WO2012011785A2 - 리튬 이차전지용 양극활물질의 제조방법, 그에 의하여 제조된 리튬 이차전지용 양극활물질 및 그를 이용한 리튬 이차전지 - Google Patents
리튬 이차전지용 양극활물질의 제조방법, 그에 의하여 제조된 리튬 이차전지용 양극활물질 및 그를 이용한 리튬 이차전지 Download PDFInfo
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- WO2012011785A2 WO2012011785A2 PCT/KR2011/005445 KR2011005445W WO2012011785A2 WO 2012011785 A2 WO2012011785 A2 WO 2012011785A2 KR 2011005445 W KR2011005445 W KR 2011005445W WO 2012011785 A2 WO2012011785 A2 WO 2012011785A2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a method for producing a cathode active material for a lithium secondary battery, to a cathode active material for a lithium secondary battery and a lithium secondary battery using the same, more specifically a continuous concentration gradient of the concentration of lithium gradually from inside to outside the particles
- the present invention relates to a method of manufacturing a cathode active material for a lithium secondary battery that implements a mold structure, a cathode active material for a lithium secondary battery manufactured thereby, and a lithium secondary battery using the same.
- lithium ion secondary battery Since the lithium ion secondary battery appeared in 1991, it has been widely used as a power source for portable devices. Recently, with the rapid development of electronics, telecommunications, and computer industry, camcorders, mobile phones, notebook PCs, etc. have emerged and are developing remarkably. The demand for lithium ion secondary battery as a power source for driving these portable electronic information communication devices is increasing day by day. It is increasing. In particular, research on power sources for electric vehicles by hybridizing an internal combustion engine and a lithium secondary battery has been actively conducted in the United States, Japan, and Europe.
- LiCoO 2 is an excellent material having stable charge and discharge characteristics, excellent electronic conductivity, high stability, and flat discharge voltage characteristics. However, since Co is low in reserve, expensive, and toxic to humans, development of other cathode materials is desired. LiNiO 2 having a layered structure such as LiCoO 2 exhibits a large discharge capacity but has not been commercialized due to problems in cycle life, thermal instability, and safety at high temperatures.
- Japanese Patent Application Laid-open No. Hei 8-171910 discloses mixing an alkaline solution in a mixed aqueous solution of Mn and Ni to coprecipitate Mn and Ni, and then calcining LiNi x Mn 1-x after mixing lithium hydroxide with the coprecipitation compound.
- a method for producing a cathode active material of O 2 (0.7 ⁇ x ⁇ 0.95) is disclosed.
- Japanese Patent Application No. 2000-227858 discloses a positive electrode active material having a new concept of dissolving a transition metal to LiNiO 2 or LiMnO 2 to form a solid solution by uniformly dispersing Mn and Ni compounds at atomic level. .
- Ni 4 + due to the reactivity of Ni 4 + not only has a problem to commercialize, but still does not solve the thermal stability of the active material containing Ni.
- Nickel from a material having a layered crystal structure the most attention as an alternative material LiCoO 2-manganese and nickel-cobalt-manganese are each 1: 1 or 1: 1: Li [Ni 1/2 Mn 1/2] mixed in a 1 O 2 and Li [Ni 1/3 Co 1/3 Mn 1/3 ] O 2 .
- these materials have low electronic conductivity (J. of Power Sources, 112 (2002) 41-48), so that the high power characteristics of the hybrid power source for electric vehicles are higher than those of LiCoO 2 , LiNiO 2 , and LiMn 2 O 4 . Falls.
- these materials have a uniform composition on and inside the particle surface.
- the function of the inside and the surface of the anode powder particles must be different. That is, the composition inside the particles should be structurally stable with a lot of insertion / desorption sites of lithium, but should minimize the reactivity with the electrolyte on the particle surface.
- the coating amount is 1 to 2wt% or less compared to the positive electrode active material
- the coating layer is known to suppress side reactions with the electrolyte by forming a very thin film layer of about several nanometers or when the heat treatment temperature after coating is high.
- a solid solution may be formed on the surface of the particles to have a metal composition different from that inside the particles.
- the surface layer combined with the coating material is known to be tens of nanometers or less, and there is a drastic compositional difference between the coating layer and the bulk of the particle, which reduces the effect of long-term use of hundreds of cycles. In addition, the effect is halved due to incomplete coating in which the coating layer is not evenly distributed on the surface.
- a lithium transition metal oxide having a concentration gradient of a metal composition has been proposed as a method of synthesizing an internal material, coating a material having a different composition to the outside, preparing a double layer, and then mixing the mixture with a lithium salt and performing heat treatment.
