KR20170011357A - Porous Lithium Electrode and Method for Manufacturing thereof and Lithium Secondary Battery using the same - Google Patents

Abstract

The present invention relates to a porous lithium electrode, a method for manufacturing the same, and a lithium secondary battery using the same, which can prevent lithium dendrites from growing during driving of the lithium secondary battery through uniformity of current density in the lithium electrode. The porous lithium electrode according to the present invention comprises: a lithium metal substrate; and lithium sulfide which is formed in the lithium metal substrate in the form of micropores. The method for manufacturing the porous lithium electrode comprises: a step of preparing a mixed powder by mixing a lithium metal powder with a sulfur powder; and a calcination step of forming lithium sulfide in the lithium metal substrate in the form of micropores by thermally calcinating the mixed powder and thus decomposing the sulfur powder. The lithium secondary battery according to the present invention comprises the porous lithium electrode of the present invention as a negative electrode thereof. According to the present invention, lithium dendrites can be prevented from growing during driving of the lithium secondary battery through uniformity of current density in the lithium electrode, and the lithium sulfide formed in the lithium metal in the form of micropores performs a passivation function for the lithium metal substrate and thus enhances the effect of preventing lithium dendrites from growing during driving of the lithium secondary battery, thereby improving stability of the lithium secondary battery.

Description

TECHNICAL FIELD The present invention relates to a porous lithium electrode, a method of manufacturing the same, and a lithium secondary battery using the porous lithium electrode,

The present invention relates to a porous lithium electrode, a manufacturing method thereof, and a lithium secondary battery using the porous lithium electrode. More particularly, the present invention relates to a porous lithium electrode capable of preventing lithium dendrite growth An electrode, a manufacturing method thereof, and a lithium secondary battery using the same.

Recently, interest in energy storage technology is increasing. As the application fields of cell phones, camcorders, notebook PCs and even electric vehicles are expanding, efforts for research and development of electrochemical devices are becoming more and more specified. The electrochemical device has received the most attention in this respect. Of these, the development of a rechargeable secondary battery has become a focus of attention. Recently, in developing such a battery, Research and development on the design of electrodes and batteries are underway.

Among the currently applied secondary batteries, the lithium secondary battery developed in the early 1990s has advantages such as higher operating voltage and higher energy density than conventional batteries such as Ni-MH, Ni-Cd and sulfuric acid-lead batteries using an aqueous electrolyte solution .

Generally, a lithium secondary battery includes a positive electrode, a negative electrode, and an electrode assembly including a positive electrode and a separator interposed between the positive electrode and the negative electrode, which are laminated or wound into a battery case, and a non-aqueous electrolyte is injected into the battery case.

In this case, when a lithium electrode is used as the cathode, a lithium electrode formed by attaching a lithium foil on a planar current collector has been used.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a view showing an electron movement path in a lithium electrode produced by adhering a lithium foil on a conventional planar current collector. FIG. As shown in Fig. 1, in a general lithium electrode, electrons moving to the lithium foil 2 through the current collector 1 move in a single direction flow when the battery is driven. This results in non-uniformity of the electron density on the lithium surface, whereby lithium dendrite can be formed.

Such lithium dendrites may ultimately cause damage to the separator, and short-circuiting of the lithium secondary battery may occur, which may lead to a problem of deteriorating the safety of the lithium secondary battery.

In order to solve such a problem, in order to improve the contact surface area between the lithium metal and the current collector and to prevent the growth of lithium dendrite during the operation of the lithium secondary battery through uniform distribution of electrons in the lithium electrode, Discloses a lithium electrode and a lithium secondary battery including the lithium electrode disclosed in Korean Patent Publication No. 2015-0030157.

Korean Patent Laid-Open Publication No. 2015-0030157 discloses a structure comprising a porous metal current collector and a lithium metal inserted into pores formed in a metal current collector, wherein the contact surface area between the lithium metal and the current collector is improved to improve the performance of the lithium secondary battery And the distribution of the electrons in the lithium electrode is made uniform so as to prevent the growth of the lithium dendrite upon driving the lithium secondary battery, thereby improving the stability of the lithium secondary battery.

It is an object of the present invention to further improve the conventional lithium electrode to maximize the contact surface area between the lithium metal and the electrolyte thereby to improve the uniformity of the current density in the lithium electrode and to improve the lithium dendrite growth An electrode, a manufacturing method thereof, and a lithium secondary battery using the same.

