WO2011025080A1 - 리튬 이차전지용 양극 활물질 및 그 제조방법과 이를 포함하는 리튬 이차전지 - Google Patents
리튬 이차전지용 양극 활물질 및 그 제조방법과 이를 포함하는 리튬 이차전지 Download PDFInfo
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
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- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a cathode active material for a lithium secondary battery, a method of manufacturing the same, and a lithium secondary battery including the same. More particularly, the present invention relates to a cathode active material having improved safety, in particular, thermal stability, high temperature durability, overcharge safety, and the like, in a cathode active material for a lithium ion secondary battery or a lithium ion polymer battery, and a method of manufacturing the same.
- lithium cobalt oxide (LiCoO 2 ) was mainly used as a cathode active material of a lithium secondary battery
- lithium nickel oxide Li (Ni-Co-Al) O 2
- lithium composite metal oxide are currently used as other layered cathode active materials.
- Li (Ni-Co-Mn) O 2 lithium nickel oxide
- Li (Ni-Co-Mn) O 2 lithium composite metal oxide
- low-cost, highly stable spinel-type lithium manganese oxide LiMn 2 O 4
- olivine-type iron phosphate compound LiFePO 4
- lithium secondary batteries using lithium cobalt oxide, lithium nickel oxide, lithium composite metal oxide and the like are excellent in basic battery characteristics, but are not sufficiently safe, particularly thermally stable and overcharged.
- various safety mechanisms such as a shut-down function of the separator, an electrolyte additive, a protection circuit, and a safety device such as PTC are introduced, but these mechanisms are designed under a situation where the filling of the cathode active material is not very high. For this reason, when the filling property of the positive electrode active material is increased to satisfy the demand for higher capacity, the operation of various safety mechanisms tends to be insufficient, and there is a problem that the safety is further lowered.
- the olivine-type iron phosphate compound has low cost and high safety characteristics, but it is difficult to expect excellent battery characteristics due to its low electronic conductivity, and does not meet the demand for high capacity due to low average operating potential.
- Japanese Patent Laid-Open No. 2001-143705 discloses a positive electrode active material in which lithium cobalt oxide and lithium manganese oxide are mixed. However, simply mixing a lithium manganese oxide with excellent safety is not enough improvement effect.
- Japanese Laid-Open Patent Publication No. 2002-143708 proposes a positive electrode active material having two layers of lithium nickel composite oxides having different compositions, but since the positive electrode active material having two layers of lithium nickel composite oxides having different compositions is applied, Fundamentally, the safety of overcharging cannot be sufficiently improved.
- Japanese Laid-Open Patent Publication No. 2007-012441 employs a positive electrode having a positive electrode active material layer of two or more layers for the purpose of improving overcharging characteristics, wherein an olivine-type iron phosphate lithium or spinel-type manganese oxide is applied to a layer in contact with the positive electrode current collector. It is proposed to constitute.
- the improvement effect on the improvement of the overcharge characteristic is expected, since the thickness of these oxide layers is hard to be formed below the average particle diameter, it is formed in the thickness of several micrometers, and it does not contain a conductive material or a conductive support material, and is high current discharge. The characteristics are not enough.
- Japanese Laid-Open Patent Publication No. 2006-19229 proposes a coating of the surface of secondary particles with lithium cobalt zirconium oxide for the purpose of improving the safety of lithium nickel oxide, which is not safe.
- the wet coating process is applied to coat the surface of the lithium nickel oxide secondary particles with lithium cobalt zirconium oxide, there is a problem that the productivity is limited even if the improvement effect is obvious.
- the problem to be solved by the present invention is the positive electrode active material and excellent reproducibility and productivity of the positive electrode active material that can dramatically improve the safety, in particular thermal stability, high temperature durability and overcharge safety, etc. without deteriorating basic battery characteristics It is to provide a manufacturing method.
- the cathode active material for lithium secondary battery of the present invention is a lithium metal oxide secondary particle core portion formed by agglomeration of a plurality of lithium metal oxide primary particles; A first shell part formed by coating a plurality of barium titanate particles and metal oxide particles on a surface of the secondary particle core part; And a second shell portion formed by coating a plurality of olivine-type iron phosphate particles and conductive material particles on the surface of the first shell portion.
- the cathode active material of the present invention may include a first shell portion including barium titanate particles and metal oxide particles, thereby improving thermal stability and high temperature durability while maintaining excellent electrical characteristics.
- the first shell part including the barium titanate and the metal oxide prevents contact between the core part and the electrolyte and suppresses heat generation due to side reactions of the electrolyte, thermal stability and high temperature durability may be improved.
- the inventors of the present invention confirmed that barium titanate has a property of changing the crystal structure at about 125 ° C. to increase the electrical resistance, and introducing the same into the cathode active material improves the thermal safety of the cathode active material.