- the Republic of Korea Patent Publication No. 2005-0083869 can be a gradual gradient of the metal composition through the heat treatment process, but at a high heat treatment temperature of more than 850 °C a concentration gradient due to the thermal diffusion of metal ions hardly occurs, synthesized
- the powder is not suitable for use as a cathode active material for lithium secondary batteries due to its low tap density and low energy density.
- the method cannot control the amount of lithium in the outer layer, thereby reducing reproducibility.
- lithium carbonate and lithium hydroxide remain on the surface, so that a large amount of gas is generated at high temperature during cell assembly, and the battery case is easy to swell, and gelation occurs easily when mixing electrodes for cell assembly.
- agglomeration occurs when the electrode is coated, resulting in surface defects.
- the present invention implements a continuous concentration gradient structure in which lithium concentration gradually decreases with respect to the concentration of metallic elements from the outside to the inside of the lithium secondary battery having thermal stability, high capacity, and excellent life characteristics. It is an object of the present invention to provide a method for producing a cathode active material for a battery, a cathode active material for a lithium secondary battery produced thereby, and a lithium secondary battery using the same.
- the present invention provides a) a first metal salt aqueous solution, a chelating agent and a basic aqueous solution containing nickel, cobalt, manganese and optionally a transition metal at the same time, and then mixed and calcined with a lithium raw material.
- a core comprising a compound of Formula 1;
- M is Mg, Zn, Ca, Sr, Cu, Zr, P, Fe, Al At least one metal selected from Ga, In, Cr, Ge, Sn)
- M is Mg, Zn, Ca, Sr, Cu, Zr, P, At least one metal selected from Fe, Al, Ga, In, Cr, Ge, Sn)
- step c) mixing the center portion obtained in step a) with the compound for forming an outer portion obtained in step b) to form an outer portion on the central surface;
- step d) heat-treating the compound obtained in step c) at 500 to 800 to form a double layer structure in which lithium is present in a continuous concentration gradient from the contact interface of the central part and the outer part to the surface part of the outer part;
- a method of manufacturing a cathode active material for a lithium secondary battery is provided.
- the average particle diameter of the central portion in the step a) is characterized in that 3 to 20.
- the average particle diameter of the compound for forming an outer portion in step b) is characterized in that 20 to 600nm.
- the thickness of the outer portion formed on the surface of the center in steps c) and d) is characterized in that 0.5 to 5 ⁇ m.
- the present invention provides a cathode active material for a lithium secondary battery is produced by any one of the above manufacturing method, the lithium is present in a continuous concentration gradient from the contact interface of the central portion and the outer portion to the surface portion of the outer portion.
- the present invention is manufactured by any one of the above manufacturing method, the distance to a certain point in the outer portion on the basis of the surface portion of the outer portion is referred to as D, the concentration ratio of lithium to the concentration of metal elements at the D position When D is P, the relationship between D and P satisfies the following equation when D changes from the surface portion of the outer portion to the contact interface between the central portion and the outer portion.
- the present invention provides a lithium secondary battery using the cathode active material for lithium secondary battery.
- the method for producing a cathode active material for a lithium secondary battery of the present invention and the cathode active material for a lithium secondary battery manufactured thereby have a double-layer concentration gradient structure in which lithium concentration gradually increases from the outermost part to the inside, thereby exhibiting high capacity and heat. With stability and excellent lifespan, it can be used not only for small secondary batteries but also for large batteries for electric vehicles and power storage systems.
- FIG. 6 shows the initial discharge capacity and the efficiency of Example 1 in which the dissimilar metal was introduced later, while having a higher capacity than Comparative Example 1, which was a co-precipitated product, while Example 2 is a photograph showing a low capacity.
- FIG. 7 illustrates the observation of particles with a projection electron microscope (TEM) to observe the shape of the center and core of all the double-layered lithium metal composite oxides prepared in Example 2.
- TEM projection electron microscope
- the present invention comprises the steps of: a) mixing a first aqueous metal salt solution, a chelating agent and a basic aqueous solution containing nickel, cobalt, manganese and optionally a transition metal at the same time in a reactor, followed by mixing and baking with a lithium raw material to prepare a core, b ) Simultaneously mixing the second metal salt aqueous solution, chelating agent and basic aqueous solution containing nickel, cobalt, manganese and optionally transition metal in the reactor, and then mixing and baking with lithium raw material, pulverizing it to nano size for forming the outline Preparing a compound, c) mixing the center compound obtained in step a) and the compound for forming an outer portion obtained in step b) to form the outer compound on the surface of the center, and d)
- the compound obtained in the step c) is heat-treated at 500 to 800 to remove the liquor from the contact interface between the central portion and the outer edge formed on the central surface. It provides a method
- a) a first metal salt aqueous solution, a chelating agent and a basic aqueous solution containing nickel, cobalt, manganese and optionally a transition metal are simultaneously mixed in a reactor and then mixed and calcined with a lithium raw material to prepare a central portion.
