• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    ACTIVE ANODY MATERIAL HAVING HIGH DENSITY AND ITS PREPARATION METHOD An active anode material including lithium metal oxide particles with an internal porosity ranging from 3% to 8% and an average particle diameter (D50) is provided. varies between 5 (MI) m and 12 (MI) m. According to the present invention, since high density lithium metal oxide particles are included, adhesion to an anode can be significantly improved, even using the same or lesser amount of a binder that is needed during preparation of an anode slurry, and high-rate characteristics of a secondary battery can be improved by decreasing the average particle diameter of the lithium metal oxide particles.
    公开号:BR112014001839B1
    申请号:R112014001839-1
    申请日:2013-07-11
    公开日:2020-12-29
    发明作者:Byung Hun Oh；Je Young Kim；Hyun Woong Yun；Ye Ri Kim
    申请人:Lg Chem, Ltd；
    IPC主号:
    专利说明:

    TECHNICAL FIELD
    [0001] The present invention relates to an anode active material including high density lithium metal oxide particles, a secondary lithium battery including the same, and a method of preparing the anode active material. TECHNICAL FUNDAMENTALS
    [0002] The prices of energy sources have increased due to the depletion of fossil fuels, interest in environmental pollution has been amplified, and the demand for alternative sources of eco-friendly energy has become an indispensable factor for the future life. Thus, research on various energy generation techniques, such as nuclear energy, solar energy, wind energy and tidal energy, has been continuously carried out, and great interests in energy storage devices to more effectively use the energy generated in this way as well has grown.
    [0003] In particular, with regard to secondary lithium batteries, demand as an energy source has increased rapidly as technological development and demand for mobile devices has increased, its use as electric vehicle power sources (EVs) ) or hybrid electric vehicles (HEV) recently performed, and the application area has been extended to include uses, such as an auxiliary power source through power grids and the like.
    [0004] A carbon-based compound that allows reversible intercalation and non-intercalation of lithium ions, as well as the structural and electrical properties that are maintained, has been mainly used as an anode active material of an anode of a secondary lithium battery typical. However, a significant amount of research on titanium and lithium oxides has recently been conducted.
    [0005] Since lithium titanium oxides are a zero stress material in which structural changes are extremely low during loading and unloading, life characteristics are relatively excellent, a relatively high voltage range is obtained, and dendrites do not occur . Thus, titanium and lithium oxides are known as a material that has excellent safety and stability.
    [0006] However, with regard to titanium and lithium oxides, since their electrical conductivities may be less than those of carbon materials, such as graphite, and atomization may be necessary to improve rates charge, there may be a limitation that a binder content can increase to form an electrode. DISCLOSURE OF THE INVENTION TECHNICAL PROBLEM
    [0007] The present invention provides an active anode material including lithium metal oxide particles with specific internal porosity and average particle diameter. In addition, a secondary battery including the anode's active material is provided.
    [0008] The present invention also provides a method of preparing lithium metal oxide particles.
    [0009] The object of the present invention is not limited to the above, but other objects that are not described herein will be clearly understood by those skilled in the art from the descriptions below. TECHNICAL SOLUTION
    [0010] In accordance with an aspect of the present invention, an active material of the anode is provided including the lithium metal oxide particles, wherein an internal porosity of the lithium metal oxide particles is in the range of 3% to 8% % and an average particle diameter (D50) of the same is in a range of 5 μm to 12 μm.
    [0011] According to another aspect of the present invention, there is provided a method of preparing lithium metal oxide particles having an internal porosity ranging from 3% to 8% and an average particle diameter (D50) that varies between 5 μm and 12 μm, including the preparation of a precursor solution by adding a lithium salt and a metal oxide to a volatile solvent and stirring, providing the precursor solution in a dryer chamber by spraying and spraying the precursor solution in the chamber and drying.
    [0012] Furthermore, according to another aspect of the present invention, an anode is provided, including the anode's active material.