Another object of the present invention is to provide a porous lithium electrode that further enhances the effect of preventing lithium dendrite growth at the time of operating a lithium secondary battery by allowing lithium sulfide formed of lithium metal to serve as a passivation for lithium metal, And a lithium secondary battery using the same.

The porous lithium electrode according to the present invention includes a lithium metal base material and lithium sulfide formed as fine pores in the lithium metal base material.

The lithium sulfide may be 1 to 50% by volume based on the total volume of the porous lithium electrode.

The size of the fine holes may be 10 to 80 탆.

The lithium electrode comprising lithium metal substrate and lithium sulfide formed by micropores may be deposited or formed on a metal current collector formed of any one selected from the group consisting of copper, nickel, iron, chromium, zinc and stainless steel or a mixture of two or more thereof. Can be applied and formed. The porosity of the metal current collector may be 50 to 99%, and the size of the pores formed in the metal current collector may be 5 to 500 탆. The metal current collector may be a metal mesh or a metal foam.

The method for producing a porous lithium electrode according to the present invention includes the steps of preparing a mixed powder by mixing a lithium metal powder and sulfur powder and calcining the mixed powder to decompose the sulfur powder to form fine particles of lithium sulfide Lt; RTI ID = 0.0 > a < / RTI >

The heating temperature in the calcination step is 120 to 170 ° C, and the heating time is 1 to 3 hours. After the calcination step, the calcined mixture may be further subjected to pressure molding. After the calcination step, the calcined mixture may be further deposited or applied to the metal current collector. After the step of pressure-forming, the step of sintering the press-molded mixture may further be included.

Meanwhile, the lithium secondary battery according to the present invention includes an electrode assembly including a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, a battery case accommodating the electrode assembly, Aqueous electrolyte solution impregnated with a non-aqueous electrolyte. The negative electrode is a negative electrode using the lithium electrode or lithium electrode manufacturing method of the present invention.

In this case, the anode may be made of LiCoO ₂ , LiNiO ₂ , LiMn ₂ O ₄ , LiCoPO ₄ , LiFePO ₄ , LiNiMnCoO ₂ and LiNi 1 _-xyz Co _x M _{y y} M2 _z O ₂ , X, y and z are independently selected from the group consisting of Co, Fe, Mn, V, Cr, Ti, W, Ta, Mg and Mo, 0 < y < 0.5, 0 < z &lt; 0.5, and x + y + z &lt; = 1) or a mixture of two or more thereof.

The separator may be made of a material selected from the group consisting of polyethylene, polypropylene, polybutylene, polypentene, polyethylene terephthalate, polybutylene terephthalate, polyesters, polyester, polyacetal, polyamide, polycarbonate, polyimide, polyetheretherketone, polyethersulfone, polyphenylene oxide, ), Polyphenylene sulfide, and polyethylene naphthalate, or a mixture of two or more thereof.

The nonaqueous electrolyte solution may include an organic solvent and an electrolyte salt.

The organic solvent may be selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, (DEC), diethyl carbonate (DEC), dipropyl carbonate, ethyl methyl carbonate (EMC), dimethyl carbonate (DMF) Methyl ethyl ketone, ethyl propyl carbonate, dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methyl propyl ether, ethyl propyl ether, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, Propyl propionate,? -Butyrolactone,? -Valerolactone,? -Caprolactone,? -Valerolactone and? -Caprolactone , Or a mixture of two or more thereof.

In addition, the electrolyte salt is a negative ^{ion, F -, Cl -, Br} -, I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, PF 6 -, (CF 3) 2 _{^{PF 4 -, (CF 3)}} 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, CF 3 SO 3 -, CF 3 CF 2 SO 3 _{^{-, (CF 3 SO 2)}} 2 N -, (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, (SF 5) 3 C -, _{(CF 3 SO 2) 3 C} -, CF 3 (CF 2) 7 SO 3 -, CF 3 CO 2 -, CH 3 CO 2 -, SCN - , and _{(CF 3 CF 2 SO 2)} 2 N - the group consisting of Or two or more of them.

The battery case may have a cylindrical shape, a rectangular shape, a pouch shape, or a coin shape.

