KR20220109584A - Electrolyte for lithium secondary battery and lithium secondary battery comprising the same - Google Patents

Abstract

The present invention relates to an electrolyte for a lithium secondary battery and a lithium-sulfur secondary battery including the same, wherein the electrolyte for a lithium secondary battery includes: a first solvent including a heterocyclic compound including at least one double bond and at the same time including any one of an oxygen atom and a sulfur atom; a second solvent including at least one of an ether-based compound, an ester-based compound, an amide-based compound, and a carbonate-based compound; lithium salt; lithium nitrate; and an additive for an organic redox mediator (ORM).

Description

Electrolyte for lithium secondary battery and lithium secondary battery comprising same

The present invention relates to an electrolyte solution for a lithium secondary battery and a lithium secondary battery comprising the same, and more particularly, by appropriately combining a solvent, a lithium salt and an additive included in the electrolyte solution of a lithium secondary battery, the lifespan characteristics of a lithium secondary battery and lithium It relates to an electrolyte solution for a lithium secondary battery capable of improving cycle efficiency, and a lithium secondary battery including the same.

As the application area of secondary batteries expands to electric vehicles (EVs) and energy storage devices (ESS), lithium-ion secondary batteries with a relatively low energy storage density (~250 Wh/kg) to weight ratio are suitable for these products. There are limits to its application. In contrast, lithium-sulfur secondary batteries are in the spotlight as a next-generation secondary battery technology because they can theoretically implement high energy storage density (~2,600 Wh/kg) compared to weight.

A lithium-sulfur secondary battery refers to a battery system in which a sulfur-based material having an S-S bond is used as a positive electrode active material and lithium metal is used as a negative electrode active material. Sulfur, which is the main material of the positive electrode active material, is advantageous in that it has abundant resources worldwide, is non-toxic, and has a low weight per atom.

In a lithium-sulfur secondary battery, lithium, which is an anode active material, is ionized by releasing electrons during discharging and is oxidized, and a sulfur-based material, a cathode active material, is reduced by accepting electrons. Here, the oxidation reaction of lithium is a process in which lithium metal is converted into a lithium cation form by giving up electrons. In addition, the reduction reaction of sulfur is a process in which the SS bond accepts two electrons and is converted into a sulfur anion form. The lithium cation generated by the oxidation reaction of lithium is transferred to the positive electrode through the electrolyte, and combines with the sulfur anion generated by the reduction reaction of sulfur to form a salt. Specifically, sulfur before discharge has a cyclic S ₈ structure, which is converted into lithium polysulfide (LiS _x ) by a reduction reaction. When lithium polysulfide is completely reduced, lithium sulfide (Li ₂ S) is generated.

Since sulfur, which is a cathode active material, has low electrical conductivity, it is difficult to secure reactivity with electrons and lithium ions in a solid state. Existing lithium-sulfur secondary batteries induce a liquid phase reaction and improve reactivity by generating an intermediate polysulfide in the form of Li ₂ S _x to improve the reactivity of sulfur. In this case, an ether-based solvent such as dioxolane or dimethoxyethane, which is highly soluble in lithium polysulfide, is used as a solvent of the electrolyte solution.

However, when such an ether-based solvent is used, there is a problem in that the lifespan characteristics of the lithium-sulfur secondary battery are deteriorated due to various causes. For example, the lifespan characteristics of the lithium-sulfur secondary battery may be deteriorated due to the elution of lithium polysulfide from the positive electrode, the occurrence of a short due to the growth of dendrites on the lithium negative electrode, and the deposition of by-products due to the decomposition of the electrolyte. can

In particular, when such an ether-based solvent is used, a large amount of lithium polysulfide can be dissolved and the reactivity is high. However, due to the characteristics of lithium polysulfide soluble in the electrolyte, the reactivity and lifespan characteristics of sulfur are affected according to the content of the electrolyte.

In order to develop a high-energy-density lithium-sulfur secondary battery of 500Wh/kg or more required for recent aircraft and next-generation electric vehicles, it is required that the loading amount of sulfur in the electrode is large and the content of the electrolyte is minimized.

However, due to the characteristics of the ether-based solvent, as the content of the electrolyte decreases, the viscosity increases rapidly during charging and discharging, thereby causing overvoltage and deterioration.

Accordingly, research on adding a separate additive to the electrolyte to prevent decomposition of the electrolyte and secure excellent lifespan characteristics is continuously being conducted. Nevertheless, the components and compositions of the electrolyte, which can improve lifespan characteristics and lithium cycle efficiency, have not been clearly identified.

Japanese Patent Laid-Open No. 2013-016456 Korean Patent Publication No. 2020-0076074

Accordingly, in the present invention, in order to improve the lifespan characteristics and lithium cycle efficiency of a lithium secondary battery, the electrolyte solution for a lithium secondary battery contains one or more double bonds and a heterocyclic compound containing any one of an oxygen atom and a sulfur atom. By including a first solvent, an ether-based compound, an ester-based compound, a second solvent including any one or more of an amide-based compound and a carbonate-based compound, lithium salt, lithium nitrate, and an additive for ORM, - The present invention was completed by confirming that the performance of the sulfur secondary battery could be improved.

Accordingly, an object of the present invention is to provide an electrolyte solution for a lithium-sulfur secondary battery capable of improving the lifespan characteristics and lithium cycle efficiency of a lithium-sulfur secondary battery. In addition, another object of the present invention is to provide a lithium-sulfur secondary battery having improved battery performance by providing the electrolyte solution.

In order to achieve the above object, the present invention, a first solvent comprising a heterocyclic compound containing one or more double bonds and at the same time containing any one of an oxygen atom and a sulfur atom; a second solvent including at least one of an ether-based compound, an ester-based compound, an amide-based compound, and a carbonate-based compound; lithium salt; lithium nitrate; and an additive for ORM; provides an electrolyte solution for a lithium secondary battery comprising.

