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WO2018105791A1 - Matériau actif de cathode destiné à une batterie secondaire au lithium, son procédé de fabrication, et batterie secondaire au lithium le comprenant - Google Patents

Matériau actif de cathode destiné à une batterie secondaire au lithium, son procédé de fabrication, et batterie secondaire au lithium le comprenant Download PDF

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Publication number
WO2018105791A1
WO2018105791A1 PCT/KR2016/014474 KR2016014474W WO2018105791A1 WO 2018105791 A1 WO2018105791 A1 WO 2018105791A1 KR 2016014474 W KR2016014474 W KR 2016014474W WO 2018105791 A1 WO2018105791 A1 WO 2018105791A1
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Prior art keywords
metal oxide
lithium
particles
active material
particle size
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English (en)
Korean (ko)
Inventor
권수지
최수안
정호준
신준호
전상훈
권성상
안지선
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L&F Co Ltd
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L&F Co Ltd
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Priority to PCT/KR2016/014474 priority Critical patent/WO2018105791A1/fr
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Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • 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
    • H01M4/58—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
    • 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

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.
  • a battery generates electric power by using an electrochemical reaction material for the positive electrode and the negative electrode.
  • a typical example of such a battery is a lithium secondary battery that generates electrical energy by a change in chemical potential (chemi cal potent al) when lithium ions are intercalated / deintercalated at a positive electrode and a negative electrode.
  • lithium silver is detached from the positive electrode during layer charging of the battery, and the phenomenon of being inserted from the positive electrode during discharge occurs.
  • the format ion efficiency of the lithium secondary battery is based on a case where 100% of lithium ions inserted at the same amount (at the time of discharge of the battery) are inserted in the same amount (at the time of discharge of the battery).
  • phase change of the positive electrode active material occurs due to the detachment and insertion of lithium ions, and it is known to use a positive electrode active material containing Co as a method of alleviating such phase shift. In other cases, it has been found that the phase change is less mitigating.
  • the more the use of the positive electrode active material having a smaller particle size the higher the chemical conversion efficiency of the battery. Since the layer discharge of the battery is a redox reaction from a broad viewpoint, the reaction is the higher the reaction area of the positive electrode active material. It is increasing. This phenomenon is called Kinetic ic.
  • the improvement in reaction by this Kinetic i phenomenon is not limited to the removal and insertion of lithium ions, but also applies to reaction with electrolyte. That is, the smaller the size of the positive electrode active material, the more active the formation of a solid electrolyte interphase (SEI) layer that acts as a resistance on the surface, which is deepened as the charge and discharge of the battery is repeated to increase the capacity retention rate. It is a factor to reduce.
  • SEI solid electrolyte interphase
  • a positive electrode active material In order to solve the above-mentioned problems, a positive electrode active material, a method for manufacturing the same, and a lithium secondary battery including the same, which exhibit excellent chemical conversion efficiency and capacity retention rate, and which can implement a high energy density. To provide.
  • a cathode active material for a lithium secondary battery in which the small particles occupy a volume of 10 vol% or less (excluding 0 vo l%) of the total volume (100 vol%) of the aggregate of the lithium metal oxide particles.
  • the small particles (C) may include lithium metal oxide particles having a molar ratio of lithium / metal less than 1, lithium metal oxide particles having a molar ratio of lithium / metal of 1 or more, and including Ti as a dopant, or a combination thereof.
  • the small particles (C) may each include 300 ppm or more of Ti as a dopant.
  • the small particles (C), respectively, do not contain Mg as a dopant, or may include less than 3000ppm (except 0 ppm).
  • the small particles (C) may be lithium metal oxide particles each containing 300 ppm or more of Ti and less than 3000 ppm of Mg (excluding 0 ppm) as a dopant.
  • the small particles (C) may be lithium metal oxide particles each containing Co as an essential element.
  • the volume of 10 vol% or less (excluding 0 vol%) of the total volume (100 vol%) of the lithium metal oxide particle set more specifically, 0.01 vol% or more, 1 vol% or less, 0.5 vol%
  • the small particles (C) may occupy a volume of 1 vol% or more.
  • the lithium metal oxide particles having a larger particle size than the small particles in the lithium metal oxide particle set include lithium metal oxide particles (A) having a particle size of more than 7 jm; And lithium metal oxide particles (B) having a particle size of more than 2 and 7 urn or less.
  • At least 10 vol% of the total volume of the lithium metal oxide particle aggregate may be occupied by the sum of the volume of the small particles (C) and the particles (B), and the balance may be occupied by the particles (A). .