- metal oxides may be further improved in various physical properties according to specific types.
- the cathode active material of the present invention may include a second shell portion including olivine-type lithium phosphate particles and a conductive material particle on the surface of the first shell portion, thereby improving overcharge safety and discharge characteristics.
- the inventors of the present invention confirmed that the positive electrode active material of the present invention includes two coating layers of the first shell portion and the second cell portion, and exhibits a significant synergistic effect without degrading the characteristics expressed from each shell portion. It was.
- the method for producing a positive electrode active material for a lithium secondary battery of the present invention (S1) by firing a metal hydroxide and lithium salt, a lithium metal oxide secondary particle core portion in which a plurality of lithium metal oxide primary particles are aggregated Manufacturing step; (S2) dry-coating a plurality of barium titanate particles and metal oxide particles on the surface of the core part and performing heat treatment to form a first shell part outside the core part; And (S3) dry-coating a plurality of olivine-type iron phosphate particles and conductive material particles on the surface of the first shell portion to form a second shell portion.
- the method of manufacturing a cathode active material for a lithium secondary battery of the present invention can not only enable efficient coating with excellent reproducibility by using a dry coating method, but also improve the powder properties of active material particles, thereby improving the electrical properties of the cathode manufactured from the active material particles. have.
- the positive electrode active material for a lithium secondary battery of the present invention can be used in the production of a lithium secondary battery positive electrode and a lithium secondary battery containing such a positive electrode.
- Example 1 is a SEM photograph of a cathode active material of the present invention prepared according to Example 1 (a: core cathode active material, b: first cathode active material, c: second cathode active material).
- FIG. 2 is a Mapping SEM photograph of the positive electrode active material particles of the present invention prepared according to Example 1. (a: Mapping Image, b: Fe mapping, c: Ti mapping, d: C mapping)
- FIG. 3 is a graph showing particle size distribution of the cathode active material powders of Example 1 and Comparative Example 5.
- a metal hydroxide and a lithium salt are fired to prepare a lithium metal oxide secondary particle core part in which a plurality of lithium metal oxide primary particles are aggregated (S1).
- the lithium metal oxide that may be used in the present invention may be used without limitation except for an olivine-type iron phosphate lithium oxide, as long as it is a lithium metal oxide used as a cathode active material of a lithium secondary battery in the art.
- LiMn 2 O 4 any one or mixture of two or more selected from the group
- the lithium metal oxide secondary particles used as the core part are prepared by aggregating lithium metal oxide primary particles, and are manufactured by firing a metal hydroxide and a lithium salt, and the specific manufacturing method thereof is as follows.
- the metal hydroxide mentioned above uses each raw material corresponding to the target positive electrode active material.
- As the main raw material sulfates, nitrates, acetates and the like can be used.
- An aqueous solution containing such a metal salt is continuously added in a coprecipitation environment, and a slurry containing a metal hydroxide is continuously taken to prepare a metal hydroxide by washing with water, filtration and drying.
- the use of such metal hydroxides limits the influx of impurities contained in the respective metal salts, enables composition control at the atomic level, and the addition of heterogeneous elements introduced in trace amounts. The effect can be maximized, and lithium metal oxide of a uniform crystal structure with almost no impurities can be easily produced.
- the metal hydroxide prepared by the hydroxide coprecipitation method from the raw material precursor is heat-treated at a predetermined temperature, mixed with various lithium salts to a desired composition, and then calcined under ordinary firing conditions to produce the lithium metal oxide of the present invention. can do.
- the lithium metal oxide thus prepared is obtained as lithium metal oxide secondary particles in which lithium metal oxide primary particles are aggregated.
- the average particle diameter of the primary particles constituting the secondary particles may be variously changed depending on the coprecipitation environment and the firing conditions according to the composition ratio of the metal hydroxide, but is not limited thereto.
- the average particle diameter of the secondary particles may be variously changed depending on the use and manufacturing environment, for example, 7 ⁇ 15um (micrometer), but is not limited thereto.
- the average particle diameter of the secondary particles has the above range, the stability of the secondary particles is excellent during the subsequent dry coating process of barium titanate and metal oxide, and the efficiency and reproducibility of the coating process are further improved.
- the shape of the secondary particles is not particularly limited, the spherical case may have a higher efficiency of the coating process of coating the surface of the secondary particles with the first shell portion and the second shell portion.
- a plurality of barium titanate particles and metal oxide particles are dry coated on the surface of the core part and heat treated to form a first shell part outside the core part (S2).
- the first shell portion formed of a plurality of barium titanate particles and metal oxide particles is formed of particles having an average particle diameter smaller than those of the olivine-type iron phosphate particles and the conductive material particles forming the second shell portion described later, 2 It is possible to effectively suppress the side reaction of the electrolyte by blocking more faithfully the electrolyte that the shell portion does not block enough.