In addition, the present invention, the positive electrode; cathode; a separator interposed between the anode and the cathode; and an electrolyte solution for the lithium secondary battery.

According to the electrolyte solution for a lithium secondary battery according to the present invention and a lithium secondary battery comprising the same, the electrolyte of the lithium secondary battery contains one or more double bonds and a heterocyclic compound containing one of an oxygen atom and a sulfur atom. A lithium secondary battery comprising the electrolyte solution by including a second solvent, lithium salt, lithium nitrate, and an ORM additive for one solvent, an ether-based compound, an ester-based compound, an amide-based compound, and a carbonate-based compound It shows the effect of improving the lifespan characteristics and lithium cycle efficiency.

1 is a graph showing high-rate discharge characteristics of lithium-sulfur secondary batteries prepared according to Examples 1 to 3 and Comparative Example 1 of the present invention.
2 is a graph showing the lifespan characteristics of lithium-sulfur secondary batteries prepared according to Examples 1 to 3 and Comparative Example 1 of the present invention.

Hereinafter, the present invention will be described in detail.

The embodiments provided according to the present invention can all be achieved by the following description. It is to be understood that the following description is to be understood as describing preferred embodiments of the present invention, and the present invention is not necessarily limited thereto.

The present invention, A) a first solvent comprising a heterocyclic compound containing at least one double bond and at the same time containing any one of an oxygen atom and a sulfur atom; B) a second solvent comprising at least one of an ether-based compound, an ester-based compound, an amide-based compound, and a carbonate-based compound; C) lithium salts; D) lithium nitrate; and E) an additive for ORM; provides an electrolyte solution for a lithium secondary battery comprising.

Hereinafter, each of A) the first solvent, B) the second solvent, C) lithium salt, D) lithium nitrate, and E) the additive for ORM included in the electrolyte solution for a lithium secondary battery of the present invention will be described in detail.

A) first solvent

The electrolyte solution for a lithium secondary battery according to the present invention may include a first solvent including a heterocyclic compound including at least one double bond and at the same time containing any one of an oxygen atom and a sulfur atom.

The first solvent may include a heterocyclic compound containing one or more double bonds and at the same time containing any one of an oxygen atom and a sulfur atom. The heterocyclic compound has a property that it is difficult to dissolve a salt due to delocalization of lone pair electrons of a hetero atom (oxygen atom or sulfur atom).

In a lithium secondary battery using a lithium-based metal as a negative electrode, a polymer protective film (solid electrolyte) on the surface of the lithium-based metal (cathode) by a ring opening reaction of the heterocyclic compound in the initial discharge stage of the battery interface, SEI layer), thereby suppressing the generation of lithium dendrites, and further improving the lifespan characteristics of the lithium secondary battery by reducing the decomposition of the electrolyte on the surface of the lithium-based metal and consequent side reactions can do it

Therefore, in the heterocyclic compound of the present invention, in order to form a polymer protective film on the surface of the lithium-based metal, it is essential that at least one double bond is present. In addition, the heterocyclic compound of the present invention contains oxygen or sulfur to make it polar, thereby increasing affinity with other organic solvents of the electrolyte to facilitate utilization as a component of the electrolyte, so that the hetero atom (oxygen atom or sulfur atom ) must also be included.

The heterocyclic compound may be a 3 to 15 membered, preferably 3 to 7 membered, more preferably 5 to 6 membered heterocyclic compound. In addition, such a heterocyclic compound is an alkyl group having 1 to 4 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a halogen group, a nitro group (-NO ₂ ), an amine group (-NH ₂ ) and a sulfonyl group (-SO ₂ ) It may be a heterocyclic compound substituted or unsubstituted with one or more selected from the group consisting of. In addition, the heterocyclic compound may be a multicyclic compound of a heterocyclic compound with at least one of a cyclic alkyl group having 3 to 8 carbon atoms and an aryl group having 6 to 10 carbon atoms.

When the heterocyclic compound is substituted with an alkyl group having 1 to 4 carbon atoms, it is preferable because the radicals are stabilized and side reactions between the electrolytes can be suppressed. In addition, when substituted with a halogen group or a nitro group, it is preferable to form a functional protective film on the surface of the lithium-based metal, in this case, the formed functional protective film is stable as a compact protective film, and There are advantages in that uniform deposition is possible and a side reaction between polysulfide and lithium-based metal can be suppressed.

Specific examples of the heterocyclic compound include furan (furan), 2-methylfuran (2-methylfuran), 3-methylfuran (3-methylfuran), 2-ethylfuran (2-ethylfuran), 2-propylfuran (2 -propylfuran), 2-butylfuran (2-butylfuran), 2,3-dimethylfuran (2,3-dimethylfuran), 2,4-dimethylfuran (2,4-dimethylfuran), 2,5-dimethylfuran (2 ,5-dimethylfuran), pyran, 2-methylpyran, 3-methylpyran, 4-methylpyran, benzofuran, 2-( 2-nitrovinyl)furan (2-(2-Nitrovinyl)furan), thiophene, 2-methylthiophene, 2-ethylthiophene (2-ethylthiphene), 2-propylthiophene (2-propylthiophene), 2-butylthiophene, 2,3-dimethylthiophene, 2,4-dimethylthiophene, and 2,5 -Dimethylthiophene (2,5-dimethylthiophene) and the like, and preferably 2-methylfuran.

The content of the first solvent containing such a heterocyclic compound is 5% to 50% by volume based on the total volume of the organic solvent (ie, the first solvent + the second solvent) included in the lithium-sulfur secondary battery electrolyte of the present invention. %, preferably 10% by volume to 40% by volume, and more preferably 10% by volume to 30% by volume (the remainder corresponds to the second solvent). When the content of the first solvent is less than the above range, the ability to reduce the elution amount of polysulfide is reduced, so that it is impossible to suppress the increase in the resistance of the electrolyte solution, or a problem that a protective film is not completely formed on the surface of the lithium-based metal may occur. have. In addition, when the content of the first solvent exceeds the above range, there is a risk that the capacity and lifespan of the battery may decrease due to an increase in the surface resistance of the electrolyte and the lithium-based metal. Accordingly, the content of the first solvent preferably satisfies the above range.