- an aqueous first metal salt solution, a chelating agent and a basic aqueous solution containing nickel, cobalt, manganese and optionally transition metals are mixed in a reactor to prepare a metal complex hydroxide precipitate as a precursor.
- the first metal salt aqueous solution may be prepared by adding a salt including nickel salt, cobalt salt, manganese salt and transition metal to a solvent, and each nickel salt; Cobalt salts; Manganese; And at least one element selected from the group consisting of Mg, Zn, Ca, Sr, Cu, Zr, P, Fe, Al, Ga, In, Cr, Ge, Sn, and combinations thereof.
- the metal salt sulfates, nitrates, acetates, halides, hydroxides, and the like may be used, and are not particularly limited, as long as they can be dissolved in water.
- the first metal salt aqueous solution is mixed by adjusting the molar ratio of nickel, cobalt, manganese, and transition metal to have a high capacity characteristics. This molar ratio can be easily calculated according to the metal composition of the final inner center to be obtained.
- 1-y 1 -z 1 -w 1 is represented by nickel
- y 1 is cobalt
- z 1 is manganese
- w 1 is represented by the ratio of transition metal M, 0.9 ⁇ x 1 ⁇ 1.3, 0.1 ⁇ y 1 ⁇ 0.3, 0.0 ⁇ z 1 ⁇ 0.3, 0 ⁇ w 1 ⁇ 0.1
- the ratio of nickel, cobalt and manganese is, for example, 3: 1: 6, 4: 1: 5, 4: 0: 6, etc.
- an aqueous ammonia solution As the chelating agent, an aqueous ammonia solution, an aqueous ammonium sulfate solution, a mixture thereof, and the like may be used. It is preferable that it is 0.2-0.5: 1, and, as for the molar ratio of the said chelating agent and the 1st metal salt aqueous solution, it is more preferable that it is 0.2-0.4: 1.
- the molar ratio of the chelating agent is 0.2 to 0.5 with respect to 1 mol of the first metal aqueous solution, the chelating agent reacts with the metal at least 1 to 1 to form a complex, but the complex is mixed with a basic aqueous solution such as NaOH. This is because the remaining chelating agent can be converted into an intermediate product and recovered and used as a chelating agent, which is also an optimal condition for increasing and stabilizing crystallinity of the positive electrode active material.
- Examples of the basic aqueous solution may include NaOH and KOH, but are not limited thereto, and any basic aqueous solution may be used. It is preferable to use 4M-5M as the density
- the reaction of the step of preparing a metal hydroxide precipitate, nickel salt, manganese salt, cobalt salt, and optionally transition metal salts are dissolved in distilled water, and then added to the reactor with a chelating agent and a basic aqueous solution to precipitate
- a chelating agent and a basic aqueous solution to precipitate causes Coprecipitation method is a method of obtaining a composite hydroxide by simultaneously precipitated two or more elements by using a neutralization reaction in an aqueous solution.
- the average time of the mixed solution staying in the reactor is adjusted to 4 to 12 hours, the pH is adjusted to 10 to 12.5, preferably 10.5 to 11.5, the temperature of the reactor is maintained at 50 °C to 80 °C .
- the reason for raising the temperature of the reactor is that it is difficult to obtain a high-density complex hydroxide because the cobalt hydroxide produced is precipitated in complex salt form at a low temperature.
- the reaction time in the reactor is preferably controlled to 8 to 30 hours, preferably 10 to 30 hours. After collecting the first metal hydroxide precipitate prepared by the above method in the form of a slurry, the slurry solution is filtered and washed and dried at 100 to 150 ° C. to obtain a metal complex hydroxide.
- the dry metal composite hydroxide and the lithium raw material dried as described above are mixed at a constant ratio and thermally calcined at 900 to 1000 ° C. under air flow to obtain a lithium metal composite oxide.
- the lithium raw material is not particularly limited as long as it is a lithium salt containing lithium such as lithium carbonate or lithium nitrate.
- the ratio of the metal complex oxide and the lithium salt is preferably 1: 1.1 to 1: 1.5.
- the lithium metal composite oxide obtained as described above becomes a "center part" located at the center of the cathode active material, and the center part may be represented by the following Chemical Formula 1.
- M is Mg, Zn, Ca, Sr, Cu, Zr, P, Fe, Al At least one metal selected from Ga, In, Cr, Ge, Sn)
- the average particle diameter of the said central part becomes like this. Preferably it is 3-20 micrometers, More preferably, it is 5-15 micrometers. This is because when the average particle diameter of the central portion is smaller than 3 ⁇ m, the discharge capacity is reduced, and when the average particle diameter is 20 ⁇ m or more, the thermal safety is deteriorated.