    [0013] In addition, according to another aspect of the present invention, a secondary battery including the anode is provided. ADVANTAGE EFFECTS
    [0014] As described above, an anode active material according to the technical idea of the present invention includes high density lithium metal oxide particles, and thus the adhesion to an anode can be significantly improved. That is, an amount of a binder is needed to obtain the same bond strength to the electrode can be significantly reduced compared to a typical anode active material having a typical density.
    [0015] High density lithium metal oxide particles can be formed when the internal porosity of the lithium metal oxide particles decreases. As a result, the amount of the binder required to prepare an anode slurry can be reduced, and thus, it is advantageous for the mass production of secondary batteries.
    [0016] Since the realization of high density lithium metal oxide and the resulting good adhesion to the electrode may be possible, an average particle diameter of the lithium metal oxide particles can be further reduced. As a result, the high speed characteristics of the secondary battery can be improved.
    [0017] The active material of the high density anode can be formed by a specific preparation method according to an embodiment of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a micrograph of the scanning electron microscope (SEM) of LI4T5O12 from comparison example 3, and Figure 2 is a high density SEM micrograph of LI4T5O12 from example 1 according to an embodiment of the present invention. . MODE FOR CARRYING OUT THE INVENTION
    [0018] Preferred embodiments of the present invention will be described in more detail with reference to the accompanying drawings. However, the following embodiments are only presented to exemplify the present invention, and the scope of the present invention is not limited to them.
    [0019] An active anode material according to an embodiment of the present invention includes lithium metal oxide particles, wherein an internal porosity of lithium metal oxide particles in a range of 3% to 8% % and an average particle diameter (D50) of it is in a range from 5 pm to 12 pm.
    [0020] According to an embodiment of the present invention, since high density lithium metal oxide particles having specific internal porosity and average particle diameter (D50) are included, adhesion to an anode it can be significantly improved, even using the same or lesser amount of a binder that is required when preparing an anode suspension. In addition, the high speed characteristics of a secondary battery can be improved by further decreasing the average particle diameter of the 25 lithium metal oxide particles.
    [0021] The lithium metal oxide particle according to an embodiment of the present invention, when a secondary particle in which two or more primary particles are agglomerated, can be a porous particulate material.
    [0022] In the event that lithium metal oxide particles, like primary particles, are used in the active material of the secondary lithium battery anode, adhesion to the electrode may not be problematic, but the high speed characteristics can degrade. In order to resolve the above limitations, a primary particle diameter can be reduced to 300 nm or less. However, in this case, limitations in an anode paste preparation process, for example, an increase in production costs due to the use of a large amount of the binder or a decrease in electrical conductivity, may occur due to an increase in one the specific surface area. Therefore, in order to resolve the limitations caused by the use of primary particles, the lithium metal oxide particle according to the embodiment of the present invention can be in the form of a secondary particle, in which two or more primary particles are clustered.
    [0023] Typically, since the secondary particle may have a porous shape, a large amount of the binder is required in order to maintain the electrode's adhesion. As a result, the capacity of the battery can be decreased due to the use of a large amount of binder.
    [0024] However, since the lithium metal oxide particles according to the embodiment of the present invention are high density secondary particles having an internal porosity ranging from 3% to 8%, sufficient adhesion of the electrode can not only be obtained but excellent high-speed characteristics can also be obtained, even in the case where a small amount of binder is used, compared to typical secondary particles, for example, the binder is used in an amount ranging from 20 % to 50% of a typical amount of the binder used.
    [0025] In the event that the internal porosity of the lithium metal oxide particles is less than 3%, practical difficulties in terms of a preparation process can occur in consideration of the fact that the secondary particles are formed by the agglomeration of the particles primary. In the case where the internal porosity of the lithium metal oxide particles is greater than 8%, the amount of binder needed to maintain the adhesion of the appropriate electrode can increase and, in this way, the conductivity can be reduced and the capacity can be decreased. Therefore, the effect of the present invention for the purpose of using a small amount of binder can be insignificant.
    [0026] According to an embodiment of the present invention, the internal porosity of the lithium metal oxide particles can be defined as follows: Internal porosity = pore volume per unit mass / (specific volume + pore volume per mass unit)
    [0027] The measurement of internal porosity is not particularly limited. For example, according to an embodiment of the present invention, internal porosity can be measured using gas absorption, such as nitrogen, and BELSORP (Brunauer-Emmett-Teller (BET) instrument) by BEL Japan, Inc.