- barium titanate used in the present invention is not only pure barium titanate, but also a small amount (0.1 to 1.5% by weight) of elements such as La, Ce, Nd, Pr, Sm, Gd, Nb, Bi, Sb, and Ta are added. It also includes barium titanate. Barium titanate is a high dielectric constant material, and is a PTC (Positive Temperature Coefficient) thermistor whose resistance increases with increasing temperature. The barium titanate used in the present invention not only suppresses side reactions of the electrolyte by coating the core portion, but also has a property that the electrical resistance is significantly increased by changing the crystal structure around 125 ° C as described above.
- the battery when the battery is placed in a high temperature environment or an excessive current is generated inside the battery such as an overcurrent occurs due to an internal short circuit, it can act as a resistance to block the flow of electrons, thereby improving thermal stability and high temperature durability of the positive electrode active material. Can be.
- the average particle diameter of the barium titanate used in the present invention may be variously changed depending on the use and the manufacturing environment, it is preferable that it is 1 um (micrometer) or less for the purpose of the present invention, and the average particle diameter thereof is 1 um (micrometer). Smaller than) There is no particular lower limit because the efficiency of the dry coating process of the present invention can be maximized. For example, it may have an average particle diameter of 1nm, but is not limited thereto. If the average particle diameter exceeds 1 um (micrometer), the efficiency and reproducibility of the surface coating process of the lithium metal oxide corresponding to the core is inferior, which is undesirable.
- the specific surface area of the coating material (first shell portion forming material) must be sufficiently secured. If the average particle diameter exceeds 1 um (micrometer), it is not preferable because some of the barium titanate is not coated and simply remains in mixed form.
- the content of barium titanate according to the present invention may be appropriately selected depending on the type of specific battery in which the cathode active material is used, and may be, for example, 0.05 to 1 part by weight based on 100 parts by weight of the core part, but is not limited thereto. .
- the content is less than 0.05 parts by weight, the use effect of barium titanate is insignificant, and when the content is more than 1 part by weight, the specific capacity of the positive electrode active material may increase with increasing content.
- a metal oxide is coated together with barium titanate on the core part according to the present invention to form a first shell part.
- the metal oxide particles act as a binder to strengthen the bond between the core portion and the barium titanate particles to prevent direct contact between the core portion and the electrolyte, thereby improving thermal stability, high temperature durability, and the like. Affect
- various additional physical properties can be improved depending on the type of specific metal oxide.
- titanium oxide TiO 2
- Y 2 O 3 yttrium oxide
- MgO magnesium oxide
- ZnO zinc oxide
- the metal oxide according to the present invention may further include a lithium metal oxide, it can be expected to improve the fast charge, discharge characteristics or cycle characteristics without reducing the capacity of the battery.
- lithium metal oxides include various lithium metal oxides such as layered lithium composite metal oxides, lithium cobalt oxides, spinel type lithium manganese oxides, and the like.
- the metal oxide applied to the first shell portion is not limited thereto, and various kinds of nano-level metal oxide materials may be applied to the first shell portion to improve its functionality, that is, safety, high temperature characteristics, and conductivity. It can be used in combination.
- the average particle diameter of the metal oxide used in the present invention may be variously changed depending on the use and manufacturing environment, for example, 1 to 100 nm, but is not limited thereto.
- Productivity is excellent in the above range and the effect of forming the first shell portion can be maximized by maximally preventing a decrease in capacity of the battery.
- the average particle diameter is smaller, the specific surface area that may be involved in the coating is maximized, so that the first shell portion may be formed in a small amount, and the effect thereof may be maximized. If the size of the metal oxide is less than 1 nm, it is difficult to easily obtain the material itself, which may raise the cost of manufacturing the core-shell type cathode active material.
- the average particle diameter of the metal oxide of the present invention may have a value that can be located in the gap formed between the barium titanate particles.
- the metal oxide particles can fill the voids between the barium titanate particles, thereby forming the first shell portion more densely, and the function as a binder can be maximized.
- Commonly known coating methods for producing the core-shell type cathode active material according to the present invention include a dry coating method and a wet coating method.
- the wet method has been mostly applied for uniform dispersion of the coating material. That is, it was common to coat by dispersing or dispersing the coating material or an organic solution or aqueous solution in which the coating material was dissolved, or spraying and impregnating the positive electrode active material and then drying.
- the dry coating method used in the present invention is to coat the coating material corresponding to the shell portion on the surface of the positive electrode active material corresponding to the core portion by a mechanical method, according to the equipment used for the purpose of coating, shear force, impact force , Compressive force and the like are expressed.
- a positive electrode active material obtained by firing a metal precursor and lithium as raw material precursors at a high temperature is sintered by a hydroxide raw material precursor having a slightly lower spherical shape or an excess of lithium by high temperature firing, and thus grinding and classification are required. It was practically impossible to grind the prepared cathode active material to have an average particle diameter value of a metal hydroxide as a raw material precursor while maintaining sphericity.