- the center part manufactured by the above method has a high capacity and a high energy density, and has an advantage of excellent thermal stability and high voltage characteristics.
- a second aqueous metal salt solution, a chelating agent and a basic aqueous solution containing nickel, cobalt, manganese and optionally transition metals are then mixed in a reactor at the same time, and then mixed and calcined with a lithium raw material and pulverized to nano size
- a compound for forming a spherical outline is prepared.
- a second aqueous metal salt solution, a chelating agent and a basic aqueous solution containing nickel, cobalt, manganese and optionally a transition metal are mixed in the reactor to prepare a metal complex hydroxide precipitate as a precursor.
- the second metal salt aqueous solution may be prepared by adding a salt including nickel salt, cobalt salt, manganese salt and transition metal to a solvent, each of nickel salts; Cobalt salts; Manganese; And at least one element selected from the group consisting of Mg, Zn, Ca, Sr, Cu, Zr, P, Fe, Al, Ga, In, Cr, Ge, Sn, and combinations thereof.
- the metal salt sulfates, nitrates, acetates, halides, hydroxides, and the like may be used, and are not particularly limited, as long as they can be dissolved in water.
- the first metal salt aqueous solution is mixed by adjusting the molar ratio of nickel, cobalt, manganese, and transition metal to have a high capacity characteristics. This molar ratio can be easily calculated according to the metal composition of the final inner center to be obtained.
- 1-y 2 -z 2 -w 2 is represented by nickel
- y 2 is cobalt
- z 2 is manganese
- w 2 is represented by the ratio of transition metal M, 0.9 ⁇ x 2 ⁇ 1 + z 2 , 0 ⁇ y 2 ⁇ 0.33, 0 ⁇ z 2 ⁇ 0.5, 0 ⁇ w 2 ⁇ 0.1
- the ratio of nickel, cobalt, manganese may be, for example, 1: 1: 1 and 5: 2: 3, etc. have.
- the kind and the amount of the chelating agent and the basic aqueous solution are the same as those used in the manufacturing method of the center portion.
- the dry metal composite oxide and the lithium raw material are mixed in a predetermined ratio in the same manner as in the manufacturing method of the center portion, and then calcined at 900 to 1000 ° C. under air flow to obtain a lithium metal composite oxide.
- the lithium raw material is not particularly limited as long as it is a lithium salt containing lithium such as lithium carbonate or lithium nitrate.
- the ratio of the metal complex oxide and the lithium salt is preferably 1: 0.6 to 1: 1.1.
- a small amount of lithium is included in the outer portion of the outer portion of the positive electrode active material particles as compared to the center portion, and a smaller concentration than the central portion is formed in order to form a concentration gradient in which lithium is continuously decreased from the boundary surface of the center portion to the surface portion of the outer portion.
- the lithium metal composite oxide obtained as described above is pulverized to several nanometers (nanometer) using an air jet mill. When the particles are ground to have an average particle diameter of several nm, the electrical conductivity is improved.
- the lithium metal composite oxide obtained as described above is referred to as a compound for forming an outer portion since it becomes a raw material for forming an outer portion located at the outer portion of the cathode active material.
- the average particle diameter of the compound for forming an outer portion is preferably 20 to 600 nm, more preferably 30 to 500 nm. The average particle diameter must be in the above range to form the desired coating thickness in the core coating.
- the outer compound for forming may be represented by the following formula (2).
- M is Mg, Zn, Ca, Sr, Cu, Zr, P, At least one metal selected from Fe, Al, Ga, In, Cr, Ge, Sn)
- step c) by mixing the center portion obtained in step a) and the compound for forming the outer portion obtained in step b) to form an outer portion on the surface of the center, d) the compound obtained here is heat-treated at 500 to 800 °C A double layer structure is formed in which lithium is present in a continuous concentration gradient from the contact interface of the center portion and the outer portion to the surface portion of the outer portion.
- the center forming compound obtained in step a) and the compound for forming the outer portion obtained in step b) are put together in a high speed dry coater and mixed at a speed of 5000 to 15000 rpm.
- the compound for forming the outer portion of the size of several nanometers surrounds the central portion with a certain thickness to form the outer portion.
- the outer portion covering the center portion can be adjusted by adjusting the residence time, temperature, rotation speed in the reactor, such as a high-speed dry coating machine.
- the thickness of the outer portion formed in the present invention is preferably 0.5 to 5 ⁇ m, more preferably 1 to 3 ⁇ m.
- the thickness of the outer portion is preferably within the above range because there is an advantage to improve the thermal safety, and if outside the above range there is a problem that the discharge capacity is reduced is not preferred.