    [0028] Likewise, a specific surface area (BET) of lithium metal oxide particles can be in the range of 2 m2 / g to 8 m2 / g.
    [0029] According to an embodiment of the present invention, the specific surface area of the lithium metal oxide particles can be measured by a BET method. For example, the specific surface area can be measured by a 6-point BET method according to a nitrogen gas adsorption-flow method, using a porosimetry analyzer (Belsorp-II mini by Bell Japan Inc.).
    [0030] The average particle diameter (D50) of the lithium metal oxide particles can be in the range of 5 μm to 12 μm, and an average particle diameter of the primary particles that constitute the lithium metal oxide particles can be in the range of 100 nm to 400 nm.
    [0031] In the present invention, the average particle diameter (D5Q) of the lithium metal oxide particles can be defined as a particle diameter of 50% in a cumulative particle diameter distribution. The average particle diameter (D5Q) of the lithium metal oxide particles according to the embodiment of the present invention, for example, can be measured by means of a laser diffraction method. The laser diffraction method can generally measure a particle diameter ranging from a submicron level to a few mm, and can obtain highly reproducible, high-resolution results.
    [0032] Typically, since the lithium metal oxide particles have a low conductivity, it is advantageous to have a small average particle diameter in order to be applied to a fast charge cell. However, in this case, a large amount of the binder is required in order to maintain the adhesion of the appropriate electrode, due to the increase in the specific surface area, as described above. That is, in the case where the average particle diameter of the lithium metal oxide particles is less than 5 μm, the amount of binder needed to maintain the desired electrode adhesion may increase due to the increase in the specific surface area of the material. anode, and as a result, reduced conductivity of the electrode can occur. In the case where the average particle diameter of the metal lithium oxide particles is greater than 12 μm, fast charge characteristics can degrade. Therefore, with respect to lithium metal oxide particles with an average particle diameter ranging between 5 μm and 12 μm, while those with a high density of lithium metal oxide particles according to the mode of realization of the present invention, the amount of binder required to maintain the electrode adhesion can not only be decreased, but the fast charge characteristics can also be improved by increasing the area, where a direct reaction with lithium ions (Li) may be possible .
    [0033] In the case where the average particle diameter of the primary particles is less than 100 nm, the electrode adhesion may decrease due to the increase in the porosity of the lithium metal oxide particles formed by the agglomeration of the primary particles. In the case where the average particle diameter of the primary particles is greater than 400 nm, the moldability of the lithium metal oxide particles can decrease and the granulation can be difficult to control.
    [0034] The lithium metal oxide according to an embodiment of the present invention is a material that can store and release lithium ions, in which the lithium metal oxide can be expressed by a compositional formula of LixMyOz (where M is at least one element independently selected from the group consisting of titanium (Ti), tin (Sn), copper (Cu), lead (Pb), antimony (Sb), zinc (Zn), iron (Fe ), indium (In), aluminum (Al), or zirconium (Zr), ex, y, and z are determined according to the oxidation number of M).
    [0035] According to an embodiment of the present invention, the lithium metal oxide can be titanium and lithium oxide, which is any one selected from the group consisting of LÍ4TÍ5O12, LiTi2O4, Li2TiO3, and Li2Ti3O7, or a mixture of two or more of them, taking into account the charging and discharging characteristics and the characteristics of the necessary lifetime as an active material of the secondary battery anode.
    [0036] The lithium metal oxide according to the embodiment of the present invention can be included in an amount ranging from 50% by weight to 100% by weight based on the total weight of the anode's active material. The case in which the amount of lithium metal oxide is 100% by weight based on the total weight of the anode's active material, a case in which the anode's active material is composed of only lithium metal oxide.
    [0037] In a secondary battery according to an embodiment of the present invention, the anode's active material may further include at least one active material selected from the group consisting of carbon-based materials that are typically used in a active anode material, transition metal oxides, materials based on silicon (Si) and materials based on Sn, in addition to lithium metal oxide. However, an active material type of the anode is not limited to them.