- the spherical effect and the disintegration effect of the core part may be simultaneously caused by the nanometer-sized metal oxide corresponding to the shell part, thereby improving the powder properties.
- the electrical properties of the positive electrode active material to be produced may be produced.
- the heat treatment process is performed.
- the heat treatment conditions may be appropriately selected according to the manufacturing environment such as the type of the cathode active material of the core portion, for example, may be performed for 4 to 12 hours at 300 ⁇ 600 °C, but is not limited thereto.
- the shell portion has a very high density, can sufficiently compensate for the crystal structure defects of the core portion, and can stably maintain the structure of the core portion.
- the heat treatment time can be sufficiently obtained the effect in the above range, and if more than 12 hours, it is difficult to expect any additional effects due to the increase of the heat treatment time.
- a plurality of olivine-type iron phosphate particles and conductive material particles are dry coated on the surface of the first shell portion and heat treated to form a second shell portion (S3).
- the olivine-type iron phosphate particles and the conductive material particles are coated on the first shell portion as the second shell portion forming material.
- the olivine-type lithium iron phosphate has lower hardness than barium titanate or metal oxide of the first shell portion. Therefore, when the olivine-type lithium iron phosphate changes the coating order with barium titanate or metal oxide to form the first shell portion, micropowder may occur or the core portion may not be able to withstand the coating process of forming the second shell portion with barium titanate or metal oxide. The phenomenon which separates from the thing generate
- the second shell portion formed of the olivine name iron phosphate particles and the conductive material particles serves to primarily block the contact between the external electrolyte and the core portion.
- olivine-type lithium iron phosphate is known to have the largest increase in resistance due to overcharging. This limits the amount of lithium released from the core positive electrode active material, thereby reducing the amount of lithium deposited on the negative electrode, thereby reducing the amount of heat generated due to the reaction with the electrolyte solution, and therefore, in particular, an effect of improving safety during overcharging. Can be represented.
- the average particle diameter of the olivine-type lithium iron phosphate (LiFePO 4 ) particles used in the present invention may vary depending on the use and the manufacturing environment, but for the purpose of the present invention, it is preferable that it is 1 um (micrometer) or less.
- the specific surface area of the material forming the second shell portion If the average particle diameter exceeds 1 um (micrometer) because it must be sufficiently secured, the proportion of coated olivine-type lithium iron phosphate particles to be reduced will be reduced and uncoated materials will simply remain in mixed form. not.
- the content of the olivine-type lithium iron phosphate constituting the second shell portion according to the present invention can be appropriately selected depending on the type of specific battery in which the positive electrode active material is used, for example, 0.05 to 5 based on 100 parts by weight of the core portion. It may be part by weight, but is not limited thereto. If the content is less than 0.05 parts by weight, the purpose of the coating of the olivine-type iron phosphate, that is, the effect of improving overcharge characteristics is insignificant. This is not preferable because it can cause adverse effects such as a decrease in the average discharge voltage.
- the olivine-type lithium iron phosphate has a very low conductivity, which causes difficulty in commercializing the battery due to a decrease in capacity of the battery.
- the materials used in the first shell portion according to the present invention are also electrically inert, which causes a increase in powder resistance.
- the present invention can additionally introduce a conductive material to the second shell portion to prevent the battery from being lowered due to the use of olivine-type lithium iron phosphate, and to maintain excellent electrical properties of the active material.
- the conductive material particles are introduced into the second shell portion, the lithium ion blocking effect of the olivine-type lithium iron phosphate is not substantially reduced. Therefore, even when the conductive material particles are introduced, the stability of the positive electrode active material does not decrease, but rather, the electrical characteristics are improved.
- a conductive metal, a conductive polymer, conductive carbon, and the like may be used.
- Specific examples of the conductive carbon include carbon nanotubes, katchen black, acetylene black, super P (super-P), graphite, and activated carbon. Etc., but is not limited thereto.
- the average particle diameter of the conductive material that can be used is preferably 1 um (micrometer) or less, the smaller the average particle diameter is less than 1 um (micrometer), the specific surface area of the present invention can be increased to reduce the amount of addition, so the lower limit is no limits. For example, it may have a thickness of 1nm, but is not limited thereto.
- the average particle diameter of the conductive material particles may be similar to the average particle diameter of the olivine-type lithium iron phosphate particles introduced at the same time, especially in the case of using conductive carbon as the conductive material, deformation or cracking of the conductive carbon particles may occur during the coating process. Since the average particle diameter of the particle
- the content of the conductive material included in the second shell part according to the present invention may be appropriately selected depending on the type of the specific battery in which the positive electrode active material is used, and may be included, for example, at least 0.1 part by weight based on 100 parts by weight of the core part. However, the present invention is not limited thereto. If the content is less than 0.1 part by weight, the effect of using the conductive material is insignificant.