B) second solvent

The electrolyte for a lithium secondary battery according to the present invention may include a second solvent including any one or more of an ether-based compound, an ester-based compound, an amide-based compound, and a carbonate-based compound.

The second solvent may include any one or more of an ether-based compound, an ester-based compound, an amide-based compound, and a carbonate-based compound. The second solvent not only dissolves the lithium salt so that the electrolyte has lithium ion conductivity, but also elutes sulfur, which is the positive electrode active material, to facilitate an electrochemical reaction with lithium. The carbonate-based compound may be a linear carbonate-based compound or a cyclic carbonate-based compound.

Specific examples of the ether-based compound include dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methyl propyl ether, ethyl propyl ether, dimethoxyethane, diethoxyethane, methoxyethoxyethane, diethylene glycol dimethyl Ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol methyl ethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetra At least one selected from the group consisting of ethylene glycol methyl ethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol diethyl ether, and polyethylene glycol methyl ethyl ether may be exemplified, but not limited thereto, preferably dimethoxyethanyl can

In addition, as the ester-based compound, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, γ-butyrolactone, γ-valerolactone, γ-caprolactone, σ - At least one member selected from the group consisting of -valerolactone and ε-caprolactone may be exemplified, but the present invention is not limited thereto. In addition, the amide-based compound may be a conventional amide-based compound used in the art.

In addition, as the linear carbonate-based compound, dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethylmethyl carbonate (EMC), methylpropyl At least one selected from the group consisting of carbonate (methylpropyl carbonate, MPC) and ethylpropyl carbonate (EPC) may be exemplified, but the present invention is not limited thereto.

In addition, as the cyclic carbonate-based compound, ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate , 2,3-pentylene carbonate, vinylene carbonate, vinylethylene carbonate, and at least one selected from the group consisting of halides thereof (fluoroethylene carbonate (FEC), etc.), The present invention is not limited thereto.

On the other hand, when the second solvent is included in an amount less than an appropriate amount, there is a risk that the lithium salt cannot be sufficiently dissolved, so that the lithium ion conductivity is lowered and the active material sulfur is precipitated in excess of the soluble concentration. When included, sulfur, which is a positive electrode active material, is excessively eluted, which may cause a problem in that the shuttle phenomenon between lithium polysulfide and the lithium negative electrode is severe and the lifespan is reduced.

On the other hand, the organic solvent comprising the first solvent and the second solvent is 70 to 97 wt%, preferably 75 to 96 wt%, more preferably 80 to the total weight of the lithium-sulfur secondary battery electrolyte of the present invention. to 95% by weight. If the organic solvent is included in less than 70% by weight based on the total weight of the lithium-sulfur secondary battery electrolyte, the electrolyte viscosity increases, the ionic conductivity decreases, or the lithium salt or additive is not completely dissolved in the electrolyte. may occur, and when it is included in an amount exceeding 97 wt %, the lithium salt concentration in the electrolyte is lowered and there may be a problem in that the ionic conductivity is reduced, so the content of the first solvent and the second solvent satisfies the above range It is preferable to do

In addition, the volume ratio of the first solvent and the second solvent may be 1:0.5 to 1:6, preferably 1:2.5 to 1:6, more preferably 1:4 to 1:6 can be When the volume ratio of the first solvent and the second solvent is less than the above range, there is a risk that the lithium salt cannot be sufficiently dissolved, so that the lithium ion conductivity is lowered and the active material, sulfur, is precipitated in excess of the soluble concentration. And, when the volume ratio of the first solvent and the second solvent exceeds the above range, sulfur, which is a positive electrode active material, is excessively eluted, resulting in severe shuttle phenomenon between lithium polysulfide and lithium negative electrode and a decrease in lifespan. Therefore, the volume ratio of the first solvent and the second solvent preferably satisfies the above range.

C) lithium salt

The electrolyte for a lithium secondary battery according to the present invention may include a lithium salt as an electrolyte salt used to increase ion conductivity.

Examples of the lithium salt include LiCl, LiBr, LiI, LiClO ₄ , LiBF ₄ , LiB ₁₀ Cl ₁₀ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , LiC ₄ BO ₈ , LiAsF ₆ , LiSbF ₆ , LiAlCl ₄ , CH ₃ SO ₃ Li, CF ₃ SO ₃ Li, (C ₂ F ₅ SO ₂ ) ₂ NLi, (SO ₂ F) ₂ NLi, (CF ₃ SO ₂ ) ₃ CLi, chloroborane lithium, lower aliphatic car with 4 or less carbon atoms At least one selected from the group consisting of lithium main acid, 4-phenyl lithium borate, and lithium imide may be mentioned, but is not limited thereto, and preferably LiFSI ((SO ₂ F) ₂ NLi) is included as an essential component. can do.

The concentration of the lithium salt may be determined in consideration of ionic conductivity and the like, and may be, for example, 0.2M to 2M, preferably 0.5M to 1M. When the concentration of the lithium salt is less than the above range, it may be difficult to secure ionic conductivity suitable for driving a battery. Since the reaction may increase and the performance of the battery may be deteriorated, the concentration of the lithium salt preferably satisfies the above range.

D) lithium nitrate

In addition, the electrolyte for a lithium secondary battery according to the present invention may include lithium nitrate (LiNO ₃ ). However, if necessary, lanthanum nitrate (La(NO ₃ ) ₃ ), potassium nitrate (KNO ₃ ), cesium nitrate (CsNO ₃ ), magnesium nitrate (MgNO ₃ ), barium nitrate (BaNO ₃ ), lithium nitrite (LiNO ₂ ) , potassium nitrite (KNO ₂ ) and cesium nitrite (CsNO ₂ ) It may further include one or more selected from the group consisting of.