    [0038] Furthermore, the present invention provides a method of preparing lithium metal oxide particles with an internal porosity ranging from 3% to 8% and an average particle diameter (DSQ) ranging between 5 μm and 12 μm, including the preparation of a precursor solution by adding lithium salt and metal oxide to a volatile and stirring solvent, providing the precursor solution in a spray dryer chamber, and spraying the precursor solution in the chamber and drying.
    [0039] According to an embodiment of the present invention, the secondary particles of the lithium metal oxide particles can be formed by a separate granulation process, after the preparation of the primary particles. However, secondary particles can typically be prepared using a primary particle preparation method and, simultaneously, agglomerate the primary particles by means of a single process. Examples of the above method can include a spray drying method. Hereinafter, the process of preparing an anode active material according to the embodiment of the present invention will be described using the spray drying method, as an example.
    [0040] According to an embodiment of the present invention, the metal oxide can be titanium oxide.
    [0041] Specifically, the method of preparing lithium metal oxide particles with an internal porosity ranging from 3% to 8% and an average particle diameter (D50) ranging from 5 μm to 12 μm of the present invention can include the preparation of a precursor solution, adding a lithium salt and titanium oxide with a volatile solvent and stirring.
    [0042] More particularly, the lithium salt is dissolved in the volatile solvent, and the precursor solution can then be prepared by adding titanium oxide as the metal oxide thereof, while being stirred.
    [0043] Here, the volatile solvent is not particularly limited in that it is easily volatile at a spray temperature. However, the volatile solvent, for example, can be water, acetone or alcohol.
    [0044] In addition, lithium salt can be a source of lithium in a spray drying process for the preparation of lithium metal oxide particles, and can be any one selected from the group consisting of lithium hydroxide. lithium, lithium oxide, and lithium carbonate or a mixture of two or more of them. In addition, titanium oxide can be a source of titanium.
    [0045] The method of preparation according to the embodiment of the present invention can include providing the precursor solution in a chamber that is included in a spray dryer.
    [0046] A spray dryer typically used can be used as the spray dryer above, and for example, an ultrasonic spray dryer, an air nozzle spray dryer, an ultrasonic nozzle spray dryer, an aerosol generator expansion of the filter, or an electrostatic spray dryer can be used. However, the present invention is not limited to them.
    [0047] According to an embodiment of the present invention, a rate of feeding the precursor solution into the chamber can be in the range of 10 m / min to 1000 m / min. In the case where the feed rate is less than 10 m / min, the average particle diameter of the agglomerated lithium metal oxide particles can decrease and, thus, the formation of the high density lithium metal oxide particles can be difficult. In the event that the feed rate is greater than 1000 ml / min, since the average particle diameter of the lithium metal oxide particles can relatively increase, achieving the desired high speed characteristics can be difficult.
    [0048] In addition, the method of preparation according to the embodiment of the present invention can include spraying the precursor solution in the chamber and drying.
    [0049] The precursor solution can be sprayed by means of a rotating disc at high speed in the chamber and the spraying and drying can be carried out in the same chamber.
    [0050] In addition, the internal porosity of the present invention can be achieved by controlling the spray drying conditions, for example, the carrier gas flow, the retention time in a reactor, and the internal pressure.
    [0051] According to an embodiment of the present invention, the internal porosity of the lithium metal oxide particles can be controlled by adjusting the drying temperature, and drying can be carried out at a temperature ranging from 20 ° C to 300 ° C. However, drying can be carried out at as low a temperature as possible for the high density of the lithium metal oxide particles.
    [0052] In addition, the average particle diameter of the lithium metal oxide particles can be controlled by changing the concentration of a solids content in the precursor solution.
    [0053] High density lithium metal oxide particles can be prepared by carrying out a heat treatment process on the prepared precursor using a sintering furnace in general at a temperature between about 700 ° C and about 850 ° C for about 5 hours to about 20 hours in an air atmosphere or an oxygen atmosphere.
    [0054] The present invention can also provide an anode, including the active material of the anode, and a secondary lithium battery including the anode.