- the upper limit of the content of the conductive material of the second shell portion is not particularly limited, it is within the range for preparing a conventional positive electrode slurry, the excess conductive material is present on the surface of the positive electrode active material even if an excessive amount of the conductive material is used, and further in the slurry manufacturing step No addition of conductive agent is required, which shortens the slurry manufacturing process time.
- the conductive material of the shell portion is 10 parts by weight or less, preferably 5 parts by weight or less, most preferably 1 weight. It may be included below, but is not limited thereto.
- the heat treatment process is performed, and the heat treatment conditions may be the same as or similar to the heat treatment process of step (S2), and the same effect as the heat treatment of step (S2) may be expected. have.
- the heat treatment step atmosphere is preferably performed in an inert atmosphere.
- the cathode active material for a lithium secondary battery of the present invention which may be manufactured by the above method, may be bonded to at least one surface of a cathode current collector using a binder resin to form a cathode of a lithium secondary battery.
- the binder resin and the positive electrode current collector may be used without limitation those conventionally used in the art.
- the positive electrode for a lithium secondary battery of the present invention may be manufactured as a lithium secondary battery together with a negative electrode, a separator and an electrolyte interposed between the positive electrode and the negative electrode.
- the negative electrode, the separator and the electrolyte can be used without limitation those conventionally used in the art.
- Nickel sulfate (NiSO 4 ⁇ 6H 2 O), manganese sulfate (MnSO 4 ⁇ H 2 O) and cobalt sulfate (CoSO 4 ⁇ 7H 2 O) were purified so that the molar ratio of nickel, cobalt and manganese was 0.4: 0.3: 0.3 It was dissolved in the ion-exchanged water to prepare a metal aqueous solution. In addition, an aqueous sodium hydroxide solution and an aqueous ammonia solution were prepared.
- the coprecipitation reactor was supplied at a rate of 5 L / hr for the aqueous metal solution and 0.5 L / hr for the aqueous ammonia solution using a metering pump at a pH of 11.0, a rotational speed of 400 rpm, and an inert nitrogen atmosphere.
- the sodium hydroxide aqueous solution was intermittently added to maintain a constant pH of the solution in the reactor to 11.0.
- the reaction proceeded for 48 hours or longer to obtain a slurry containing a complex metal hydroxide of a constant size.
- the slurry was washed with water using a centrifugal filter until the pH of the filtrate was 9.0 or lower, and then filtered.
- the obtained composite metal hydroxide powder was dried at 120 ° C. for at least 24 hours to prepare a composite metal hydroxide.
- the composite metal hydroxide was heat-treated at a temperature of 300 ° C. or higher for at least 12 hours in order to match the exact stoichiometry with the lithium salt, and then mixed with the lithium salt such that the stoichiometric ratio with the lithium salt was 1: 1.1.
- the mixture was calcined at 950 ° C. for 24 hours at 500 ° C. for 24 hours in a high temperature kiln with temperature control.
- the lithium composite metal oxide prepared by grinding and classification had a Ni: Co: Mn ratio of 0.40: 0.30: 0.30, and an average particle diameter D 50 of 9.8 um (micrometer).
- a core-shell type positive electrode active material was prepared by using the obtained lithium composite metal oxide as a core, and using a barium titanate powder having an average particle diameter (D 50 ) of 220 nm and a titanium oxide powder having an average particle diameter of D 50 of 20 nm as a coating material.
- a barium titanate powder having an average particle diameter (D 50 ) of 220 nm and a titanium oxide powder having an average particle diameter of D 50 of 20 nm as a coating material.
- dry coating equipment Hogawa Micron Co., Japan
- 600 g of composite metal oxide such that the weight ratio of barium titanate and titanium oxide corresponding to the shell part is 1 part by weight and 0.1 part by weight with respect to 100 parts by weight of the core part, respectively.
- the mixture was treated at a rotational speed of 2700 rpm for 3 minutes and then heat treated at 500 ° C. for 4 hours to prepare a core-shell type first positive electrode active material having a first shell portion.
- the core is made of olivine-type lithium iron phosphate powder having an average particle diameter (D 50 ) of 200 nm and conductive carbon powder having an average particle diameter (D 50 ) of 500 nm as a coating material.
- a shell type cathode active material was prepared.
- the first shell portion is provided such that the weight ratio of the olivine-type lithium iron phosphate powder and the conductive carbon powder corresponding to the second shell portion is 1.5 parts by weight and 0.2 parts by weight, respectively, with respect to 100 parts by weight of the core-shell positive electrode active material having the first shell.
- a core-shell type second positive electrode active material having a second shell part was prepared by the same method as the coating method of the first shell part.
