KR20090010373A - Lithium ion battery containing oxygen adsorbent - Google Patents

Abstract

The present invention relates to a lithium ion battery including an oxygen adsorption material, and the oxygen adsorption material and the ceramic material combine to form a thin film on the ceramic coating layer of the negative electrode, thereby preventing damage to the negative electrode plate by suppressing side reactions between the negative electrode active material and oxygen. This increases the capacity of the battery.

Description

Lithium ion battery containing oxygen adsorption material {LITHIUM ION BATTERY INCLUDING OXYGEN SCAVENGER}

The present invention relates to a lithium ion battery comprising an oxygen adsorption material.

Recently, with the development of the high-tech electronic industry, the miniaturization and light weight of electronic equipment is enabled, and the use of portable electronic devices is increasing. As a power source for such portable electronic devices, the need for a battery having a high energy density has been increased, and thus research on lithium secondary batteries has been actively conducted.

The lithium secondary battery includes a positive electrode, a negative electrode, and an electrolyte, and a separator is generally disposed between the positive electrode and the negative electrode in order to prevent a phenomenon in which the positive electrode and the negative electrode directly contact and short-circuit.

When using this lithium ion battery, oxygen is generated by electrolyte contamination and decomposition of the positive electrode itself. Oxygen generated at this time not only causes the swelling phenomenon of the battery, but also acts as a cause of additional heat generation due to side reactions. The by-products which cause side reactions with lithium ions and additionally produce secondary side reactions to improve battery performance and safety. It acts to deteriorate. In addition, in a battery having a ceramic porous membrane on the negative electrode surface, by-products caused by such an addition reaction block the porous membrane, thereby affecting charge transfer, thereby degrading rate-specific characteristics and low-temperature characteristics.

An object of the present invention for solving the above problems is to form a thin film on the surface of the ceramic coating layer of the negative electrode by combining the oxygen adsorption material and the ceramic material to remove the oxygen generated in the battery negative electrode plate by reducing the side reaction of oxygen and the negative electrode active material It is to provide a lithium ion battery containing an oxygen adsorption material to reduce the damage of.

Lithium ion battery comprising the oxygen adsorption material of the present invention for achieving the above object,

An electrolyte comprising a non-aqueous organic solvent, a lithium salt and an oxygen adsorbent;

A cathode capable of reversibly inserting and detaching lithium; And

It includes a negative electrode comprising a carbon-based negative electrode active material layer capable of reversibly inserting and detaching lithium.

The oxygen adsorbent may be selected from at least one of 1,2,5-trimethylpyrrole, triphenylphosphine or copper dioxide.

The present invention is at least one oxygen adsorbent material selected from 1,2,5-trimethylpyrrole, triphenylphosphine or copper dioxide in the electrolyte in order to lower the permeability of oxygen generated inside the battery due to contamination of the electrolyte or decomposition of the positive electrode. Is added to the electrolyte solution. The added oxygen adsorbent material is combined with the ceramic material to form a thin film on the surface of the ceramic coating layer of the negative electrode to suppress side reactions between oxygen and the negative electrode active material to reduce damage to the negative electrode plate. Oxygen adsorbent material can be inferred to prevent the damage to the negative electrode plate because the amount of oxygen that can participate in the side reaction is reduced because the adsorption of oxygen in the thin film or oxygen is prevented from passing through the thin film.

The 1,2,5-trimethylpyrrole has the following structural formula,

The molecular formula is C ₇ H ₁₁ N, molecular weight is 109.17, boiling point 173 ° C., freezing point 126 ° F., and density at 0.807 g / ml at room temperature.

The trimethyl phosphine has the following structural formula,

PPh _3, or Ph ₃ P P represented by (C ₆ H ₅₎ an organic phosphorus compound having a _3. The molecular formula of trimethylphosphine is C ₁₈ H ₁₅ P, molecular weight is 262.29 g / mol, appearance is white solid, density is 1.1 g / cm 3, insoluble in water, melting point is 80 ° C., boiling point 377 ℃. PPh ₃ is relatively stable in air and is colorless crystals at room temperature. It is also soluble in nonpolar organic solvents such as benzene or diethyl ether.