- the double layer structure thus obtained is heat-treated at 500 to 800 ° C. to obtain a double layer structure in which lithium is present in a continuous concentration gradient from the contact interface between the center portion and the outer portion coated on the surface of the central portion to the surface portion of the outer portion.
- the heat treatment atmosphere is preferably an oxidizing atmosphere of air or oxygen, and the heat treatment time is preferably 10 to 30 hours. It is also possible to carry out preliminary firing at 250 to 650 ° C. for 5 to 20 hours before the heat treatment step. In addition, the annealing process may be performed at 600 to 750 ° C. for 10 to 20 hours after the heat treatment process.
- concentration distribution in which the concentration of the metal changes gradually.
- concentration distribution is continuously realized from the outermost part of the central part inside the positive electrode active material to the surface part of the outer part.
- Such a continuous concentration gradient can prevent the formation of impurity phases caused by a sharp difference in the transition metal and lithium composition at the interface between the center and the outer portion, and stabilization of the crystal structure because no sharp phase boundary region appears. Can be.
- the distance from the surface portion of the outer portion to the contact interface between the central portion and the outer portion of the outer portion is referred to as a distance D from the outer portion on the basis of the surface portion of the outer portion, and the metal element at the D position.
- D the ratio of the concentration of lithium to the concentration of P
- P the relation between D and P provides a cathode active material for a lithium secondary battery that satisfies the following formula.
- the concentration of lithium with respect to the concentration of metal elements increases from the surface of the outer portion to the inside, but when a is less than 0.07, the difference in lithium concentration between the center and the outer portion is hardly noticeable.
- the concentration is high, the excessive amount of lithium is formed and remains, and the problem remains as it is.
- a is 0.7 or more, the concentration of lithium in the central part and the outer part changes abruptly, resulting in structural instability.
- the cathode active material for a lithium secondary battery manufactured by the above-described manufacturing method and having a continuous concentration gradient of lithium from the contact interface of the central part and the outer part to the surface part of the surgical part, has high capacity, high energy density, thermal stability, and high voltage characteristics at the center part.
- the outer part minimizes the problem of excessive lithium, which is a disadvantage of the core material, and has overall thermal stability, high capacity, and excellent life characteristics.
- Examples of electrolytes that may be used in the lithium secondary battery include esters such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and Cyclic carbonates such as vinylene carbonate (VC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC) and di Aliphatic carbonates such as prophylcarbonone (DPC), methyl formate (IMF), methyl acetate (MA), methyl propionate (MP) and ethyl propionate (MA) And cyclic carboxylic acid esters such as carboxylic acid ester and butyrolactone (GBL).
- esters such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and Cyclic carbonates such as vinylene carbonate (VC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC) and di Aliphatic carbonates
- cyclic carbonate ethylene carbonate (EC), propylene carbonate (PC), vinylene carbonate (VC), etc. are particularly preferable. Moreover, it is also preferable to use aliphatic carboxylic acid ester in 20% or less range as needed.
- Lithium salts dissolved in the solvent include LiClO 4 , LiBF 4 , LiPF 6 , LiAlCl 4 , LiSbF 6 , LiSCN, LiCF 3 SO 3 , LiCF 3 CO 2 , Li (CF 3 SO 2 ) 2 , LiAsF 6 , LiN ( CF 3 SO 2 ) 2 , LiB 10 Cl 10 , Lithium Bis (oxalato) borate (LiBOB), lower aliphatic lithium carbonate, lithium chloroborane, lithium tetraphenylborate, and LiN (CF 3 SO 2 ) (C 2 F 5 SO 2 ), Imides such as LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ), and the like can be used. .
- the lithium salts may be used alone or in any combination within a range that does not impair the effects of the present invention. It is particularly
- carbon tetrachloride ethylene trifluoride chloride, or phosphate containing phosphorus may be included in the electrolyte.
- Inorganic solid electrolytes include Li 4 SiO 4 , Li 4 SiO 4 -Lil-LiOH, xLi 3 PO 4- (1-x) Li 4 SiO 4 , Li 2 SiS 3 , Li 3 PO 4 -Li 2 S-SiS 2 , Phosphorus sulfide compounds and the like are preferable.
- organic solid electrolyte it is preferable to use polyethylene oxide, polypropylene oxide, polyvinyl alcohol, polyvinylidene fluoride, fluoropropylene or the like, or polymer materials such as derivatives, mixtures and composites.
- the separator is preferably a polyethylene or polypropylene polymer such as porous polyethylene.