- a core-shell type cathode active material was prepared in the same manner as in Example 1 except that the composition of the lithium composite metal oxide was prepared such that the ratio of Ni: Co: Mn was 0.50: 0.20: 0.30 and used as the core part.
- the lithium composite metal oxide cores prepared in Examples 1 and 2 were used as final cathode active materials, respectively.
- the first positive electrode active material having only the first shell portion prepared in Example 1 was used as the final positive electrode active material.
- a positive electrode active material was manufactured in the same manner as in Example 1, except that only the first shell part was formed by first coating the lithium composite metal oxide core part prepared in Example 1 with the second shell part forming material of Example 1.
- a core-shell composite metal oxide was prepared in the same manner as in Example 1 except that the secondary coating was performed to form the second shell portion from the material.
- the cathode active material particles of the present invention have excellent surface shape. That is, it can be seen that the fine pores on the surface seen in the core cathode active material are uniformly coated by the coating material forming the shell portion.
- FIG. 2 the map shapes of the respective constituent elements of the core-shell type positive electrode active material particles obtained in Example 1 are shown in FIG. 2 (a: Mapping Image, b: Fe mapping, c: Ti mapping, and d: C mapping).
- the average particle size was measured using a particle size distribution analyzer (Malvern, Mastersizer 2000E).
- the average particle diameter D 50 was calculated
- the tap density was measured from the volume change before and after 500 strokes using a 100 ml measuring cylinder.
- Comparative Example 5 in which the olivine-type iron phosphate oxide was first coated, and then the second coating of barium titanate and titanium oxide was carried out, the nanometer-sized barium titanate particles and titanium oxide particles were formed.
- the coating process separation of the olivine-type lithium iron phosphate particles forming the first shell part occurred, and it was confirmed that the first shell part could not be maintained intact.
- the core-shell composite metal oxide of the comparative example 5 it was confirmed that microparticles
- Example 1 and Comparative Example 5 particle size distributions of Example 1 and Comparative Example 5 are shown in FIG. 3. Referring to FIG. 3, in the case of Comparative Example 5, the presence of the fine particles may be confirmed.
- the slurry was mixed with NMP solution in which teflonized acetylene black and binder PVDF were dissolved as a positive electrode active material and a conductive material.
- NMP solution in which teflonized acetylene black and binder PVDF were dissolved as a positive electrode active material and a conductive material.
- the mass ratio of the positive electrode active material, the conductive material and the binder in the slurry was 90: 5: 5.
- the slurry was applied onto a 30um (micrometer) Al current collector, dried, compressed to a constant thickness, and punched out to a diameter of 13 mm to prepare a positive electrode.
- the coin type battery of the 2032 standard was manufactured through the thickness of 20 micrometers separator.
- a 1.2 mol LiPF 6 solution of an ethylene carbonate and diethyl carbonate mixed solvent (volume ratio 1: 3) was used as the electrolyte.
- the battery was charged and discharged at a constant current-constant voltage condition (end of charge 0.02C) and discharge at a constant current condition at a current density of 0.2 C at a voltage range of 25 ° C. and 2.5 to 4.2 V using a charge and discharge cycle device.
- the measurement results are shown in Table 2.
- the positive electrode active material of the present invention having a double coating layer has almost the same electrical properties as the comparative examples having no coating layer or one coating layer.
- batteries were manufactured.
- a slurry was prepared by mixing the prepared cathode active material with an NMP solution in which carbon, a conductive material, and PVDF, a binder, were dissolved.
- the mass ratio of the positive electrode active material, the conductive material and the binder in the slurry was 92: 4: 4.
- a graphite as a negative electrode, the negative electrode and the positive electrode faced each other through a separator, and then a 113 ⁇ m-thick aluminum exterior material was applied and sealed and heat-sealed in a glove box in an argon atmosphere to prepare a pouch-type battery.
- the battery standard size was 60 mm thick x 216 mm wide x 216 mm long, and the design capacity was 25 Ah.
- the battery was first charged and discharged at a current density of 0.2 C (5h) at 25 ° C. and a voltage range of 3.0 to 4.2 V using a charge and discharge cycle device, and then charged and discharged at various current densities.
- the high rate characteristic was evaluated from the ratio of the discharge capacity at 15C current density using discharge capacity at 0.5C current density as a reference capacity.
- Table 3 summarizes the high rate characteristics of the positive electrode active material obtained in Examples and Comparative Examples.
- the examples of the present invention can be seen that the high rate characteristics are slightly reduced as having a double coating layer, it can be seen that the thermal stability is improved compared to the comparative examples. However, in the case of Comparative Example 3, the results of high rate characteristics and thermal stability evaluation is not bad, but it can be confirmed that the results of high temperature durability and overcharge safety evaluation are not preferable.