According to the lithium electrode of the present invention, the method of manufacturing the same, and the lithium secondary battery using the same, maximization of the contact surface area between the lithium metal and the electrolyte enables uniformity of the current density in the lithium electrode to achieve lithium dendrite growth Can be further prevented.

Further, the lithium sulfide formed by the micro-pores in the lithium metal acts as a passivation for the lithium metal, thereby further enhancing the effect of preventing lithium dendrite growth at the time of operating the lithium secondary battery.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a view showing an electron movement path in a lithium electrode produced by adhering a lithium foil on a conventional planar current collector. FIG.
2 is a schematic view showing a porous lithium electrode according to an embodiment of the present invention.
3 is a flowchart showing a method of manufacturing a porous lithium electrode according to an embodiment of the present invention.
4 is a partially exploded perspective view of a lithium secondary battery using a porous lithium electrode according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to the drawings. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

Therefore, the embodiments described in the present specification and the constitutions described in the drawings are merely the most preferred embodiments of the present invention, and are not intended to represent all of the technical ideas of the present invention. Therefore, It is to be understood that equivalents and modifications are possible.

FIG. 2 is a schematic view showing a porous lithium electrode according to an embodiment of the present invention. FIG. 2 (a) shows a mixed powder state in which a lithium metal powder and a sulfur powder are mixed to produce a porous lithium electrode, (b) shows a state in which the mixed powder is heated. 3 is a flowchart showing a method of manufacturing a porous lithium electrode according to an embodiment of the present invention.

As shown in FIG. 2B, the porous lithium electrode 100 includes a lithium metal base 110 and lithium sulfide (Li ₂ S) 120 formed by micropores in the lithium metal base 110. As shown in FIG. 3, the porous lithium electrode manufacturing method includes a step S110 of preparing a mixed powder, a calcining step S120, a pressing step S130, a sintering step S140, (S150). &Lt; / RTI &gt;

The porous lithium electrode 100 of the present invention is obtained by mixing lithium metal powder 11 and sulfur powder 12 and calcining the mixture by heating to decompose the sulfur powder 12 to form lithium lithium Li ₂ S) 120 as shown in FIG. The porous lithium electrode 100 manufactured according to this manufacturing method maximizes the contact surface area between the lithium metal and the electrolyte, thereby making it possible to further prevent the growth of lithium dendrite during the operation of the lithium secondary battery by uniformizing the current density in the lithium electrode In addition, since lithium sulfide formed as a micropore in the lithium metal acts as a passivation for the lithium metal base material, the effect of preventing lithium dendrite growth is further enhanced at the time of operating the lithium secondary battery, The stability can be improved.

The lithium sulfide 120 may be 1 to 50% by volume, preferably 3 to 30% by volume, more preferably 5 to 20% by volume based on the total volume of the lithium electrode. When the content ratio is satisfied, the growth of lithium dendrite can be suppressed and short-circuiting can be prevented even if the charge / discharge is continuously performed. On the other hand, if the content of the lithium sulfide 120 is less than 1% by volume, it may be difficult to serve as a passivation. If the content of the lithium sulfide 120 exceeds 50% by volume, The effect is low.

The size of the fine pores formed by the lithium sulfide 120 may be 10 to 80 탆. Accordingly, even if the charge / discharge is continuously performed, the growth of the lithium dendrite can be suppressed and short-circuiting can be prevented. The smaller the size of the micropores, the better the effect of inhibiting the growth of lithium dendrites.

The porous lithium electrode 100 including the lithium metal base 110 and the lithium sulfide 120 formed of micropores may be any one selected from the group consisting of copper, nickel, iron, chromium, zinc, and stainless steel, (Not shown) formed of the above mixture. The metal current collector is not limited as long as it is a metal that is stable in a voltage range to be used. The porosity of the metal current collector may be 50 to 99%. The higher the porosity of the metal current collector and the smaller the pore size, the better the lithium dendrite growth inhibiting effect. The size of the pores formed in the metal current collector may be 5 to 500 mu m. The metal current collector may be a metal mesh or a metal foam.

The preparation of the mixed powder in the method of manufacturing the porous lithium electrode (S110) is a step of preparing the mixed powder by mixing the lithium metal powder (11) and the sulfur powder (12). The size of the metal powder 11 and the sulfur powder 12 is preferably 10 to 80 mu m in accordance with the size of the micro pores.