The oxygen adsorbent may be 0.005 to 5% by weight. When the content of the oxygen adsorption material is 0.005% by weight or less, the thin film formed by combining the oxygen adsorption material and the ceramic material is too thin to reduce oxygen permeation. When the oxygen adsorbent is 5% by weight or more, the content of the basic non-aqueous organic solvent may be relatively reduced, thereby reducing conductivity, mobility of lithium ions, and electrochemical stability.

The fluoroethylene carbonate may be included 0.1 to 10.0% by weight.

Fluoroethylene carbonate is a material used as an electrolyte additive, an organic solvent, and an intermediate of pharmaceuticals in lithium ion batteries. In the case of using propylene carbonate as an organic solvent, which is a component of the electrolyte, in particular, fluoroethylene carbonate is added. Forming a stable protective film on the surface of the serves to increase the capacity of the battery.

The negative electrode may be formed of a graphite-based negative electrode active material layer and a ceramic coating layer on the negative electrode current collector.

The ceramic coating layer has at least one ceramic material particle selected from alumina, silica, zirconia, zeolite, magnesia, titanium oxide, and barium titanium has high temperature retention characteristics such as 1 to 5 wt% of an acrylate-based or methylacrylate-based binder. It can be formed by bonding to a good material. In addition, the thickness of the ceramic coating layer is preferably 2 ~ 20 ㎛.

The binder is mainly composed of a polymer resin, and the polymer resin is preferably composed of a polymer of acrylate or methacrylate or a copolymer thereof that can withstand heat of 200 ° C. or higher. In addition, it is preferable that the said binder is used a small amount in the slurry for porous film formation. When the content of the binder is 1 to 5% by weight relative to the ceramic material, it is possible to prevent the ceramic material filler from being completely covered by the binder. That is, the problem that the binder covers the filler material and the ion conductivity is limited into the filler material can be avoided.

In general, when the separator of the porous film is short-circuited, a ceramic coating layer is formed of a ceramic material on the active material layer of the positive electrode or the negative electrode in order to prevent the positive electrode and the negative electrode from contacting each other. The ceramic coating layer has a high oxygen permeability, so that the generated oxygen participates in side reactions, thereby reducing the capacity of the battery. Therefore, by adding oxygen adsorbent material of at least one of 1,2,5-trimethylpyrrole, triphenylphosphine or copper dioxide to the electrolyte solution and combining it with a ceramic material, a thin film is formed on the ceramic coating layer to cause side reaction between the negative electrode active material and oxygen. It can suppress and reduce the damage of a negative electrode plate.

The lithium ion battery is preferably cylindrical.

The present invention can also be applied to cells in the form of squares or pouches, preferably to cylindrical cells. In general, a cylindrical battery has a disadvantage in that an internal phenomenon such as oxygen cannot be estimated because an appearance of an internal gas such as oxygen does not greatly occur. Therefore, the use of such an electrolyte can solve the reduction of the capacity of the battery due to oxygen.

Hereinafter, the present invention will be described in more detail.

The electrolyte of the present invention also includes a non-aqueous organic solvent and a lithium salt. The lithium salt acts as a source of lithium ions in the battery to enable operation of the basic lithium battery, and the non-aqueous organic solvent serves as a medium through which Li ⁺ ions involved in the electrochemical reaction of the battery can move.

In the present invention, the lithium salt may be LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiAsF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , LiN (SO ₂ CF ₃ ) ₂ , LiN (SO ₂ C ₂ F ₅ ) ₂ , LiC (SO ₂ CF ₃ ) ₃ , LiN (SO ₃ CF ₃ ) ₂ , LiC ₄ F ₉ SO ₃ , LiAlO ₄ , LiAlCl ₄ , one or two or more selected from the group consisting of LiI can be used in combination. The concentration of the lithium salt is preferably used in the range of 0.6 to 2.0M, more preferably in the range of 0.7 to 1.6M. If the concentration of the lithium salt is less than 0.6M, the conductivity of the electrolyte is lowered, the performance of the electrolyte is lowered, and if it exceeds 2.0M, the viscosity of the electrolyte is increased, there is a problem that the mobility of lithium ions decreases. An electrolyte solution excellent in reduction resistance is preferable because it withstands high voltage (oxidation) at the anode side and lithium itself exhibits an extremely low potential. The order of oxidation resistance of the lithium salts described above is LiPF ₆ > LiBF ₄ 〉 LiCF ₃ SO ₃ 〉 LiClO ₄ The order of reduction resistance is LiPF ₆ 〉 LiAsF ₆ 〉 LiSbF ₆ to be. Therefore, LiPF ₆ is most preferred as a lithium salt.