- the storage capacity was stored for 2 weeks in a 60 ° C. high temperature oven in a state of full charge of 4.2V, and the storage capacity and recovery capacity before and after storage were evaluated and shown in Table 4.
- the storage capacity and the recovery capacity after storage were evaluated by setting the discharge capacity before storage to 100%.
- the batteries prepared from the examples are all excellent in high temperature durability than the batteries of the comparative examples. This is considered to be because the shell portion of the two-layer structure of the present invention minimized contact between the core portion and the electrolyte solution.
- Examples 1 to 2 and Comparative Examples 4 to 5 that contain an olivine-type lithium iron phosphate compound as the shell material it can be seen that safety due to overcharging is improved compared to Comparative Examples 1 to 3.
- Examples 1 to 2 which further include a first shell portion formed of barium titanate and a metal oxide as the first shell portion, exhibit the best characteristics. This shows that the positive electrode active material of the present invention is excellent in overcharge safety and is suitable for high capacity batteries.
- the positive electrode active material for a lithium secondary battery of the present invention includes two layers of shell portions formed of different materials in lithium metal oxide, thereby maintaining safety, in particular thermal stability, high temperature durability, and overcharge safety, while maintaining excellent basic electrical characteristics of the lithium secondary battery. To improve.
- the method for producing a cathode active material for a lithium secondary battery of the present invention has excellent reproducibility and productivity in manufacturing the cathode active material of the present invention.
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Abstract
Description
구 분 | 코어부 양극 활물질 | 1차 코팅(제1쉘부 형성) | 2차 코팅(제2쉘부 형성) | |||
D50, micrometer | g/cc | D50, micrometer | g/cc | D50, micrometer | g/cc | |
실시예 1 | 9.83 | 2.49 | 9.62 | 2.58 | 9.64 | 2.59 |
실시예 2 | 9.66 | 2.48 | 9.54 | 2.56 | 9.55 | 2.55 |
비교예 1 | 9.83 | 2.49 | X | X | ||
비교예 2 | 9.66 | 2.48 | X | X | ||
비교예 3 | 9.83 | 2.49 | 9.62 | 2.58 | X | |
비교예 4 | 9.83 | 2.49 | 9.72 | 2.54 | X | |
비교예 5 | 9.83 | 2.49 | 9.72 | 2.54 | 9.65 | 2.43 |
구 분 | 1st 0.2C 충전용량(mAh/g) | 1st 0.2C 방전용량(mAh/g) | 1st 효율(%) | 1st 비가역용량(mAh/g) | 정전압충전비율(%) |
실시예 1 | 167.4 | 150.1 | 89.6 | 17.3 | 0.9 |
실시예 2 | 171.7 | 154.7 | 90.0 | 17.0 | 0.8 |
비교예 1 | 168.2 | 150.3 | 89.3 | 17.9 | 0.9 |
비교예 2 | 172.5 | 154.8 | 89.7 | 17.7 | 1.0 |
비교예 3 | 166.3 | 149.5 | 89.8 | 16.8 | 0.8 |
비교예 4 | 166.5 | 149.7 | 89.9 | 16.8 | 0.9 |
비교예 5 | 165.7 | 148.3 | 89.0 | 17.4 | 1.2 |
구 분 | 15C 방전 특성(@0.5C, %) | 열적 안정성 시험 결과 |
실시예 1 | 87.2 | Pass |
실시예 2 | 89.3 | Pass |
비교예 1 | 90.1 | Fail |
비교예 2 | 90.5 | Fail |
비교예 3 | 89.6 | Pass |
비교예 4 | 88.5 | Fail |
비교예 5 | 86.3 | Fail |
구 분 | 저장 전 | 유지 용량 | 회복 용량 | ||
용량(Ah) | 용량(Ah) | % | 용량(Ah) | % | |
실시예 1 | 25.7 | 22.5 | 87.8 | 24.4 | 95.3 |
실시예 2 | 25.6 | 22.3 | 87.4 | 24.6 | 96.2 |
비교예 1 | 25.4 | 20.5 | 81.0 | 22.7 | 89.4 |
비교예 2 | 25.7 | 21.0 | 82.1 | 23.4 | 91.2 |
비교예 3 | 25.3 | 21.2 | 84.0 | 23.5 | 93.2 |
비교예 4 | 25.6 | 21.3 | 83.3 | 23.7 | 92.6 |
비교예 5 | 25.5 | 21.3 | 83.4 | 23.7 | 92.8 |
구 분 | 시험 결과 | |||
A | B | C | D | |
실시예 1 | O | |||
실시예 2 | O | |||
비교예 1 | O | O | ||
비교예 2 | O | O | ||
비교예 3 | O | |||
비교예 4 | O | O | ||
비교예 5 | O | O |
Claims (9)
- 다수의 리튬 금속 산화물 일차입자가 응집하여 형성된 리튬 금속 산화물 이차입자 코어부;상기 이차입자 코어부 표면에 다수의 티탄산 바륨 입자 및 금속 산화물 입자를 코팅하여 형성된 제1 쉘부; 및상기 제1 쉘부 표면에 다수의 올리빈형 인산철 리튬 입자 및 도전재 입자를 코팅하여 형성된 제2 쉘부;를 포함하여 이루어지는 리튬 이차전지용 양극 활물질.