The lithium nitrate may be included in an amount of 1 to 7% by weight, preferably 2 to 6% by weight, and more preferably 3 to 5% by weight based on the total weight of the electrolyte for a lithium secondary battery. When the content of the lithium nitrate is less than 1 wt % based on the total weight of the electrolyte for a lithium secondary battery, the coulombic efficiency may be sharply lowered, and if it exceeds 7 wt %, the viscosity of the electrolyte may increase and driving may be difficult. Accordingly, the content of the lithium nitrate preferably satisfies the above range.

E) Additives for ORM (Organic Redox Mediator)

The electrolyte for a lithium secondary battery according to the present invention may include an additive for an organic redox mediator (ORM).

For the ORM (Organic Redox Mediator) The additive is an additive serving as an ORM, and may improve overvoltage, and may improve high-rate discharge performance, thereby improving the output of the battery.

The additive for ORM is 2-methyl-1,4-naphtoquinone (2-methyl-1,4-naphtoquinone), pyrroloquinoline quinone, 8-hydroxyquinoline-5-sulfonic acid (8- hydroxyquinoline-5-sulfonic acid), Phenazine methosulfate, Tetrathiafulvalence, Poly(vinylferrocene), 1-hydroxybenzotriazole (1-hydroxybenzotriazole, HBT) ), N-hydroxyphthalimide (HPI), 2,2,6,6-tetramethyl-1-piperidinyloxy (2,2,6,6-Tetramethyl-1-piperidinyloxy, TEMPO ), violuric acid (VA), syringaldehyde (SA), vanillin (Vanillin, VA), 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) D Ammonium salt (2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt, ABTS), 9,10-anthraquinone-2,7-disulfonic acid (9,10-Anthraquinone-2,7 -disulphonic acid), dimethylphenazine (Dimethylphenazine, DMPZ), lithium bromide (LiBr), lithium iodide (LiI), 1,4-benzoquinone (1,4-Benzoquinone), 2, 3-dichloro-5,6-dicyano-1,4-benzoquinone (2,3-Dichloro-5,6-dicyano-1,4-benzoquinone), phenyl-1,4-benzoquinone (Phenyl-1, 4-benzoquinone), hydroquinone, 2,3-dichloro-5,8-dihydroxy-1,4-naphthoquinone (2,3-Dichloro-5,8-dihydroxy-1,4-naphthoquinone) ), 2-Me Toxy-1,4-benzoquinone (2-Methoxy-1,4-benzoquinone), 2,3-dimethoxy-1,4-benzoquinone (2,3-Dimethoxy-1,4-benzoquinone), 2,6 -Dimethoxy-1,4-benzoquinone (2,3-Dimethoxy-1,4-benzoquinone) and 7,7,8,8-tetracyanoquinodimethane (TCNQ, 7,7,8.8-Tetracyanoquinodimethane) It may include one or more selected from the group consisting of.

In addition, the additive for ORM may be a quinone-based additive, preferably a cyanoquinone-based additive, and the quinone-based additive is 7,7,8,8-tetracyanoquinodimethane (TCNQ, 7,7,8.8-) Tetracyanoquinodimethane), 1,4-benzoquinone (1,4-Benzoquinone), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (2,3-Dichloro-5,6-dicyano-1) ,4-benzoquinone), phenyl-1,4-benzoquinone (Phenyl-1,4-benzoquinone), hydroquinone, 2,3-dichloro-5,8-dihydroxy-1,4-naphtho Quinone (2,3-Dichloro-5,8-dihydroxy-1,4-naphthoquinone), 2-methoxy-1,4-benzoquinone (2-Dimethoxy-1,4-benzoquinone), 2,3-dimethoxy Group consisting of -1,4-benzoquinone (2,3-Dimethoxy-1,4-benzoquinone) and 2,6-dimethoxy-1,4-benzoquinone (2,6-Dimethoxy-1,4-benzoquinone) It may be one or more selected from, preferably 7,7,8,8-tetracyanoquinodimethane (TCNQ, 7,7,8.8-Tetracyanoquinodimethane).

The content of the additive for ORM may be 0.01 wt% to 0.8 wt%, preferably 0.05 wt% to 0.7 wt%, more preferably 0.1 wt%, based on the total weight of the lithium-sulfur secondary battery electrolyte. to 0.6% by weight. If the content of the cyanoquinone-based additive is less than 0.01% by weight, it may not react sufficiently because it is a very small amount and may not have an effect. If it exceeds 0.8% by weight, the resistance in the battery may increase, so the content of the additive for ORM It is preferable to satisfy the above range.

Next, a lithium secondary battery according to the present invention will be described. The lithium secondary battery includes a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte solution for the lithium secondary battery.

As described above, the electrolyte for a lithium secondary battery includes A) a first solvent, B) a second solvent, C) a lithium salt, and D) lithium nitrate and E) an additive for ORM. comply with

In addition, the lithium secondary battery may be a lithium-sulfur secondary battery.

Hereinafter, in the lithium secondary battery according to the present invention, the positive electrode, the negative electrode, and the separator will be described in more detail.