    [0055] An anode current collector is coated with a paste that is prepared by mixing an anode slurry including the anode's active material with a solvent, such as N-methylpyrrolidone (NMP), and the anode can then , be prepared by drying and rolling the anode current collector. The anode paste can selectively include a conductive agent, a binder, or a filler, in addition to the anode's active material.
    [0056] The anode current collector is not particularly limited as long as it does not generate chemical changes in the battery, as well as having a high conductivity. Examples of the anode current collector can be copper, stainless steel, aluminum, nickel, titanium, sintered carbon, copper or stainless steel surface treated with coal, nickel, titanium, or silver, aluminum-cadmium alloy, etc. Fine irregularities can also be formed on a surface of the anode current collector to increase the adhesion of the anode active material, and the anode current collector can be used in various forms, such as a film, plate, sheet, mesh, porous body, foam, or non-woven fabric.
    The conductive agent can typically be added in an amount ranging from 1% by weight to 30% by weight based on the total weight of a mixture that includes the anode's active material. The conductive agent is not particularly limited as long as it does not generate chemical changes in the battery, as well as having conductivity. Examples of the conductive agent can be graphite, such as natural graphite and artificial graphite; carbon black, such as acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal black; conductive fibers such as carbon fibers and metal fibers, metal powder, such as fluorocarbon powder, aluminum powder and nickel powder; conductive burrs such as zinc oxide burrs and potassium titanate burrs, conductive metal oxide, such as titanium oxide, a conductive material, such as a polyphenylene derivative, etc.
    [0058] The binder is a component that helps in the connection between the active material and the conductive bonding agent and in relation to the current collector, and the binder can generally be added in an amount ranging from 1% by weight to 30% in weight based on the total weight of the mixture including the anode's active material. Examples of binder can be polyvinylidene fluoride (PVdF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, EP-ethylene-propylene-dipropylene, (EP) -methylene dipropylene (di) , styrene-butadiene rubber, fluorine rubber, various copolymers, etc.
    [0059] The filler is used selectively as a component that prevents anode expansion and is not particularly limited as long as it does not generate chemical changes in the battery, as well as being a fibrous material. Examples of the filler material can be olefin-based polymers, such as polyethylene and polypropylene, and fibrous materials, such as glass fibers and carbon fibers.
    [0060] A method of uniformly coating the anode current collector with the anode paste can be selected from known methods in consideration of the characteristics of the material, or it can be carried out by a new suitable method. For example, a paste is distributed over the current collector, and the paste is then dispersed evenly, using a blade. In some cases, a method of carrying out distribution and dispersion processes in a single process can also be used. In addition, a method, such as casting, comma coating, and screen printing, can be selected, or the anode paste can be molded on a separate substrate and the molded anode paste can then be glued with the current collector by pressing or lamination.
    [0061] For example, a cathode current collector is coated with a cathode paste that includes an active cathode material, and the cathode can be prepared by drying the cathode current collector. The cathode paste, if necessary, can include the components described above.
    [0062] In particular, as the active material of the cathode, the secondary lithium battery can use a compound of layers, such as lithium cobalt oxide (LiCo02) or nickel and lithium oxide (LiNiO2), or a substituted compound with one or more transition metals; manganese and lithium oxides such as Lii + x Mn2_x O4 (where x is 0 to 0.33), LiMnO3, LiMn2O3 and LiMnO2; copper and lithium oxide (Li2CuO2); vanadium oxides such as LiV30g, LiFe3O4, V2O5, and CU2V2O7; nickel and lithium oxides type Ni expressed by a chemical formula of LiNii-xMxO2 (where M is cobalt (Co), manganese (Mn), Al, Cu, Fe, magnesium (Mg), boron (B), or gallium ( Ga), ex is 0.01 to 0.3); complex manganese and lithium oxides expressed by a chemical formula of LiMn2-xMxO2 (where M is Co, nickel (Ni), Fe, chromium (Cr), Zn, or tantalum (Ta), ex is between 0.01 and 0 , 1) or Li2Mn3MO8 (where M is Fe, Co, Ni, Cu, or Zn); LiMn2O4 having a part of Li replaced by alkaline earth metal ions, a disulfide compound, or Fe2 (Mo04) 3. However, LiNixMn2-x04 (where x is 0.01 to 0.6) can be used and, for example, either LiNio, sMni, 5O4 or LiNio, 4Mni, gO4 can be used. That is, in the present invention, LiNixMn2-xO4 manganese and lithium spinel oxide (where x is 0.01 to 0.6) having relatively high potential due to the high potential of the anode active material can be used as cathodic active material.