The calcination step S120 is a step of calcining the mixed powder to decompose the sulfur powder 120 to form fine pores of the lithium sulfide 120 in the lithium metal base 110. [ Since the melting point of the lithium metal is about 180 ° C and the melting point of sulfur is about 115 ° C, the heating temperature in the calcining step (S120) is preferably 120 to 170 ° C in an air atmosphere. The heating time is preferably 1 hour to 3 hours. At this time, it is effective to sublimate sulfur for a long time at a low temperature rather than at a high temperature, and the working temperature may vary depending on the heating time.

The step of press molding (S130) is a step of press molding the calcined mixture to the size of the electrode. The molding pressure is preferably 50 to 300 bar.

The step of sintering (S140) is a step of sintering together the unmodified powder in the calcined mixture. The sintering temperature is preferably in the range of 160 to 175 DEG C in an air atmosphere. The sintering time is preferably 30 minutes to 1 hour.

The step of depositing or applying (S150) is a step of depositing or applying the calcined mixture on the metal current collector without press-molding the calcined mixture after the calcination step (S120). The deposition or coating is preferably carried out by depositing or applying the calcined mixture into a slurry state.

4 is a partially exploded perspective view of a lithium secondary battery using a porous lithium electrode according to an embodiment of the present invention (a battery case and a non-aqueous electrolyte are omitted). As shown, the lithium secondary battery 200 according to the embodiment of the present invention includes a cathode 210, a cathode 220, and a separator 230 interposed between the anode 210 and the cathode 220 And a non-aqueous electrolyte that is embedded in the battery case and impregnates the electrode assembly. The cathode 220 may be formed of the porous lithium electrode 100 of the present invention or the porous lithium electrode of the present invention And is a negative electrode manufactured by a method of manufacturing a lithium electrode.

The anode 210 may be composed of a cathode current collector and a cathode active material layer coated on one side or both sides thereof. The positive electrode active material layer may be formed of a material selected from the group consisting of LiCoO ₂ , LiNiO ₂ , LiMn ₂ O ₄ , LiCoPO ₄ , LiFePO _4, LiNiMnCoO ₂ and _{LiNi 1 -xyz Co x M1 y M2} z O 2 (M1 and M2 are independently selected from Al, Ni, Co, Fe, Mn, V, Cr, Ti, W, Ta, Mg and Mo each other X, y and z are independently selected from the group consisting of 0? X <0.5, 0? Y <0.5, 0? Z <0.5, x + y + z? , Or a mixture of two or more thereof.

The cathode active material layer may further include a conductive material to improve electrical conductivity. At this time, the conductive material is not particularly limited as long as it is an electron conductive material that does not cause a chemical change in the lithium secondary battery. In general, carbon black, graphite, carbon fiber, carbon nanotube, metal powder, conductive metal oxide, organic conductive material and the like can be used. Commercially available products as the conductive material include acetylene black series (manufactured by Chevron Chemical Co., (Chevron Chemical Company or Gulf Oil Company products), Ketjen Black EC series (Armak Company), Vulcan XC-72 (Cabot Company) and Super P (MM (MMM)). For example, acetylene black, carbon black and graphite.

As a binder having a function of holding the positive electrode active material on the positive electrode collector and connecting the active materials therebetween, for example, polyvinylidene fluoride-hexafluoropropylene (PVDF-co-HFP), polyvinylidene Polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate, styrene butadiene rubber (SBR), carboxyl methyl cellulose (CMC) ) May be used.

The separator may be formed of a porous substrate. The porous substrate may be any porous substrate commonly used in an electrochemical device. For example, a polyolefin porous membrane or a nonwoven fabric may be used. However, , And is not particularly limited thereto.

Examples of the polyolefin-based porous film include polyolefin-based polymers such as polyethylene, polypropylene, polybutylene, and polypentene, such as high-density polyethylene, linear low density polyethylene, low density polyethylene and ultra high molecular weight polyethylene, One membrane can be mentioned.