As described above, the positive electrode included in the lithium secondary battery of the present invention includes a positive electrode active material, a binder, a conductive material, and the like. The positive active material may be one applied to a conventional lithium-sulfur secondary battery, and may include, for example, elemental sulfur (S ₈ ), a sulfur-based compound, or a mixture thereof, and the sulfur-based compound Specifically, Li ₂ S _n (n≥1), an organosulfur compound, or a carbon-sulfur complex ((C ₂ S _x ) _n : x=2.5 to 50, n≥2), and the like. In addition, the positive active material may include a sulfur-carbon composite, and since the sulfur material alone does not have electrical conductivity, it may be used in combination with a conductive material. The carbon material (or carbon source) constituting the sulfur-carbon composite may have a porous structure or a high specific surface area, and any one commonly used in the art may be used. For example, the porous carbon material may include graphite; graphene; carbon black such as denka black, acetylene black, ketjen black, channel black, furnace black, lamp black, and summer black; carbon nanotubes (CNTs) such as single-walled carbon nanotubes (SWCNT) and multi-walled carbon nanotubes (MWCNT); carbon fibers such as graphite nanofibers (GNF), carbon nanofibers (CNF), and activated carbon fibers (ACF); And it may be one or more selected from the group consisting of activated carbon, but is not limited thereto, and the shape is spherical, rod-shaped, needle-shaped, plate-shaped, tube-shaped or bulk-shaped, as long as it is applicable to a lithium secondary battery.

In addition, pores are formed in the carbon material, and the porosity of the pores is 40 to 90%, preferably 60 to 80%, and when the porosity of the pores is less than 40%, lithium ion transfer is not performed normally It may cause a problem by acting as a In addition, the pore size of the carbon material is 10 nm to 5 μm, preferably 50 nm to 5 μm. In this case, a battery short circuit and safety problems may occur due to contact between electrodes.

The binder is a component that assists in bonding between the positive electrode active material and the conductive material and bonding to the current collector, for example, polyvinylidene fluoride (PVdF), polyvinylidene fluoride-polyhexafluoropropylene copolymer (PVdF / HFP), polyvinyl acetate, polyvinyl alcohol, polyvinyl ether, polyethylene, polyethylene oxide, alkylated polyethylene oxide, polypropylene, polymethyl (meth) acrylate, polyethyl (meth) acrylate, polytetrafluoroethylene (PTFE) ), polyvinyl chloride, polyacrylonitrile, polyvinylpyridine, polyvinylpyrrolidone, styrene-butadiene rubber, acrylonitrile-butadiene rubber, ethylene-propylene-diene monomer (EPDM) rubber, sulfonated EPDM rubber, styrene - At least one selected from the group consisting of butylene rubber, fluororubber, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, and mixtures thereof may be used, but must be The present invention is not limited thereto.

The binder is usually added in an amount of 1 to 50% by weight, preferably 3 to 15% by weight, based on 100% by weight of the total weight of the positive electrode. If the content of the binder is less than 1% by weight, the adhesive force between the positive electrode active material and the current collector may be insufficient, and if it exceeds 50% by weight, the adhesive strength is improved, but the content of the positive electrode active material is reduced by that amount, thereby lowering the battery capacity.

The conductive material included in the positive electrode is not particularly limited as long as it does not cause side reactions in the internal environment of the lithium secondary battery and has excellent electrical conductivity without causing chemical changes in the battery. Typically, graphite or conductive carbon may be used. and, for example, graphite such as natural graphite and artificial graphite; carbon black, such as carbon black, acetylene black, ketjen black, denka black, thermal black, channel black, furnace black, lamp black, and summer black; a carbon-based material having a crystal structure of graphene or graphite; conductive fibers such as carbon fibers and metal fibers; carbon fluoride; metal powders such as aluminum powder and nickel powder; Conductive whiskey, such as zinc oxide and potassium titanate; conductive oxides such as titanium oxide; and conductive polymers such as polyphenylene derivatives; may be used alone or in mixture of two or more, but is not necessarily limited thereto.

The conductive material is typically added in an amount of 0.5 to 50% by weight, preferably 1 to 30% by weight, based on 100% by weight of the total weight of the positive electrode. If the content of the conductive material is too small, less than 0.5% by weight, it is difficult to expect an effect of improving electrical conductivity or the electrochemical properties of the battery may be deteriorated. This may reduce the capacity and energy density. A method of including the conductive material in the positive electrode is not particularly limited, and a conventional method known in the art, such as coating on the positive electrode active material, may be used. In addition, if necessary, since the second conductive coating layer is added to the positive electrode active material, the addition of the conductive material as described above may be substituted.

In addition, a filler may be selectively added to the positive electrode of the present invention as a component for suppressing its expansion. Such a filler is not particularly limited as long as it can suppress the expansion of the electrode without causing a chemical change in the battery, and for example, an olipine-based polymer such as polyethylene or polypropylene; fibrous materials such as glass fiber and carbon fiber; etc. can be used.

The positive electrode may be manufactured by dispersing and mixing a positive electrode active material, a binder, and a conductive material in a dispersion medium (solvent) to make a slurry, coating it on a positive electrode current collector, and drying and rolling. As the dispersion medium, N-methyl-2-pyrrolidone (NMP), dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), ethanol, isopropanol, water, and mixtures thereof may be used, but is not limited thereto.

As the positive electrode current collector, platinum (Pt), gold (Au), palladium (Pd), iridium (Ir), silver (Ag), ruthenium (Ru), nickel (Ni), stainless steel (STS), aluminum (Al) ), molybdenum (Mo), chromium (Cr), carbon (C), titanium (Ti), tungsten (W), ITO (In doped SnO ₂ ), FTO (F doped SnO ₂ ), and alloys thereof , aluminum (Al) or stainless steel surface treated with carbon (C), nickel (Ni), titanium (Ti) or silver (Ag) may be used, but the present invention is not limited thereto. The shape of the positive electrode current collector may be in the form of a foil, a film, a sheet, a punched body, a porous body, a foam, and the like.

The negative electrode is a lithium-based metal, and may further include a current collector at one side of the lithium-based metal. The current collector may be a negative electrode current collector. The anode current collector is not particularly limited as long as it has high conductivity without causing a chemical change in the battery, and copper, aluminum, stainless steel, zinc, titanium, silver, palladium, nickel, iron, chromium, alloys thereof and these It can be selected from the group consisting of a combination of. The stainless steel may be surface-treated with carbon, nickel, titanium or silver, and an aluminum-cadmium alloy may be used as the alloy. can also be used. In general, a thin copper plate is applied as a negative electrode current collector.