    [0063] Any battery case typically used in the art can be selected as a battery case used in the present invention. A form of the secondary lithium battery according to its use is not limited, and, for example, a cylindrical type using a can, a prismatic type, a type of bag, or a type of coin can be used.
    [0064] The secondary lithium battery according to the present invention can not only be used in a battery cell, which is used as a power source for a small device, but can also be used as a unit cell in a module of medium and large size batteries including a plurality of battery cells.
    [0065] Preferred examples of the medium and large size device may be an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, or an energy storage system, but the medium and large size device is not limits it to that.
    [0066] Hereinafter, the present invention will be described in more detail according to specific embodiments. The present invention can, however, be realized in many different ways and should not be construed as being limited to the embodiments set forth herein. Examples Example 1: Preparation of Li4Ti50i2 with an average particle diameter of 5.4 μm and an internal porosity of 3.5%
    [0067] LiOH »H2θ and TiO2 (anatase) were mixed at a molar ratio of 4:05. The mixture was dissolved in pure water and a solution was then stirred. In this case, a ratio of a total solid material is defined as a solids content of the solution, and a precursor solution was prepared by adjusting the solids content to 30% and stirring. The precursor solution was supplied to a spray dryer chamber (by EIN Systems, Co., Ltd.). Then, the precursor solution was sprayed in the chamber and dried. Spray drying was carried out under conditions including a drying temperature of 130 ° C, an internal pressure of -20 mbar, and a feed rate of 30 ml / min, and an active material of the L4T5O12 anode with an average particle diameter. 5.4 μm and an internal porosity of 3.5% was then obtained by sintering the precursor thus obtained at 800 ° C in the air. Examples 2 to 4: Preparation of LI4TÍ5O12
    [0068] Active materials of the Li4Ti5O12 anode having average particle diameters and internal porosities listed in table 1 were obtained in the same way as in example 1 except that the spray conditions listed in the following table 1 have been changed. Comparative examples 1 to 5: Preparation of LI4T5O12
    [0069] Active materials of the Li4Ti5O12 anode having average particle diameters and internal porosities listed in table 1 were obtained in the same way as in example 1 except that the spray conditions listed in the following table 1 have been changed. Table 1
    1. Average particle diameter: laser diffraction method (MicroTAC MT 3000) 2. Internal porosity = pore volume per unit mass / (specific volume + pore volume per unit mass) (use of BELSORP (BET instrument) by BEL Japan 10 Inc., usage values calculated using the Barrett-Joyner-Halenda (BJH) method, that is, a mesoporous measurement method) Examples 5 to 8: Preparation of the secondary lithium battery Anode preparation
    [0070] LIN4TÍ5O12 of examples 1 to 4 listed in table 1 as an anode active material, carbon black (Super P) as a conductive agent, and PVDF as a binder were mixed in an 88: 4: 8 weight ratio, and the mixture was then added N-methyl-2-pyrrolidone as a solvent to prepare a paste. A surface of a copper current collector was coated with the paste prepared to a thickness of 65 μm, and then dried and laminated. Then, the anodes were prepared by puncture to a predetermined size. Preparation of the secondary lithium battery
    [0071] Ethylene carbonate (CE) and diethyl carbonate (DEC) were mixed at a volume ratio of 30:70, to prepare a non-aqueous solvent electrolyte, and LiPF6 was added thereto, to prepare an electrolyte solution non-aqueous LiPFe 1 M.