- 제1항에 있어서,상기 코어부의 리튬 금속 산화물은 LiCoO2, Li(NiaCobAlc)O2(0<a<1, 0<b<1, 0<c<1, a+b+c=1), Li(NiaCobMnc)O2(0<a<1, 0<b<1, 0<c<1, a+b+c=1), Li(LixNiaCobMnc)O2(0<x<0.5, 0<a<1, 0<b<1, 0<c<1, a+b+c=1) 및 LiMn2O4로 이루어진 군에서 선택되는 어느 하나 또는 이들의 2종 이상의 혼합물인 것을 특징으로 하는 리튬 이차전지용 양극 활물질.
- 제1항에 있어서,상기 금속 산화물은 산화알루미늄, 산화 티타늄, 산화 이트륨, 산화 마그네슘, 산화 아연 및 리튬 금속 산화물로 이루어진 군에서 선택되는 어느 하나 또는 2종 이상의 혼합물인 것을 특징으로 하는 리튬 이차전지용 양극 활물질.
- 제1항에 있어서,상기 제2 쉘부의 도전재는 도전성 금속, 도전성 고분자 및 도전성 탄소로 이루어진 군에서 선택된 어느 하나 또는 이들의 2종 이상의 혼합물인 것을 특징으로 하는 리튬 이차전지용 양극 활물질.
- (S1) 금속 수산화물과 리튬염을 소성시켜 다수의 리튬 금속 산화물 일차입자가 응집된 리튬 금속 산화물 이차입자 코어부를 제조하는 단계;(S2) 상기 코어부 표면에 다수의 티탄산 바륨 입자 및 금속 산화물 입자를 건식 코팅하고 열처리하여 상기 코어부 외부에 제1 쉘부를 형성하는 단계; 및(S3) 상기 제1 쉘부의 표면에 다수의 올리빈형 인산철 리튬 입자 및 도전재 입자를 건식 코팅하고 열처리하여 제2 쉘부를 형성하는 단계;를 포함하는 리튬 이차전지용 양극 활물질의 제조방법.
- 제5항에 있어서,상기 (S1) 단계에서 상기 금속 수산화물은 공침법에 따라 제조되는 것을 특징으로 하는 리튬 이차전지용 양극 활물질의 제조방법.
- 제5항에 있어서,상기 (S2) 및 (S3) 단계에서 열처리는 300~600℃에서 4~12시간 동안 수행되는 것을 특징으로 하는 리튬 이차전지용 양극 활물질의 제조방법.
- 양극 집전체; 및 상기 양극 집전체의 적어도 일면에 형성되며, 양극 활물질 및 바인더 수지를 포함하는 양극 활물질 층을 구비한 리튬 이차전지의 양극에 있어서,상기 양극 활물질이 제1항의 양극 활물질인 것을 특징으로 하는 리튬 이차전지의 양극.
- 양극, 음극 및 상기 양극과 음극 사이에 개재된 격리막을 포함하는 리튬 이차전지에 있어서,상기 양극이 제8항에 따른 양극인 것을 특징으로 하는 리튬 이차전지.
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EP09848783.8A EP2403041B9 (en) | 2009-08-28 | 2009-09-01 | Cathode active material for lithium secondary battery, preparation method thereof, and lithium secondary battery containing same |
CN200980000467.3A CN102084521B (zh) | 2009-08-28 | 2009-09-01 | 用于锂蓄电池的阴极活性材料、其制备方法以及包含其的锂蓄电池 |
JP2011528920A JP5231648B2 (ja) | 2009-08-28 | 2009-09-01 | リチウム二次電池用正極活物質、その製造方法、リチウム二次電池の正極、及びリチウム二次電池 |
US12/626,300 US8808916B2 (en) | 2009-08-28 | 2009-11-25 | Cathode active material for lithium secondary batteries, method for preparing the same, and lithium secondary batteries comprising the same |
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EP2403041B9 (en) | 2017-11-15 |
JP5231648B2 (ja) | 2013-07-10 |
JP2011526732A (ja) | 2011-10-13 |
CN102084521B (zh) | 2014-01-22 |
EP2403041A1 (en) | 2012-01-04 |
EP2403041A4 (en) | 2015-12-23 |
KR20110023067A (ko) | 2011-03-08 |
CN102084521A (zh) | 2011-06-01 |
KR101105879B1 (ko) | 2012-01-16 |
EP2403041B1 (en) | 2017-07-19 |
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