- a compound capable of adsorbing and releasing lithium ions such as lithium, lithium alloy, alloy, intermetallic compound, carbon, organic compound, inorganic compound, metal complex and organic high molecular compound is used. It is preferable to use said compound individually or in combination arbitrarily in the range which does not impair the effect of this invention, respectively.
- the lithium alloy examples include a Li-Al alloy, a Li-Al-Mn alloy, a Li-Al-Mg alloy, a Li-Al-Sn alloy, a Li-Al-In alloy, a Li-Al-Cd alloy, It is preferable to use a Li-Al-Te based alloy, a Li-Ga based alloy, a Li-Cd based alloy, a Li-In based alloy, a Li-Pb based alloy, a Li-Bi based alloy, a Li-Mg based alloy, or the like. .
- the compound of a transition metal and silicon, the compound of a transition metal, and tin, etc. can be used, Especially a compound of nickel and silicon is preferable.
- carbonaceous materials include coke, pyrolytic carbon, natural graphite, artificial graphite, meso carbon micro beads, graphitized meso phase small spheres, vapor grown carbon, glassy carbon, and carbon fiber.
- pyrolytic carbon Natural graphite, artificial graphite, meso carbon micro beads, graphitized meso phase small spheres, vapor grown carbon, glassy carbon, and carbon fiber.
- Polyacrylonitrile-based, pitch-based, cellulose-based, vapor-grown carbon-based amorphous carbon, carbon from which organic materials are fired, and the like are preferably used. It is preferable to use these individually or in combination arbitrarily in the range which does not impair the effect of this invention, respectively.
- a packaging material composed of a metal can or aluminum and several layers of polymers as the exterior material.
- NiSO 4 ⁇ 6H 2 O nickel sulfate hexahydrate
- CoSO 4 ⁇ 7H 2 O cobalt sulfate hexahydrate
- MnSO 4 manganese sulfate monohydrate
- the prepared 2.5M nickel / cobalt / manganese mixed metal solution, 28% ammonia water and 25% sodium hydroxide solution were continuously added simultaneously using a metering pump while stirring under nitrogen at a speed of 500 rpm.
- ammonia water was introduced at a rate of 1.0L / hr, sodium hydroxide was continuously reacted while adjusting the input amount to maintain a pH of 11 ⁇ 12 in the reactor Was performed.
- the reactor residence time was 10 hours. Slurry, a reaction product discharged through the reactor overflow as a continuous reaction, was collected.
- the slurry solution thus collected was filtered and washed with distilled water of high purity, and dried in a vacuum oven at 110 ° C. for 12 hours to obtain a precursor of nickel / cobalt / manganese metal composite hydroxide.
- the composition of the obtained metal composite hydroxide was [Ni 0.28 Co 0.12 Mn 0.60 (OH) 2 ].
- the chemical composition of the calcined lithium metal composite oxide was Li 1.25 [Ni 0.21 Co 0.09 Mn 0.45 ] O 2 .
- NiSO 4 ⁇ 6H 2 O nickel sulfate hexahydrate
- CoSO 4 ⁇ 7H 2 O cobalt sulfate heptahydrate
- MnSO 4 manganese sulfate monohydrate
- the prepared 2.5M nickel / cobalt / manganese mixed metal solution, 28% aqueous ammonia, and 25% sodium hydroxide solution were continuously added simultaneously using a metering pump while stirring under nitrogen at a speed of 700 rpm.
- a metering pump while maintaining the temperature in the reactor 50 °C mixed metal solution at 7L / hr, ammonia water at 0.4 L / hr rate, sodium hydroxide was continuously reacted while adjusting the input amount to maintain the pH in the reactor 11 ⁇ 12 Was performed.
- the reactor residence time was 10 hours. Slurry, a reaction product discharged through the reactor overflow as a continuous reaction, was collected.
- the slurry solution thus collected was filtered and washed with distilled water of high purity, and dried in a vacuum oven at 110 ° C. for 12 hours to obtain nickel / cobalt / manganese metal composite hydroxide.
- the composition of the obtained metal composite hydroxide was [Ni 0.333 Co 0.333 Mn 0.333 (OH) 2 ].
- the resulting fired product was pulverized to nano size using an air jet mill to obtain a lithium metal composite oxide having a layered structure of chemical composition Li [Ni 0.333 Co 0.333 Mn 0.333 ] O 2 having a size of 100 nm or less.
- the synthesized compound for forming the center portion and the outer portion was put together in a high speed dry coater at a ratio of 80:20 and mixed at a rotation speed of 10,000 rpm to synthesize a double layer structure.
- the double layer structure material synthesized in Example 1 was synthesized by heat treatment at 600 ° C. for 2 hours under an air atmosphere.
- the lithium metal composite oxide Li 1.25 [Ni 0.21 Co 0.09 Mn 0.45 ] O 2 was obtained in the same manner as in the synthesis of the central portion of Example 1.