The non-aqueous organic solvent may include one or a mixture of carbonates, esters, ethers or ketones. In the case of a carbonate-based solvent in the non-aqueous organic solvent, it is preferable to use a mixture of cyclic carbonate and chain carbonate. In this case, the cyclic carbonate and the chain carbonate are preferably used by mixing in a volume ratio of 1: 1 to 1: 9, and more preferably used by mixing in a volume ratio of 1: 1.5 to 1: 4. The performance of the electrolyte is superior to other volume ratios by mixing at the volume ratio.

As the cyclic carbonate, ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, etc. may be used. Can be. Among the high dielectric constant ethylene carbonate and propylene carbonate, ethylene carbonate has a high melting point and is mixed with other solvents. When graphite is used as a negative electrode active material, propylene carbonate having a low decomposition voltage is not used or the content is lowered.

As the chain carbonate, dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylmethyl carbonate (EMC), ethylpropyl carbonate (EPC), etc. may be used. Among these, dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate having low viscosity are mainly used.

When cyclic and chain carbonates are used as solvents of the electrolyte, the carbonates are combustible materials, and thus, the carbonates are easily combustible with oxygen generated together with structural breakdown of active materials, especially cathode active materials, when the temperature rises due to a local short circuit inside the battery or the ambient temperature rises. There is a risk of the battery exploding. Therefore, the explosion as described above may also be prevented by adding at least one oxygen adsorbent selected from trimethylpyrrole, triphenylphosphine or copper dioxide.

As ester, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, γ-valerolactone, γ-caprolactone, δ-valerolactone, ε-caprolactone, etc. Tetrahydrofuran, 2-methyltetrahydrofuran, dibutyl ether and the like may be used as the ether. As the ketone, polymethylvinyl ketone may be used.

The electrolyte of the present invention may further include an aromatic hydrocarbon organic solvent in the carbonate solvent. As the aromatic hydrocarbon organic solvent, an aromatic hydrocarbon compound represented by Chemical Formula 3 may be used.

[Formula 3]

In the above formula, R is halogen or an alkyl group having 1 to 10 carbon atoms and q is an integer of 0 to 6. Specific examples of the aromatic hydrocarbon organic solvent may include benzene, fluorobenzene, bromobenzene, chlorobenzene, toluene, xylene, mesitylene, and the like, which may be used alone or in combination. When the volume ratio of carbonate solvent / aromatic hydrocarbon-based organic solvent in an electrolyte containing an aromatic hydrocarbon-based organic solvent is 1: 1 to 30: 1, the characteristics, such as stability, safety, and ion conductivity, which are generally required of the electrolyte, are compared with those of other ratio compositions. great.

The lithium ion battery of the present invention includes a positive electrode and a negative electrode.

The positive electrode includes a positive electrode active material capable of occluding and desorbing lithium ions, and the positive electrode active material is preferably at least one selected from cobalt, manganese, nickel, and a composite metal oxide with lithium. The solid solution ratio between the metals may be various, and in addition to these metals, Mg, Al, Co, K, Na, Ca, Si, Ti, Sn, V, Ge, Ga, B, As, Zr, Mn, Cr, Fe, An element selected from the group consisting of Sr, V and rare earth elements may be further included.

The negative electrode includes a negative electrode active material capable of occluding and desorbing lithium ions. As the negative electrode active material, a carbon material such as crystalline carbon, amorphous carbon, carbon composite, carbon fiber, or the like may be used. For example, amorphous carbon includes hard carbon, coke, mesocarbon microbeads (MCMB) fired at 1500 ° C. or lower, mesophase pitch-based carbon fibers (MPCF), and the like. The crystalline carbon includes a graphite material, and specific examples thereof include natural graphite, graphitized coke, graphitized MCMB, graphitized MPCF, and the like. The carbonaceous material is preferably a material having an d002 interplanar distance of 3.35 to 3.38 Å and an Lc (crystallite size) of at least 20 nm by X-ray diffraction. Other elements alloyed with lithium may be aluminum, zinc, bismuth, cadmium, antimony, silicon, lead, tin, gallium or indium.