In addition, various forms such as a film, a sheet, a foil, a net, a porous body, a foam body, a nonwoven body, etc. in which fine irregularities are formed/unformed on the surface may be used. In addition, the negative current collector is applied to have a thickness in the range of 3 to 500 ㎛. When the thickness of the negative electrode current collector is less than 3 μm, the current collecting effect is deteriorated, whereas when the thickness exceeds 500 μm, workability is deteriorated when assembling the cell by folding.

The lithium-based metal may be lithium or a lithium alloy. In this case, the lithium alloy includes elements capable of alloying with lithium, and specifically, lithium and Si, Sn, C, Pt, Ir, Ni, Cu, Ti, Na, K, Rb, Cs, Fr, Be, Mg, Ca, It may be an alloy with at least one selected from the group consisting of Sr, Sb, Pb, In, Zn, Ba, Ra, Ge, and Al.

The lithium-based metal may be in the form of a sheet or foil, and in some cases, lithium or a lithium alloy is deposited or coated on the current collector by a dry process, or the metal and alloy on the particles are deposited or coated by a wet process, etc. may be in the form of

A conventional separator may be interposed between the positive electrode and the negative electrode. The separator is a physical separator having a function of physically separating the electrodes, and can be used without any particular limitation as long as it is used as a conventional separator, and in particular, it is preferable to have low resistance to ion movement of the electrolyte and excellent electrolyte moisture content.

In addition, the separator enables transport of lithium ions between the positive electrode and the negative electrode while separating or insulating the positive electrode and the negative electrode from each other. Such a separator may be made of a porous, non-conductive or insulating material. The separator may be an independent member such as a film, or a coating layer added to the positive electrode and/or the negative electrode.

Examples of the polyolefin-based porous membrane that can be used as the separator include polyethylene such as high-density polyethylene, linear low-density polyethylene, low-density polyethylene, and ultra-high molecular weight polyethylene, polyolefin-based polymers such as polypropylene, polybutylene, and polypentene, respectively alone or these and a film formed of a mixed polymer. Examples of the nonwoven fabric that can be used as the separator include polyphenyleneoxide, polyimide, polyamide, polycarbonate, polyethyleneterephthalate, polyethylenenaphthalate. , polybutyleneterephthalate, polyphenylenesulfide, polyacetal, polyethersulfone, polyetheretherketone, polyester, etc. alone or Nonwoven fabrics formed of polymers mixed with these are possible, and such nonwoven fabrics are in the form of fibers forming a porous web, and include a spunbond or meltblown form composed of long fibers.

The thickness of the separator is not particularly limited, but is preferably in the range of 1 to 100 μm, and more preferably in the range of 5 to 50 μm. When the thickness of the separator is less than 1 μm, mechanical properties cannot be maintained, and when it exceeds 100 μm, the separator acts as a resistance layer, and thus the performance of the battery is deteriorated. The pore size and porosity of the separation membrane are not particularly limited, but preferably have a pore size of 0.1 to 50 μm, and a porosity of 10 to 95%. When the pore size of the separator is less than 0.1 μm or the porosity is less than 10%, the separator acts as a resistance layer, and when the pore size exceeds 50 μm or the porosity exceeds 95%, mechanical properties cannot be maintained .

The lithium secondary battery of the present invention, including the positive electrode, the negative electrode, the separator and the electrolyte as described above, faces the positive electrode and the negative electrode and interposes the separator therebetween, and then through the process of injecting the electrolyte for the lithium secondary battery according to the present invention can be manufactured.

On the other hand, the lithium secondary battery according to the present invention is applied to a battery cell used as a power source for a small device, and can be particularly suitably used as a unit cell for a battery module, which is a power source for a medium or large device. In this aspect, the present invention also provides a battery module in which two or more lithium secondary batteries are electrically connected (series or parallel). Of course, the quantity of the lithium secondary battery included in the battery module may be variously adjusted in consideration of the use and capacity of the battery module. Furthermore, the present invention provides a battery pack electrically connected to the battery module according to a conventional technique in the art. The battery module and the battery pack is a power tool (Power Tool); electric vehicles including electric vehicles (EVs), hybrid electric vehicles (HEVs), and plug-in hybrid electric vehicles (PHEVs); electric truck; electric commercial vehicle; Alternatively, it may be used as a power source for any one or more medium or large devices among power storage systems, but is not limited thereto.

Hereinafter, preferred examples are presented to aid the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It goes without saying that such changes and modifications fall within the scope of the appended claims.

Example

Preparation of electrolyte for lithium-sulfur secondary battery

Example 1

In an organic solvent mixed with 2-methylfuran (first solvent) and 1,2-dimethoxyethane (second solvent) in a volume ratio (v/v) of 1:4, 3.0 wt% of lithium nitrate based on the total weight of the electrolyte (LiNO ₃ ) and 0.1% by weight of 7,7,8,8-tetracyanoquinodimethane (TCNQ) were added, and the concentration of lithium bis(fluorosulfonyl)imide (LiFSI) was 0.75M (mol/L) ) to prepare an electrolyte for a lithium-sulfur secondary battery.

Example 2

An electrolyte for a lithium-sulfur secondary battery was prepared in the same manner as in Example 1, except that 0.5% by weight of 7,7,8,8-tetracyanoquinodimethane (TCNQ) was used.

Example 3

An electrolyte for a lithium-sulfur secondary battery was prepared in the same manner as in Example 1, except that 1.0% by weight of 7,7,8,8-tetracyanoquinodimethane (TCNQ) was used.

Example 4

An electrolyte for a lithium-sulfur secondary battery was prepared in the same manner as in Example 1, except that 0.008% by weight of 7,7,8,8-tetracyanoquinodimethane (TCNQ) was used.