- Example 1 of 2. run the same way of the outer frame unit with the layered composite structure of the lithium metal composite oxide Li [Ni Co 0 .333 0 .333 0 .333 Mn] O 2 was obtained.
- the slurry was prepared by mixing the positive electrode active material synthesized in Examples 1 to 2 and Comparative Example 1 with carbon black and PVDF [Poly (vinylidene fluoride)] and 94: 3: 3 in a weight ratio of organic solvent.
- the slurry was applied to an Al foil having a thickness of 20 ⁇ m and then dried to prepare a positive electrode.
- the CR2016 coin half cell was assembled using a porous polyethylene film (CellGard 2502) as a metal lithium and a separator as the cathode together with the cathode, and 1.1M LiPF6 EC / EMC / DEC solution was used as an electrolyte.
- the coin cell prepared by the above method was subjected to a charge / discharge test at a current density of 0.1 C at 2.0 V to 4.6 V.
- Initial capacity and efficiency for this is shown in Table 1 below.
- Figure 6 the initial discharge capacity and efficiency of Example 1, the dissimilar metal is introduced later shows a higher capacity than Comparative Example 1 which is a co-precipitated product, while Example 2 showed a low capacity.
- This proves that the bilayer structure formed through the coating has the interfacial resistance of the center and the outer part, so that the capacity decreases, but the heat treatment eliminates the resistance of this interface.
- the method for producing a cathode active material for a lithium secondary battery of the present invention and the cathode active material for a lithium secondary battery manufactured thereby have a double-layer concentration gradient structure in which lithium concentration gradually increases from the outermost part to the inside, thereby exhibiting high capacity and heat. With stability and excellent lifespan, it can be used not only for small secondary batteries but also for large batteries for electric vehicles and power storage systems.
Abstract
Description
비교예1 | 실시예 1 | 실시예2 | ||
충전용량 | mAh/g | 291.0 | 287.1 | 287.4 |
방전용량 | 247.5 | 239.9 | 249.7 | |
초기효율 | % | 81.5 | 83.6 | 86.9 |
Claims (7)
- a) 니켈, 코발트, 망간 및 선택적으로 전이 금속을 함유하는 제 1 금속염 수용액, 킬레이팅제 및 염기성 수용액을 반응기에서 동시에 혼합한 후, 리튬 원료와 혼합 소성하여 하기 화학식 1의 화합물을 포함하는 중심부를 제조하는 단계;[화학식 1]Lix1[Ni1-y1-z1-w1Coy1Mnz1Mw1]O2(상기 식에서 0.9≤x1≤1.3, 0.1≤y1≤0.3, 0.0≤z1≤0.3, 0≤w1≤0.1이고 M은 Mg, Zn, Ca, Sr, Cu, Zr, P, Fe, Al, Ga, In, Cr, Ge, Sn로부터 선택되는 1종 이상의 금속임)b) 니켈, 코발트, 망간 및 선택적으로 전이 금속을 함유하는 제 2 금속염 수용액, 킬레이팅제 및 염기성 수용액을 반응기에서 동시에 혼합한 후, 리튬 원료와 혼합 소성하고, 이를 나노 크기로 분쇄하여 하기 화학식 2의 화합물을 포함하는 외곽부 형성용 화합물을 제조하는 단계;[화학식 2]Lix2[Ni1-y2-z2-w2Coy2Mnz2Mw2]O2(상기 식에서 0.9≤x2≤1+z2, 0≤y2≤0.33, 0≤z2≤0.5, 0≤w2≤0.1이고 M은 Mg, Zn, Ca, Sr, Cu, Zr, P, Fe, Al, Ga, In, Cr, Ge, Sn로부터 선택되는 1종 이상의 금속임)c) 상기 a)단계에서 얻은 중심부와 상기 b)단계에서 얻은 외곽부 형성용 화합물을 혼합하여 상기 중심부 표면에 외곽부를 형성시키는 단계; 및d) 상기 c)단계에서 얻은 화합물을 500 내지 800℃에서 열처리하여 상기 중심부와 상기 외곽부의 접촉 경계면에서부터 상기 외곽부의 표면부까지 리튬이 연속적인 농도 구배로 존재하는 이중층 구조를 형성하는 단계;를 포함하는 것을 특징으로 하는 리튬 이차전지용 양극활물질의 제조방법.
- 제 1항에 있어서,상기 a) 단계에서의 중심부의 평균 입경은 3 내지 20㎛인 것을 특징으로 하는 리튬 이차전지용 양극활물질의 제조방법.