The positive electrode or the negative electrode may be prepared by dispersing an electrode active material, a binder and a conductive material, if necessary, a thickener in a solvent to prepare an electrode slurry composition, and applying the slurry composition to an electrode current collector. As the positive electrode current collector, aluminum or an aluminum alloy may be commonly used, and as the negative electrode current collector, copper or a copper alloy may be commonly used. The positive electrode current collector and the negative electrode current collector may be in the form of a foil or a mesh.

The binder is a material that plays a role of pasting the active material, mutual adhesion of the active material, adhesion with the current collector, buffering effect on the expansion and contraction of the active material, and the like, for example, polyvinylidene fluoride (PVdF), polyhexafluoro Copolymer of propylene-polyvinylidene fluoride (P (VdF / HFP)), poly (vinylacetate), polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, alkylated polyethylene oxide, polyvinyl ether, poly ( Methyl methacrylate), poly (ethylacrylate), polytetrafluoroethylene, polyvinylchloride, polyacrylonitrile, polyvinylpyridine, styrene-butadiene rubber, acrylonitrile-butadiene rubber and the like. The content of the binder is 0.1 to 30% by weight, preferably 1 to 10% by weight based on the electrode active material. When the content of the binder is too small, the adhesion between the electrode active material and the current collector is insufficient, and when the content of the binder is too high, the adhesion is improved, but the content of the electrode active material decreases by that amount, which is disadvantageous in increasing battery capacity.

The conductive material may be at least one selected from the group consisting of a graphite-based conductive agent, a carbon black-based conductive agent, a metal or a metal compound-based conductive agent as a material for improving electronic conductivity. Examples of the graphite conductive agent include artificial graphite and natural graphite, and examples of the carbon black conductive agent include acetylene black, ketjen black, denka black, thermal black, Channel black and the like, and examples of the metal or metal compound conductive agent include perovskite such as tin, tin oxide, tin phosphate (SnPO ₄ ), titanium oxide, potassium titanate, LaSrCoO ₃ , and LaSrMnO _3. perovskite) substance. However, it is not limited to the conductive agents listed above.

The content of the conductive agent is preferably 0.1 to 10% by weight based on the electrode active material. When the content of the conductive agent is less than 0.1% by weight, the electrochemical properties are lowered, and when the content of the conductive agent is greater than 10% by weight, the energy density per weight decreases.

The thickener is not particularly limited as long as it can play a role of controlling the viscosity of the active material slurry. For example, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, or the like may be used.

As a solvent in which an electrode active material, a binder, a conductive material, etc. are disperse | distributed, a non-aqueous solvent or an aqueous solvent is used. Examples of the non-aqueous solvent include N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, N, N-dimethylaminopropylamine, ethylene oxide and tetrahydrofuran.

The lithium ion battery may include a separator that prevents a short circuit between the positive electrode and the negative electrode and provides a migration path of lithium ions. Such separators may be polypropylene, polyethylene, polyethylene / polypropylene, polyethylene / polypropylene / polyethylene, poly Polyolefin polymer membranes, such as propylene / polyethylene / polypropylene, or a multilayer of these, a microporous film, a woven fabric, and a nonwoven fabric can be used. In addition, a film coated with a resin having excellent stability in a porous polyolefin film may be used.

As described in detail above, the present invention relates to an electrolyte solution for a lithium ion battery comprising an oxygen adsorption material selected from the group consisting of 1,2,5-trimethylpyrrole, triphenylphosphine or copper dioxide, Oxygen adsorption material and ceramic material are combined to form a thin film on the ceramic coating layer of the negative electrode to prevent damage to the negative electrode plate has the effect of increasing the capacity of the battery.

Hereinafter, the present invention will be described in more detail with reference to one embodiment.