Example 5

Example 1 except that an organic solvent in which 2-methylfuran (first solvent) and 1,2-dimethoxyethane (second solvent) were mixed in a volume ratio (v/v) of 1:0.4 as an organic solvent was used. An electrolyte for a lithium-sulfur secondary battery was prepared in the same manner as described above.

Example 6

Example 1 except that an organic solvent in which 2-methylfuran (first solvent) and 1,2-dimethoxyethane (second solvent) were mixed in a volume ratio (v/v) of 1:7 as an organic solvent was used. An electrolyte for a lithium-sulfur secondary battery was prepared in the same manner as described above.

Comparative Example 1

An electrolyte for a lithium-sulfur secondary battery was prepared in the same manner as in Example 1, except that 7,7,8,8-tetracyanoquinodimethane (TCNQ) was not added.

Comparative Example 2

The same as in Example 1, except that an organic solvent in which dioxolane (first solvent) and 1,2-dimethoxyethane (second solvent) were mixed in a volume ratio (v/v) of 1:2 was used as the organic solvent. An electrolyte solution for a lithium-sulfur secondary battery was prepared by this method.

The contents of the first solvent, the second solvent, and the cyanoquinone-based additive in the lithium-sulfur secondary battery electrolytes of Examples 1 to 10 and Comparative Examples 1 and 2 are as shown in Table 1 below.

first solvent second solvent Cyanoquinone-based additives dioxolane 2-methylfuran 1,2-dimethoxyethane TCNQ Example 1 - One 4 0.1 Example 2 - One 4 0.5 Example 3 - One 4 1.0 Example 4 - One 4 0.008 Example 5 - One 0.4 0.1 Example 6 - One 7 0.1 Comparative Example 1 - One 4 - Comparative Example 2 One - 2 0.1

Experimental example 1: Life characteristics of lithium-sulfur secondary battery

After sulfur and carbon nanotube (CNT) were mixed at a weight ratio of 75:25 -B, a positive electrode active material was prepared by melt diffusion method. After mixing the positive active material and the binder (mixed binder of SBR and CMC) in a weight ratio of 95:5, water was added to prepare a positive electrode active material slurry. The positive electrode active material slurry was applied to an aluminum current collector such that the loading amount was 4.1 mAh/cm ² , and then dried to prepare a positive electrode having a porosity of 70%. Further, a lithium metal having a thickness of 45 µm was used as the negative electrode.

After positioning the positive electrode and the negative electrode prepared by the above-described method to face each other, a polyethylene separator having a thickness of 20 μm and a porosity of 45% was interposed between the positive electrode and the negative electrode.

Thereafter, the electrolytes according to Examples 1 to 6 and Comparative Examples 1 to 2 were injected into the case to prepare a lithium-sulfur secondary battery.

The lithium-sulfur secondary battery prepared by the above method is discharged at 0.1 C until it becomes 1.8 V at OCV (open circuit voltage) in CC mode at 25 ° C., and is charged at 0.1 C until it becomes 2.5 V again. 2.5 cycles were performed, and after the battery stabilization cycle, a 0.3C charge/0.5C discharge cycle was performed in a voltage range between 1.8 V and 2.5 V to evaluate the cycle life based on high-rate initial capacity 80% maintenance. is shown in Table 2 and FIGS. 1 to 2 below.

Number of cycles (based on 80% capacity retention) Example 1 287 Example 2 220 Example 3 118 Example 4 40 Example 5 52 Example 6 124 Comparative Example 1 75 Comparative Example 2 40

1 and 2 are graphs showing the lifespan characteristics of lithium-sulfur secondary batteries including electrolytes according to Examples and Comparative Examples of the present invention. As shown in FIGS. 1, 2 and Table 2, in the present invention Lithium-sulfur secondary containing a first solvent (2-methylfuran) containing a heterocyclic compound containing at least one double bond according to the A lithium-sulfur secondary battery using an electrolyte for a battery was prepared when an electrolyte not containing a cyanoquinone-based additive was used (Comparative Example 1) and when a heterocyclic compound not containing a double bond was used as the first solvent (Comparative Example 2) ), it was confirmed that the life characteristics were excellent.

All simple modifications and variations of the present invention fall within the scope of the present invention, and the specific protection scope of the present invention will become clear from the appended claims.

Claims (15)