  • the coating layer may include phosphate, lithium phosphate, or a combination thereof, and further include an oxide selected from the group consisting of lithium metal phosphate, metal phosphate, lithium metal oxide, metal oxide, and combinations thereof. can do.
  • small particles (C) which are lithium metal oxide particles having a particle size of m or less (excluding 0;); And a lithium metal oxide particle set comprising lithium metal oxide particles having a larger particle size than the small particles; and comprising a coating layer disposed on a surface of at least some of the particles forming the lithium metal oxide particle set.
  • Particles occupy less than 10 vol% (except 0 vol%) of the total volume of the lithium metal oxide particle assembly (100 vol%) and have a density of at least 3.9 g when compressed to 200 MPa at room temperature. / cc or more, discharge capacity after 40 cycles at a room temperature of 0.5C, discharge 1.0C, and 3.0V to 4.5V at room temperature is more than 97% of the discharge capacity after 1 cycle (discharge capacity after 40 cycles / 1
  • the positive electrode active material for lithium secondary batteries which has a discharge capacity * 100 ⁇ after a cycle is provided.
  • the positive electrode active material is 0.2 / 0.2C relative to Li + / Li at room temperature, And when the battery is driven under the conditions of 3.0V to 4.5V, the format ion efficiency may be 97% or more.
  • the positive electrode active material has a density (Pel let Dens i ty) of at least 4.0g / cc or more at 200 MPa in phase silver, 0.2 / 0.2C for Li + / Li, and 3.0V to 4.5 at room temperature
  • the format i on efficiency is 98% or more
  • the discharge capacity is 1 after 40 cycles when the battery is operated under the conditions of 0.5C, discharge 1.0C, and 3.0V to 4.5V at room temperature.
  • 98 3 ⁇ 4 »or more of the discharge capacity after the cycle discharge capacity after 40 cycles / discharge capacity after 100 cycles * 100%).
  • the small oxide metal oxide supply material may be particles containing Co as an essential component.
  • the molar ratio of lithium / metal may be 1 or less.
  • the mixture including the small particle metal oxide feed material and the lithium feed material may further include any one of a Ti feed material , a quality feed , and an Mg feed material, or may further include both the Ti feed material and the Mg feed material.
  • the firing temperature may be 750 to 1,050 ° C.
  • the minimum particle size is more than 0.1 / / m 0.5 ⁇ or less
  • the D50 particle diameter is 0.5 / more than 1 «m or less
  • the maximum particle size is more than 4 and 7 izm or less Powders consisting of lithium metal oxide particles can be produced.
  • the large particle metal oxide feed material may be particles having a size of 3 to 20.
  • the firing temperature may be 750 to 1, 050 ° C.
  • the firing temperature may be 650 to 950 ° C.
  • a positive electrode comprising a positive electrode active material according to system 1; A negative electrode including a negative electrode active material; And an electrolyte;
  • the chemical conversion efficiency and cycle capacity retention rate of the battery are excellently expressed, and further, the energy density may be improved.
  • FIG. 7 shows PSD analysis results of Preparation Examples 1 and 3.
  • DO.9 particle diameter is 0.1, 0.2, 0.3 .... 3, 5, , .... 10, 20, 30 ⁇
  • the particle size, D50 particle size refers to the particle size when particles are accumulated up to 50% by volume, and the particle size, D95, refers to the particle size when particles are accumulated up to 95% by volume.
  • small particles (C) which are lithium metal oxide particles having a particle size of 2 or less (excluding 0); And a lithium metal oxide particle set comprising lithium metal oxide particles having a larger particle size than the small particles; and a coating layer disposed on a surface of at least some of the particles forming the lithium metal oxide particle set.
  • the small particles occupy a volume of 10 vol% or less (excluding 0 vol%) of the total volume (100 vol%) of the lithium metal oxide particle assembly, and provides a cathode active material for a lithium secondary battery.
  • the "particle size” means the size of particles classified according to PSD (Particle Size Distribution).
  • the cathode active material provided in one embodiment of the present invention is a cathode active material in which two kinds of lithium metal oxide particles having different particle sizes are mixed by a so-called bi-modal technology, and has been compressed to 200 MPa from silver. It is advantageous to realize a compression density of 3.9g / cc or more.
  • i ty) is at least 3.9g / cc and can achieve a format ion efficiency of 97% or more when the battery is operated at a temperature of 0.2 / 0.2C for Li + / Li and 3.0V to 4.5V at room temperature.