    [0072] In addition, a lithium foil was used as a counter electrode, that is, a cathode, and a polyolefin separator was placed between the two electrodes. Then, half coin cells were prepared by injecting electrolyte solution. Comparative Examples 6 to 10: Preparation of secondary lithium battery
    [0073] Secondary lithium batteries were prepared in the same manner as in example 5, except that LI4TÍ5O12 of comparative examples 1 to 5, listed in table 1 were used as an anode active material. Experimental example 1 SEM micrographs
    [0074] Active materials of the lithium metal oxide anode prepared in comparative example 3 and example 1 respectively, were identified by electron scanning microscopy (SEM) micrographs, and the results are shown, respectively, in figures 1 and two.
    [0075] Figure 1 is a SEM micrograph of L4T5O12 with an average particle diameter of 6.5 μm and an internal porosity of 15%, in which it can be confirmed that the L4T5O12 was composed of porous secondary particles in which the pores were formed on the surface and inside of the secondary particle, due to the agglomeration of primary particles. In this case, the black regions in the particle represent pores.
    [0076] With respect to figure 2, the primary particles were agglomerated to constitute a secondary particle, and a SEM micrograph of LI4TÍ5O12 with an average particle diameter of 5.4 μm and an internal porosity of 3.5% is illustrated. It can be confirmed visually that the Li4Ti50i2 of example 1 had a higher density than the Li4Ti5O12 of comparative example 3. Experimental example 2 Adhesion measurement
    [0077] Adhesion to an anode was measured using the anodes prepared during the preparation of secondary lithium batteries of examples 5 to 8 and comparative examples 6a 10. Adhesion measurement was performed using a generally known peel test of 180 degrees. The respective results are shown in table 2 below. Analysis of the characteristics of high speed
    [0078] In order to analyze the characteristics of the high speed of the secondary lithium batteries of examples 5 5 to 8 and comparative examples 6 to 10, the characteristics of the high speed of the secondary lithium batteries were evaluated by sequentially changing the charge rates and discharge of 0.1 C, 0.2 C, 0.5 C, 1 C, 0.2 C, 2 C, 0.2 C, 5 C, 0.2 C, and 10 C, respectively. In this case, a final charge voltage 10 was defined as 1.0 V and a final discharge voltage was set at 2.5 V. The high speed characteristics for each secondary lithium battery were expressed as a percentage of the value of a capacity measured at 10C with respect to a capacity of 0.1 C.
    [0079] The respective results are shown in Table 2 below. Table 2


    [0080] As shown in Table 2, in the case that the Li4Ti50i2 particles had similar average particle diameters, it can be confirmed that there were differences in electrode adhesion due to differences in the internal porosity of the lithium metal oxide particles and in addition, the characteristics of high speed have been affected. The reason for this can be understood as follows: in the event that the internal porosity of the lithium metal oxide particles is increased, the binder can be introduced into the pores of the lithium metal oxide particles to loosen the bond between the material anode and the conductive agent, and therefore the resistance of the electrode may increase. As a result, the characteristics of high speed can degrade.
    [0081] Also, in the case where the internal porosity of the lithium metal oxide particles was relatively low, since the penetration of the electrolyte solution into the active material was not facilitated, it can cause the degradation of the characteristics of the high speed despite high adherence.
    [0082] In addition, with regard to lithium metal oxide particles with similar internal porosities, it can be confirmed that the electrode's adhesion and high-speed characteristics were different due to differences in the particle diameters of these. It can be interpreted as the result of reduced electrode adhesion, when the particle diameter was relatively small.
    [0083] In the case where the diameter of the lithium metal oxide particle was large, it can be understood that the characteristics of the high speed may decrease due to the reduction of the electrical conductivity of the active material in the lithium metal oxide particles.
    [0084] Therefore, it can be confirmed that the balance between the internal porosity of the lithium metal oxide particles and the average particle diameter of the lithium metal oxide particles was necessary to improve the characteristics of the high speed. INDUSTRIAL APPLICABILITY
    [0085] As described above, an active material of the anode according to the technical idea of the present invention includes particles of high density lithium metal oxide, and thus the adhesion to an anode can be significantly improved. That is, an amount of a binder required to obtain the same bond strength for the electrode can be significantly reduced compared to a typical anode's active material having a typical density.