The nonwoven fabric may include, in addition to the polyolefin nonwoven fabric, for example, polyethylene terephthalate, polybutylene terephthalate, polyester, polyacetal, polyamide, polycarbonate ), Polyimide, polyetheretherketone, polyethersulfone, polyphenylene oxide, polyphenylenesulfide, and polyethylene naphthalate, which are used alone or in combination, Or a nonwoven fabric formed of a polymer mixed with these. The structure of the nonwoven fabric may be a spun bond nonwoven fabric or a meltblown nonwoven fabric composed of long fibers.

The thickness of the porous substrate is not particularly limited, but it is 1 탆 to 100 탆, or 5 탆 to 50 탆. The size and porosity of the pores existing in the porous substrate are also not particularly limited, but may be 0.001 탆 to 50 탆 and 10% to 95%, respectively.

The electrolyte salt included in the nonaqueous electrolyte solution which can be used in the present invention is a lithium salt. The lithium salt can be used without limitation as those conventionally used in an electrolyte for a lithium secondary battery. For example is the above lithium salt anion ^{F -, Cl -, Br -} , I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, PF 6 -, (CF 3) 2 PF _{^{4 -, (CF 3) 3}} PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, CF 3 SO 3 -, CF 3 CF 2 SO 3 - _{, (CF 3 SO 2) 2} N -, (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, (SF 5) 3 C -, ( CF ₃ SO _{2) 3} C ^- from the group consisting of ^{_{-, CF 3 (CF 2)}} 7 SO 3 -, CF 3 CO 2 -, CH 3 CO 2 -, SCN - , and _{(CF 3 CF 2 SO 2)} 2 N Any one selected, or two or more of them.

Examples of the organic solvent included in the above-mentioned non-aqueous electrolyte include those conventionally used for an electrolyte for a lithium secondary battery, such as an ether, an ester, an amide, a linear carbonate and a cyclic carbonate, Can be mixed and used.

Among them, a carbonate compound which is typically a cyclic carbonate, a linear carbonate, or a mixture thereof may be included.

Specific examples of the cyclic carbonate compound include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, Propylene carbonate, 2,3-pentylene carbonate, vinylene carbonate, vinylethylene carbonate, and halides thereof, or a mixture of two or more thereof. Examples of such halides include, but are not limited to, fluoroethylene carbonate (FEC) and the like.

Specific examples of the linear carbonate compound include any one selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethyl methyl carbonate (EMC), methyl propyl carbonate and ethyl propyl carbonate And mixtures of two or more of them may be used as typical examples, but the present invention is not limited thereto.

In particular, ethylene carbonate and propylene carbonate, which are cyclic carbonates in the carbonate-based organic solvent, are high-viscosity organic solvents having a high dielectric constant and can dissociate the lithium salt in the electrolyte more easily. In addition, such cyclic carbonates can be used as dimethyl carbonate and diethyl carbonate When a low viscosity, low dielectric constant linear carbonate is mixed in an appropriate ratio, an electrolyte having a higher electric conductivity can be produced.

As the ether in the organic solvent, any one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methyl propyl ether and ethyl propyl ether or a mixture of two or more thereof may be used , But is not limited thereto.

Examples of the ester in the organic solvent include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate,? -Butyrolactone,? -Valerolactone,? -Caprolactone,? -Valerolactone and? -Caprolactone, or a mixture of two or more thereof, but the present invention is not limited thereto.

The injection of the nonaqueous electrolyte solution can be performed at an appropriate stage of the manufacturing process of the electrochemical device according to the manufacturing process and required properties of the final product. That is, it can be applied before assembling the electrochemical device or in the final stage of assembling the electrochemical device.

The lithium secondary battery according to the present invention can be laminated, stacked, and folded in addition to winding, which is a general process. The battery case may have a cylindrical shape, a square shape, a pouch shape, a coin shape, or the like.

The foregoing description is merely illustrative of the technical idea of the present invention, and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are intended to illustrate rather than limit the scope of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of equivalents should be construed as falling within the scope of the present invention.