- 제 1항에 있어서,상기 b)단계에서의 외곽부 형성용 화합물의 평균 입경은 20 내지 600nm인 것을 특징으로 하는 리튬 이차전지용 양극활물질의 제조방법.
- 제 1항에 있어서,상기 c)단계 및 d)단계에서 상기 중심부의 표면에 형성되는 외곽부의 두께는 0.5 내지 5㎛인 것을 특징으로 하는 리튬 이차전지용 양극활물질의 제조방법.
- 제 1항 내지 제 4항 중 어느 한 항에 의해 제조되어, 상기 중심부와 외곽부의 접촉 경계면에서부터 상기 외곽부의 표면부까지 리튬이 연속적인 농도 구배로 존재하는 리튬 이차전지용 양극활물질.
- 제 1항 내지 제 4항 중 어느 한 항에 의해 제조되어,외곽부의 표면부를 기준으로 하여 외곽부 내의 일정 지점까지의 거리를 D 라고 하고, D가 외곽부의 표면부에서부터 중심부와 외곽부의 접촉 경계면까지 변화할 경우, 상기 D 위치에서의 금속 원소들의 농도에 대한 리튬의 농도비를 P 라고 할 때, D와 P와의 관계식이 하기 식을 만족하는 리튬 이차전지용 양극활물질.P = aD + bD = 외곽부의 표면부를 기준으로 하여 외곽부 내의 일정 지점까지의 거리P = D 위치에서의 금속 원소들의 농도에 대한 리튬의 농도비0.07 ≤ a ≤ 0.7 , 0.95 ≤ b ≤ 1.05
- 제 5항 또는 제 6항의 리튬 이차전지용 양극활물질을 이용한 것을 특징으로 하는 리튬 이차전지.
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EP2698850A1 (en) * | 2012-08-14 | 2014-02-19 | Samsung SDI Co., Ltd. | Positive active material for rechargeable lithium battery, method for preparing same and rechargeable lithium battery including same |
US9614225B2 (en) | 2012-08-14 | 2017-04-04 | Samsung Sdi Co., Ltd. | Positive active material for rechargeable lithium battery, method for preparing same and rechargeable lithium battery including same |
WO2014059348A2 (en) | 2012-10-11 | 2014-04-17 | Lampe-Onnerud Maria Christina | Lithium ion battery |
EP3573136A2 (en) | 2012-10-11 | 2019-11-27 | Cadenza Innovation, Inc. | Method for manufacturing lithium ion batteries |
WO2017069410A1 (ko) * | 2015-10-20 | 2017-04-27 | 주식회사 엘지화학 | 다층 구조의 리튬 금속 산화물들을 포함하는 리튬 이차전지용 양극 활물질 및 그것을 포함하는 양극 |
WO2017069407A1 (ko) * | 2015-10-20 | 2017-04-27 | 주식회사 엘지화학 | 다층 구조의 금속 산화물들을 포함하는 양극 활물질 제조용 전구체 및 이를 사용하여 제조된 리튬 이차전지용 양극 활물질 |
US10581071B2 (en) | 2015-10-20 | 2020-03-03 | Lg Chem, Ltd. | Precursor for the production of positive electrode active material comprising metal oxides having multilayered structure and positive electrode active material for lithium secondary battery produced using the same |
US10741872B2 (en) | 2015-10-20 | 2020-08-11 | Lg Chem, Ltd. | Positive electrode active material for lithium secondary battery comprising lithium metal oxides having multilayered structure and positive electrode comprising the same |
JP2016026998A (ja) * | 2015-11-06 | 2016-02-18 | 三井金属鉱業株式会社 | 層構造を有するリチウム金属複合酸化物の製造方法 |
WO2018143783A1 (ko) * | 2017-02-06 | 2018-08-09 | 주식회사 엘지화학 | 리튬 이차전지용 양극 활물질 전구체 및 양극 활물질의 제조방법 |
US10892471B2 (en) | 2017-02-06 | 2021-01-12 | Lg Chem, Ltd. | Methods of preparing positive electrode active material precursor for lithium secondary battery and positive electrode active material |
WO2020028168A1 (en) | 2018-07-30 | 2020-02-06 | Cadenza Innovation, Inc. | Housing for rechargeable batteries |
Also Published As
Publication number | Publication date |
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CN103168381B (zh) | 2015-10-14 |
CN103168381A (zh) | 2013-06-19 |
US20130183583A1 (en) | 2013-07-18 |
WO2012011785A3 (ko) | 2012-05-31 |
US9083044B2 (en) | 2015-07-14 |
JP5759545B2 (ja) | 2015-08-05 |
JP2013535771A (ja) | 2013-09-12 |
KR20120009891A (ko) | 2012-02-02 |
KR101215829B1 (ko) | 2012-12-27 |
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