    [0086] High density lithium metal oxide particle can be formed when the internal porosity of the lithium metal oxide particles decreases. As a result, the amount of the binder required to prepare an anode paste can be reduced, and thus, it is advantageous for the mass production of secondary batteries.
    [0087] Since the realization of high density lithium metal oxide and the resulting good adhesion to the electrode may be possible, an average particle diameter of the lithium metal oxide particles can be further reduced. As a result, the high speed characteristics of the secondary battery can be improved.
    权利要求:
    Claims (12)
    [0001]
    1. Active anode material comprising lithium metal oxide particles characterized by the fact that lithium metal oxide is any one selected from the group consisting of Li4Ti5O12, LiTi2O4, Li2TiO3, and Li2Ti3O7, or a mixture of two or more of the same; wherein an internal porosity of the lithium metal oxide particles is in a range of 3% to 8% and an average particle diameter (D50) of the same is in a range of 5 μm to 12 μm; where the internal porosity is the volume of pores per unit of mass / (specific volume + volume of pores per unit of mass); where internal porosity is measured using gas absorption and BET instrument; wherein the mean particle diameter (D50) is defined as a particle diameter of 50% in a cumulative particle diameter distribution; wherein the average particle diameter (D50) is measured using a laser diffraction method.
    [0002]
    2. Active material of the anode according to claim 1, characterized by the fact that the lithium metal oxide particle is a secondary particle, in which two or more primary particles are agglomerated.
    [0003]
    3. Anode active material according to claim 2, characterized by the fact that an average particle diameter of the primary particles is in the range of 100 nm to 400 nm.
    [0004]
    4. Active anode material according to claim 1, characterized by the fact that a specific surface area (Brunauer-Emmett-Teller (BET)) of the lithium metal oxide particles is in the range of 2 m2 / g 8 m2 / g.
    [0005]
    5. Method of preparing particles of the active material of the anode comprising lithium metal oxide as defined in claim 1, the method characterized by the fact that it comprises: the preparation of a precursor solution, adding a lithium salt and an oxide of metal from a volatile and stirring solvent; the supply of the precursor solution in a chamber of a spray dryer, and the spraying of the precursor solution in the chamber and drying.
    [0006]
    6. Method according to claim 5, characterized by the fact that the lithium salt is any one selected from the group consisting of lithium hydroxide, lithium oxide, and lithium carbonate, or a mixture of two or more of them.
    [0007]
    7. Method according to claim 5, characterized by the fact that the metal oxide is titanium oxide.
    [0008]
    8. Method according to claim 5, characterized by the fact that the volatile solvent is water, alcohol or acetone.
    [0009]
    9. Method, according to claim 5, characterized by the fact that a rate of feeding the precursor solution into the chamber is in the range of 10 mL / min to 1000 mL / min.
    [0010]
    10. Method according to claim 5, characterized by the fact that drying is carried out at a temperature ranging from 20 ° C to 300 ° C.
    [0011]
    11. Anode, characterized by the fact that it comprises the active material of the anode defined in claim 1.
    [0012]
    12. Secondary battery, characterized by the fact that it comprises the anode defined in claim 11.
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    同族专利:
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    CN103733394A|2014-04-16|
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    EP2722914A1|2014-04-23|
    KR101539843B1|2015-07-27|
    JP5888418B2|2016-03-22|
    JP2014524653A|2014-09-22|
    KR20140009921A|2014-01-23|
    EP2722914B1|2015-10-21|
    TW201421785A|2014-06-01|
    US9608260B2|2017-03-28|
    TWI502796B|2015-10-01|
    EP2722914A4|2014-09-24|
    CN103733394B|2018-06-22|
    WO2014010970A1|2014-01-16|
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    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2019-09-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-10-13| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 11/07/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    KR20120076905|2012-07-13|
    KR10-2012-0076905|2012-07-13|
    KR10-2013-0066228|2013-06-11|
    KR1020130066228A|KR101539843B1|2012-07-13|2013-06-11|Anode Active Material of High Density and Methode for Preparation of The Same|
    PCT/KR2013/006216|WO2014010970A1|2012-07-13|2013-07-11|High density anode active material and preparation method thereof|
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