  • the positive electrode active material satisfying the particle size, blending ratio, and coating layer conditions presented in one embodiment of the present invention has an advantage of expressing compression density, chemical conversion efficiency of the battery, and cycle retention excellently. Can be confirmed in the evaluation examples described later.
  • the particle size is 2 / less (but, except 0) is a small particle (C) of the lithium metal oxide particles; And lithium metal oxide particles having a particle size larger than those of the small particles; lithium metal oxide particles comprising 10 vol% or less of the total volume (100 vol) of the lithium metal oxide particles (but 0 vol%).
  • the small particles occupy a volume. .
  • the small particles can fill the voids between the lithium metal oxide particles having a larger particle size than the small particles, so that a large amount of positive electrode active material can be accumulated in a unit volume.
  • the chemical conversion efficiency of the battery is improved by the excellent reaction properties of the small particles, while the improvement of the reaction properties with the electrolyte is prevented by the lithium metal oxide particles having a larger particle size than the small particles, thereby preventing a decrease in cycle capacity retention.
  • the positive electrode active material provided in one embodiment of the present invention includes a coating layer located on the surface of at least a portion of the particles forming the lithium metal oxide particle set.
  • the coating layer may be present on some or all of the small particles and on the surface of some or all of the lithium metal oxide particles having a larger particle size than the small particles.
  • the particles in which the coating layer is present are advantageous in that the phase change caused by the detachment and insertion of lithium aions is suppressed, thereby improving the cycle capacity retention rate of the battery.
  • the coating layer may include phosphate, lithium phosphate, or a combination thereof, and an oxide selected from the group consisting of lithium metal phosphate, metal phosphate, lithium metal oxide, metal oxide, and combinations thereof. It may be a composite coating layer further comprising.
  • Such a coating layer may contribute to improvement of battery characteristics by suppressing oxidative decomposition of the positive electrode active material by reaction with an electrolyte at high voltage and providing a dr iving force for increasing the degree of diffusion of Li ions into the positive electrode active material. .
  • Small particle composition
  • metal means all metals (including dopants) except lithium in the lithium metal oxide particles.
  • Small particle size precursors of 1 or less are used. However, at a normal firing temperature of 750 to 1, 050 ° C (preferably 800 to 100 C C), the larger the amount of Li, the more the growth of lithium metal oxide particles is promoted by the synthetic promoting action (Fl ux effect). Can be.
  • a method of setting the molar ratio of lithium / metal in the small particle precursor to 1 or less was considered. It was confirmed by the evaluation example mentioned later that particle growth was suppressed and the small particle which has a particle size of 2 or less (however, more than 0) is formed also at normal baking temperature.
  • a method of adding an element that suppresses grain growth during firing of the small particle size precursor as a dopant is considered.
  • Ti is one of the elements that suppress mipza growth.
  • the addition of Ti in an amount corresponding to the increased content of L i results in a particle having a particle size of 2 ⁇ or less (more than 0 m) even at a normal firing temperature. It was confirmed in the evaluation examples to be described later that is formed.
  • doping of Ti may be applied when the molar ratio of lithium / metal is less than one. ⁇
  • the size of the lithium metal oxide particles formed may vary depending on the amount of Ti added with the dopant. Specifically, when the Ti content is 300ppra or more, small particles having a particle size of 2 ⁇ m or less (but greater than 0) are formed, but when the Ti content is less than 300 ppm, particles larger than zm may be formed under the same conditions. have.
  • the reason why the size of the lithium metal oxide particles formed according to the Ti content varies in various ways is related to the extent to which the growth of grain boundaries is suppressed by the precipitates.
  • the small particles (C) may each contain 300 ppm or more of Ti as a dopant.
  • dopant does not contain Mg or, if included, the content can be controlled to less than 3000ppm (except 0 ppm).
  • the small particles (C), respectively, may be lithium metal oxide particles containing Co as an essential member element.
  • Co is an element that can alleviate the phase shift caused by the detachment and insertion of lithium ions. Specific particle size and blending ratio
  • the positive electrode active material provided in one embodiment of the present invention after mixing a large particle size lithium metal oxide powder prepared from a large particle precursor and a small particle size lithium metal oxide powder prepared from a small particle precursor, It may be obtained through a surface coating process.
  • particles having a size smaller than the minimum particle size (Dmin) of the large particle size lithium metal oxide powder (A) before mixing may have the characteristics of the small particle lithium metal oxide powder before mixing.
  • the particles having the characteristics of the small particle size lithium metal oxide powder before mixing even in the mixed powder the particle size, that is, the particle size larger than the small particles, but has a size smaller than the Dmin of the large-size lithium metal oxide powder Particles.
