMP is a residue of trimethylolpropane, and n is an integer from 1 to 100.

5. A gel polymer electrolyte for a lithium battery, wherein the mixing weight ratio of the first polymerizable monomer and the second polymerizable monomer in the first paragraph is 10:1 to 1:

10.

6. A gel polymer electrolyte for a lithium battery, wherein the content of the gel polymer in the first paragraph is 1 to 10 parts by weight based on 100 parts by weight of the total weight of the gel polymer electrolyte.

7. In the first paragraph, the lithium salt includes a first lithium salt and a second lithium salt, and the first lithium salt and the second lithium salt independently include a fluorine-containing borate lithium salt. A gel polymer electrolyte for a lithium battery, wherein the fluorine-containing borate lithium salt comprises LiBF4, LiBF3(C2F5), a compound represented by the following chemical formulas 1-1 to 12-1, or a combination thereof. <Chemical Formula 1-1> <Chemical Formula 1-2> <Chemical Formula 1-3> <Chemical Formula 1-4> <Chemical Formula 1-5> <Chemical Formula 1-6> <Chemical Formula 1-7> <Chemical Formula 1-8> <Chemical Formula 1-9> <Chemical Formula 1-10> <Chemical Formula 1-11> <Chemical Formula 1-12> 8. In the 7th paragraph, the first lithium salt contains LiBF4, A gel polymer electrolyte for a lithium battery, wherein the second lithium salt comprises a compound selected from compounds represented by the chemical formulas 1-1 to 1-12.

9. A gel polymer electrolyte for a lithium battery, wherein in paragraph 7, the contents of the first lithium salt and the second lithium salt are each more than 0 and less than or equal to 1.2 M, and the weight ratio of the first lithium salt and the second lithium salt is 1:9 to 9:

1.

10. A gel polymer electrolyte for a lithium battery, wherein the organic solvent in the first paragraph comprises at least one selected from a carbonate compound, an ester compound, an ether compound, a nitrile compound, and a ketone compound.

11. In the first paragraph, the organic solvent contains a carbonate compound, The above carbonate compounds include fluoroethylene carbonate (FEC) and diethyl carbonate (DEC). A gel polymer electrolyte for a lithium battery, wherein the mixing weight ratio of the above FEC and DEC is 1:10 to 1:

1.

12. A lithium battery comprising a positive electrode, a negative electrode current collector, and an electrolyte layer disposed between the positive electrode and the negative electrode current collector, A lithium battery, wherein the electrolyte layer comprises a gel polymer electrolyte according to any one of claims 1 to 11.

13. A lithium battery according to claim 12, further comprising a lithium metal layer between the negative electrode collector and the electrolyte layer, wherein the lithium metal layer comprises a lithium metal foil, a lithium metal powder, a lithium alloy foil, a lithium alloy powder, or a combination thereof.

14. A lithium battery according to claim 12, wherein the electrolyte layer includes a separator, and the separator includes a porous substrate.

15. In the 14th paragraph, the porous substrate is a porous membrane, The above porous membrane is a woven or non-woven fabric, The above porous substrate comprises an olefin resin, a fluorine resin, an ester resin, an imide resin, an acrylic resin, a cellulose resin or a combination thereof. The above olefin resin includes polyethylene, polypropylene or a combination thereof, The above fluorine resin includes polyvinylidene fluoride, polytetrafluoroethylene or a combination thereof, The above ester resin includes polyethylene terephthalate, polybutylene terephthalate or a combination thereof, The above imide resin includes polyamideimide, polyetherimide or a combination thereof, The above acrylic resin includes polyacrylonitrile, polyacrylate or a combination thereof, A lithium battery, wherein the cellulose-based resin comprises carboxymethyl cellulose, microbial cellulose, plant cellulose, animal cellulose, or a combination thereof.

16. A lithium battery in claim 12, wherein the negative electrode collector comprises copper (Cu), nickel (Ni), nickel-coated copper, stainless steel (SUS), iron (Fe), cobalt (Co), or an alloy thereof.

17. In the 12th paragraph, the lithium battery comprises a negative electrode active material layer, a protective layer, or a combination thereof between the negative electrode current collector and the electrolyte layer.

18. In the 13th paragraph, the lithium alloy contains lithium and a first metal, A lithium battery wherein the first metal is indium (In), silicon (Si), gallium (Ga), tin (Sn), aluminum (Al), titanium (Ti), zirconium (Zr), niobium (Nb), germanium (Ge), antimony (Sb), bismuth (Bi), gold (Au), platinum (Pt), palladium (Pd), magnesium (Mg), silver (Ag), zinc (Zn), nickel, iron, cobalt, chromium, cesium, sodium, potassium, calcium, yttrium, bismuth, tantalum, hafnium, barium, vanadium, strontium, lanthanum or a combination thereof.

19. A lithium battery according to claim 12, wherein the ionic conductivity of the gel polymer electrolyte at 25°C and 1 atm is 0.44 mS / cm or more, and the ionic conductivity at 45°C and 1 atm is 0.63 mS / cm or more.

20. In paragraph 12, The above positive electrode includes a positive electrode current collector and a positive electrode active material layer, At least one of the positive electrode current collector and the negative electrode current collector includes a base film and a metal layer disposed on one or both sides of the base film, The above base film comprises a polymer, and the polymer comprises polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polybutylene terephthalate (PBT), polyimide (PI) or a combination thereof. A lithium battery, wherein the metal layer comprises indium (In), copper (Cu), magnesium (Mg), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), lithium (Li), or an alloy thereof.

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