Example 1

LiCoO ₂ as a positive electrode active material, polyvinylidene fluoride (PVdF) as a binder and carbon as a conductive agent were mixed in a weight ratio of 92: 4: 4, and then dispersed in N-methyl-2-pyrrolidone to prepare a positive electrode slurry. It was. The slurry was coated on an aluminum foil having a thickness of 20 μm, dried, and rolled to prepare a positive electrode. Synthetic graphite as a negative electrode active material, styrene-butadiene rubber as a binder, and carboxymethyl cellulose as a thickener were mixed in a weight ratio of 96: 2: 2, and then dispersed in water to prepare a negative electrode active material slurry. The slurry was coated on a copper foil having a thickness of 15 μm, dried and rolled, and silica was coated on the negative electrode active material layer with a thickness of 5 μm as a ceramic material to prepare a negative electrode.

A lithium ion battery was manufactured by inserting a film separator of polyethylene (PE) material having a thickness of 20 μm between the electrodes, and inserting the film separator into a cylindrical can and injecting an electrolyte solution. The electrolyte solution was added 1M LiPF ₆ to a non-aqueous organic solvent of ethylene carbonate: ethyl methyl carbonate: dimethyl carbonate in a volume ratio of 1: 1: 1, 5% by weight of fluoroethylene carbonate relative to the total electrolyte weight, An electrolyte solution was prepared by adding 2% by weight of 1,2,5-trimethylpyrrole.

Example 2

Except for adding the same weight% triphenylphosphine as the oxygen adsorption material in Example 1 was carried out in the same manner as in Example 1.

Example 3

Except for adding the same weight% copper dioxide as the oxygen adsorption material in Example 1 was carried out in the same manner as in Example 1.

Experimental Example 1: Life Characteristics

The batteries prepared in Examples 1 to 3 were charged for 3 hours at 0.8 C / 4.2 V, constant current-constant voltage at room temperature, and after 10 minutes, 1 C / 3.1 V (cutoff voltage) constant current discharge. The charge and discharge was carried out for 300 cycles, and the capacity retention rate (%) at the 300th cycle was calculated.

Capacity retention rate (%) at 300th cycle = (discharge capacity at 300th cycle / discharge capacity at 1st cycle) × 100 (%)

Experimental Example 2: Discharge Capacity

The batteries prepared in Examples 1 to 3 were charged at 0.5 C / 4.2 V constant current-constant voltage for 3 hours, left for 2 hours, and discharged at 1 C / 2.75 V (cutoff voltage) constant current to measure discharge capacity.

Experimental Example 3: Low Temperature Discharge Capacity

The batteries prepared in Examples 1 to 3 were charged at 0.5 C / 4.2 V, constant current-constant voltage for 3 hours, and were left at -20 ° C. for 2 hours to produce 1 C (740 mA) /3.1 V (cutoff voltage) and constant current discharge. Low-temperature discharge capacity was measured.

Experimental Example 4: High Temperature Storage Capacity

The batteries prepared in Examples 1 to 3 were charged with 0.5 C / 4.2 V and constant current-constant voltage for 3 hours, left at 60 ° C. for 30 days, and the storage capacity of the batteries was calculated.

Table 1, the results of Experimental Example 2, Table 2, the results of Experimental Example 3, the results of Table 3 and the results of Experimental Example 4 are shown in Table 4.

Life characteristic Example 1 (1,2,5-trimethylpyrrole) 83% Example 2 (triphenylphosphine) 86% Example 3 (Copper Dioxide) 79%

As shown in Table 1, the life characteristics of the lithium ion battery using the electrolyte according to the present invention showed the highest life characteristics of the secondary battery to which triphenylphosphine was added, in addition to 1,2,5-trimethylpyrrole or The lifetime characteristics of lithium ion battery containing copper dioxide were also high.

Discharge capacity Example 1 (1,2,5-trimethylpyrrole) 99.6% Example 2 (triphenylphosphine) 99.7% Example 3 (Copper Dioxide) 96.0%

As shown in Table 2, the discharge capacity was very high when the electrolyte additive according to the present invention was added.

Low temperature discharge capacity Example 1 (1,2,5-trimethylpyrrole) 71% Example 2 (triphenylphosphine) 72% Example 3 (Copper Dioxide) 69%

As shown in Table 3, the low-temperature discharge capacity was lower than the discharge capacity at room temperature, but the discharge capacity was about 70% at low temperature.