a first solvent including a heterocyclic compound containing at least one double bond and at the same time containing any one of an oxygen atom and a sulfur atom;
a second solvent including at least one of an ether-based compound, an ester-based compound, an amide-based compound, and a carbonate-based compound;
lithium salt;
lithium nitrate; and
An electrolyte for a lithium secondary battery comprising an additive for ORM (Organic Redox Mediator). According to claim 1,
The additive for the ORM (Organic redox mediator) is 2-methyl-1,4-naphtoquinone (2-methyl-1,4-naphtoquinone), pyrroloquinoline quinone (Pyrroloquinoline quinone), 8-hydroxyquinoline-5- Sulfonic acid (8-hydroxyquinoline-5-sulfonic acid), phenazine methosulfate (Phenazine methosulfate), tetrathiafulvalence (Tetrathiafulvalence), poly (vinylferrocene) (Poly (vinylferrocene)), 1-hydroxybenzotriazole ( 1-hydroxybenzotriazole, HBT), N-hydroxyphthalimide (HPI), 2,2,6,6-tetramethyl-1-piperidinyloxy (2,2,6,6-Tetramethyl- 1-piperidinyloxy, TEMPO), violuric acid (VA), syringaldehyde (SA), vanillin (Vanillin, VA), 2,2'-azino-bis(3-ethylbenzothiazoline-6- Sulfonic acid) diammonium salt (2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt, ABTS), 9,10-anthraquinone-2,7-disulfonic acid (9,10- Anthraquinone-2,7-disulphonic acid), dimethylphenazine (DMPZ), lithium bromide (LiBr), lithium iodide (LiI), 1,4-benzoquinone (1,4- Benzoquinone), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (2,3-Dichloro-5,6-dicyano-1,4-benzoquinone), phenyl-1,4-benzoquinone (Phenyl-1,4-benzoquinone), hydroquinone, 2,3-dichloro-5,8-dihydroxy-1,4-naphthoquinone (2,3-Dichloro-5,8-dihydroxy- 1,4-naphthoquinone), 2-methoxy-1,4-benzoquinone (2-Methoxy-1,4-benzoquinone), 2,3-dimethoxy-1,4-benzoquinone (2,3-Dimethoxy- 1,4-benzoquinone), 2,6-dimethoxy-1,4-benzoquinone (2,3-Dimethoxy-1,4-benzoquinone) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) , 7,7,8.8-Tetracyanoquinodimethane) comprising at least one selected from the group consisting of, the electrolyte for a lithium secondary battery. 3. The method of claim 2,
The additive for the ORM (Organic redox mediator) is 7,7,8,8-tetracyanoquinodimethane (TCNQ, 7,7,8.8-Tetracyanoquinodimethane), 1,4-benzoquinone (1,4-Benzoquinone), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (2,3-Dichloro-5,6-dicyano-1,4-benzoquinone), phenyl-1,4-benzoquinone (Phenyl- 1,4-benzoquinone), hydroquinone (Hydroquinone), 2,3-dichloro-5,8-dihydroxy-1,4-naphthoquinone (2,3-Dichloro-5,8-dihydroxy-1,4) -naphthoquinone), 2-methoxy-1,4-benzoquinone (2-Dimethoxy-1,4-benzoquinone), 2,3-dimethoxy-1,4-benzoquinone (2,3-Dimethoxy-1,4) -benzoquinone) and 2,6-dimethoxy-1,4-benzoquinone (2,6-Dimethoxy-1,4-benzoquinone) is a quinone-based additive comprising at least one selected from the group consisting of, electrolyte for a lithium secondary battery 4. The method of claim 3,
The quinone-based additive is a cyanoquinone-based additive, an electrolyte for a lithium secondary battery. According to claim 1,
The content of the additive for the ORM is 0.01 wt% to 0.8 wt% based on the total weight of the electrolyte for a lithium secondary battery, the electrolyte for a lithium secondary battery. According to claim 1,
A volume ratio of the first solvent and the second solvent is 1:0.5 to 1:6, an electrolyte for a lithium secondary battery. According to claim 1,
The lithium salt is LiCl, LiBr, LiI, LiClO ₄ , LiBF ₄ , LiB ₁₀ Cl ₁₀ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , LiC ₄ BO ₈ , LiAsF ₆ , LiSbF ₆ , LiAlCl ₄ , CH ₃ SO ₃ Li, CF ₃ SO ₃ Li, (C ₂ F ₅ SO ₂ ) ₂ NLi, LiFSI((SO ₂ F) ₂ NLi), (CF ₃ SO ₂ ) ₃ CLi, chloroborane lithium, lower carbon number of 4 or less At least one selected from the group consisting of lithium aliphatic carboxylate, lithium 4-phenyl borate, and lithium imide, an electrolyte for a lithium secondary battery. According to claim 1,
An electrolyte for a lithium secondary battery, characterized in that the concentration of the lithium salt is 0.2 to 2.0 M. The method of claim 1,
The heterocyclic compound is one selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a halogen group, a nitro group, an amine group, and a sulfonyl group For a lithium secondary battery, which is a heterocyclic compound having 3 to 15 membered or more substituted or unsubstituted or a multicyclic compound of a heterocyclic compound with at least one of a cyclic alkyl group having 3 to 8 carbon atoms and an aryl group having 6 to 10 carbon atoms electrolyte. The method of claim 1,
The heterocyclic compound is furan, 2-methylfuran, 3-methylfuran, 2-ethylfuran, 2-propylfuran, 2-butylfuran, 2,3-dimethylfuran, 2,4-dimethylfuran, 2,5- Dimethylfuran, pyran, 2-methylpyran, 3-methylpyran, 4-methylpyran, benzofuran, 2-(2-nitrovinyl)furan, thiophene, 2-methylthiophene, 2-ethylthiophene, 2- An electrolyte for a lithium secondary battery, which is selected from the group consisting of propylthiophene, 2-butylthiophene, 2,3-dimethylthiophene, 2,4-dimethylthiophene and 2,5-dimethylthiophene. According to claim 1,
The ether-based compound of the second solvent is dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methyl propyl ether, ethyl propyl ether, dimethoxyethane, diethoxyethane, methoxyethoxyethane, diethylene glycol dimethyl Ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol methyl ethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetra At least one selected from the group consisting of ethylene glycol methyl ethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol diethyl ether and polyethylene glycol methyl ethyl ether, an electrolyte for a lithium secondary battery. According to claim 1,
The electrolyte for a lithium secondary battery further comprises at least one selected from the group consisting of lanthanum nitrate, potassium nitrate, cesium nitrate, magnesium nitrate, barium nitrate, lithium nitrite, potassium nitrite, and cesium nitrite. According to claim 1,
The electrolyte for a lithium secondary battery is 2-methylfuran as a first solvent, dimethoxyethane as a second solvent, LiFSI ((SO ₂ F) ₂ NLi) as a lithium salt, and lithium 7,7,8,8 as a cyanoquinone-based additive. - Tetracyanoquinodimethane (TCNQ, 7,7,8.8-Tetracyanoquinodimethane) and lithium nitrate, the electrolyte solution for a rechargeable lithium battery. anode;
cathode;
a separator interposed between the anode and the cathode; and
A lithium secondary battery comprising; the electrolyte for a lithium secondary battery according to claim 1 . 14. The method of claim 13,
The lithium secondary battery is a lithium-sulfur secondary battery, a lithium secondary battery.

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