11: lithium metal powder 12: sulfur powder
100: Porous lithium electrode 110: Lithium metal substrate
120: lithium sulfide 200: lithium secondary battery
210: anode 220: cathode
230: separator

Claims (19)

A lithium metal base,
And lithium sulfide formed as fine pores in the lithium metal base. The method according to claim 1,
Wherein the lithium sulfide is 1 to 50% by volume based on the total volume of the porous lithium electrode. The method according to claim 1,
Wherein the micropores have a size of 10 to 80 占 퐉. The method of claim 1,
The lithium electrode including the lithium metal substrate and the lithium sulfide formed of the micropores may be a metal electrode formed of any one selected from the group consisting of copper, nickel, iron, chromium, zinc, and stainless steel or a mixture of two or more thereof Wherein the porous lithium electrode is formed by being deposited or applied on the porous lithium electrode. The method of claim 4,
Wherein the porosity of the metal current collector is 50 to 99%. The method of claim 4,
Wherein the pores formed in the metal current collector have a size of 5 to 500 mu m. The method of claim 4,
Wherein the metal current collector is a metal mesh or a metal foam. A method for producing a porous lithium electrode according to claim 1,
Mixing the lithium metal powder and the sulfur powder to prepare a mixed powder,
And calcining the mixed powder to decompose the sulfur powder to form fine pores of lithium sulfide in the lithium metal base material. The method of claim 8,
Wherein the calcining step has a heating temperature of 120 to 170 占 폚 and the heating time is 1 to 3 hours. The method of claim 8,
Further comprising the step of press-molding the calcined mixture after the calcination step. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; The method of claim 8,
Wherein the calcining step further comprises the step of depositing or applying the calcined mixture on the metal current collector after the calcination step. The method of claim 10,
Further comprising the step of sintering the press-molded mixture after the step of press-molding. An electrode assembly comprising a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode,
A battery case accommodating the electrode assembly, and
And a nonaqueous electrolyte contained in the battery case and impregnating the electrode assembly, the lithium secondary battery comprising:
Wherein the cathode is a porous lithium electrode according to any one of claims 1 to 7 or a porous lithium electrode according to any one of claims 8 to 12 by a manufacturing method of the porous lithium electrode. 14. The method of claim 13,
The positive electrode is made of a material selected from the group consisting of LiCoO ₂ , LiNiO ₂ , LiMn ₂ O ₄ , LiCoPO ₄ , LiFePO ₄ , LiNiMnCoO ₂ and LiNi 1 _-xyz Co _x M _{y y} M2 _z O ₂ X, y and z are independently selected from the group consisting of Fe, Mn, V, Cr, Ti, W, Ta, Mg and Mo, y < 0.5, 0 < z < 0.5, and x + y + z &lt; = 1) or a mixture of two or more thereof. 14. The method of claim 13,
The separator may be made of a material selected from the group consisting of polyethylene, polypropylene, polybutylene, polypentene, polyethylene terephthalate, polybutylene terephthalate, polyester ), Polyacetal, polyamide, polycarbonate, polyimide, polyetheretherketone, polyethersulfone, polyphenylene oxide, polyphenylene oxide, Wherein the porous substrate is a porous substrate made of any one selected from the group consisting of polyphenylene sulfide and polyethylene naphthalate or a mixture of two or more thereof. 14. The method of claim 13,
Wherein the non-aqueous electrolyte comprises an organic solvent and an electrolyte salt. 18. The method of claim 16,
Examples of the organic solvent include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, (DEC), dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethyl methyl carbonate (EMC), methyl propyl carbonate A solvent such as methanol, ethanol, propanol, isopropanol, isopropanol, butanol, isopropanol, butanol, isopropanol, Pyronate,? -Butyrolactone,? -Valerolactone,? -Caprolactone,? -Valerolactone and? -Caprolactone Luer binary group either or lithium secondary battery, characterized in that a mixture of two or more of those selected from the. 18. The method of claim 16,
The electrolyte salt includes, as ^{anions, F -, Cl -, Br} -, I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, PF 6 -, (CF 3) 2 PF 4 ^{_{-, (CF 3) 3 PF}} 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, CF 3 SO 3 -, CF 3 CF 2 SO 3 -, _{(CF 3 SO 2) 2 N} -, (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, (SF 5) 3 C -, (CF ₃ SO ₂ ) ₃ C ^- , CF ₃ (CF ₂ ) ₇ SO ₃ ^- , CF ₃ CO ₂ ^- , CH ₃ CO ₂ ^- , SCN ^- and (CF ₃ CF ₂ SO ₂ ) ₂ N ^- Or a mixture of two or more of them. 14. The method of claim 13,
Wherein the battery case has a cylindrical shape, a square shape, a pouch shape, or a coin shape.

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