High temperature storage capacity Example 2 (triphenylphosphine) 85% Example 3 (Copper Dioxide) 84%

As shown in Table 4, the storage capacity at high temperature was 85% and 84% for triphenylphosphine and copper dioxide, respectively.

This result is to form a thin film on the ceramic layer coated with at least one oxygen adsorbent material of 1,2,5-trimethylpyrrole, triphenylphosphine or copper dioxide to the cathode to block the transmission of oxygen. Therefore, since the oxygen participating in the side reaction can be reduced to reduce the damage of the negative electrode plate, it can be inferred to increase the life characteristics of the battery. In addition, the secondary battery added with the electrolyte according to the present invention exhibits excellent results in low-temperature discharge capacity and high-temperature storage capacity, and thus may be inferred from preventing oxygen permeation regardless of temperature.

Although the present invention has been described with reference to the above embodiments, these are merely exemplary, and those skilled in the art will understand that various modifications and equivalent other embodiments are possible therefrom. . Therefore, the true technical protection scope of the present invention will be defined by the technical spirit of the appended claims.

Claims (19)

An electrolyte comprising a non-aqueous organic solvent, a lithium salt and an oxygen adsorbent; A cathode capable of reversibly inserting and detaching lithium; And A lithium ion battery comprising a negative electrode including a carbon-based negative electrode active material layer capable of reversibly inserting and detaching lithium. The lithium ion battery according to claim 1, wherein the oxygen adsorbent is selected from at least one of 1,2,5-trimethylpyrrole, triphenylphosphine or copper dioxide. The lithium ion battery according to claim 1 or 2, wherein the oxygen adsorption material is 0.005 to 5 wt%. The lithium ion battery according to claim 1, wherein the electrolyte further comprises 0.1 to 10.0 wt% of fluoroethylene carbonate. The lithium ion battery of claim 1, wherein the non-aqueous organic solvent is at least one solvent selected from the group consisting of carbonate, ester, ether, and ketone. The carbonate of claim 5 wherein the carbonate is dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylmethyl carbonate, ethylpropyl carbonate, ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butyl Lithium ion battery, characterized in that at least one solvent selected from the group consisting of carbonate, 1,2-pentylene carbonate or 2,3-pentylene carbonate. 6. The ester of claim 5, wherein the ester is gamma-butylolactone (GBL), methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, γ-valerolactone, γ-caprolactone , δ-valerolactone or ε-caprolactone. The lithium ion battery according to claim 5, wherein the ether is tetrahydrofuran, 2-methyltetrahydrofuran or dibutyl ether. The lithium ion battery according to claim 5, wherein the ketone is polymethylvinyl ketone. The method of claim 1, wherein the lithium salt is LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiAsF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , LiN (SO ₂ CF ₃ ) ₂ , LiN (SO ₂ C ₂ F ₅ ) ₂ , LiC (SO ₂ CF ₃ ) ₃ , LiN (SO ₃ CF ₃ ) ₂ , LiC ₄ F ₉ SO ₃ , LiAlO ₄ , LiAlCl ₄ , LiCl and LiI, characterized in that at least one selected from the group consisting of Lithium ion battery. The lithium ion battery according to claim 1, wherein the carbon-based anode active material layer is made of graphite. 12. The lithium ion battery of claim 11, wherein a ceramic coating layer is laminated on the anode active material layer. The lithium ion battery of claim 12, wherein an oxygen absorbing material thin film is formed on the ceramic coating layer. The lithium ion battery of claim 12, wherein the ceramic coating layer comprises a ceramic material and a binder. The lithium ion battery according to claim 12, wherein the ceramic coating layer has a thickness of 2 to 20 μm. 15. The lithium ion battery of claim 14, wherein the ceramic material is at least one selected from alumina, silica, zirconia, zeolite, magnesia, titanium oxide and barium titanium. The lithium ion battery according to claim 14, wherein the binder is a polymer of acrylate or methacrylate or a copolymer thereof. The method of claim 14, wherein the binder is a lithium ion battery, characterized in that 1 to 5% by weight. The lithium ion battery according to claim 1, wherein the lithium ion battery is cylindrical.