  • Dmin of the large-diameter lithium metal oxide powder may be about 7;
  • the lithium metal oxide particles having a larger particle size than the small particles in the lithium metal oxide particle set include lithium metal oxide particles (A) having a particle size greater than 7; And particles Lithium metal oxide particles (B) having a size of greater than 3 ⁇ 4 ⁇ or less than 7 // m.
  • a volume sum of the particles (C) and the particles (B) occupies a volume of at least 10 vol%, and the balance is the particles ( A) can occupy.
  • the relationship between the particles (A), the particles (B), and the particles (C) will be clearly understood.
  • the volume of 10 vol% or less (excluding 0 vol%) of the total volume (100 vol) of the lithium metal oxide particle set more specifically, the volume of 0.01 vol% or more and 1 vol% or less, 0.5 vol%
  • the small particles (C) may occupy a volume of 1 vol% or more.
  • Lithium metal oxide particles included in the positive electrode active material provided in one embodiment of the present invention may include a compound represented by the following formula (1), regardless of the particle size.
  • M may include Co and optionally include Ni, Mn, and combinations thereof
  • A may be selected from the group consisting of Mg, Ca, Sr, Ba, and combinations thereof, and D may further include Ti, Zr, Ce, Ge, Sn, Al, Sb, and combinations thereof.
  • small particles (C) which are lithium metal oxide particles having a particle size of / m or less (excluding 0; ⁇ ); And particles than the small particles Lithium metal oxide particles comprising a large size of the lithium metal oxide particles; comprising a coating layer located on the surface of at least some of the particles constituting the lithium metal oxide particles aggregate, wherein the lithium metal oxide particles
  • the small particles occupy a volume of 10 vol% or less (excluding 0 vol3 ⁇ 4) of the total volume (100 vol), and the compressive density from the silver to 200 MPa is at least 3.9 g / cc.
  • the discharge capacity after 40 cycles is at least 97% of the discharge capacity after 1 cycle (discharge capacity after 40 cycles / discharge capacity after 1 cycle) when the battery is driven at layer temperature of 0.5C, discharge 1.0C, and 3.0V to 4.5V. 100%), to provide a positive electrode active material for a lithium secondary battery.
  • the compressive density of the positive electrode active material may have a particle size similar to that of the positive electrode active material but higher than that of the positive electrode active material which is not a bimodal form.
  • the positive electrode active material may be compressed to 200 MPa at room temperature. Peel et Densi ty has at least 3.9g / cc and can express high energy density.
  • the battery to which the positive electrode active material is applied may exhibit a cycle capacity retention rate of 97% when driven at the above limited conditions at room temperature. Furthermore, the battery to which the positive electrode active material is applied may have a format ion efficiency of 97% or more when driven under conditions of 0.2 / 0.2C, and 3.0V to 4.5V with respect to Li + / Li at room temperature.
  • the positive electrode active material has a density (Pel let Densi ty) of at least 4.0g / cc or more at 200 MPa at room temperature, 0.2 / 0.2C for Li + / Li, and 3.0V to 4.5V at phase silver
  • the battery has a format ion efficiency of 98% or more, and the battery is discharged after 1 cycle after 40 cycles when operating the battery at room temperature under 0.5 C, discharge 1.0 C, and 3.0 V to 4.5 V. More than 98% of discharge capacity (after 40 cycles, after discharge cycle / 1 cycle Discharge capacity * ioo%).
  • the present invention by firing a mixture comprising a metal oxide feed material and a lithium feed material having a large particle size, preparing a large particle lithium metal oxide powder; Calcining a mixture comprising a small particle metal oxide material and a lithium feed material to produce a small particle lithium metal oxide powder; Preparing a mixture of the large particle lithium metal oxide powder and the small particle lithium metal oxide powder; Adhering a coating raw material to a surface of a mixture of the large particle lithium metal oxide powder and the lithium metal oxide small particle powder; And calcining the mixture to which the coating raw material is attached, wherein the metal oxide feed material having a small particle size is a particle having a size of 1.5 // m or less (excluding 0) and the metal oxide supply having the large particle size.
  • the material provides a method for producing a cathode active material for a lithium secondary battery, which is a particle having a size larger than that of the small particle metal oxide feed material.
  • the small particle size precursor means a metal oxide supply material having the small particle size, and is a particle having a size of 1.5 or less (excluding 0).
  • the large particle size precursor means a metal oxide supply material having the large particle size, and means a particle having a larger size than the small particle metal oxide supply material.
  • the molar ratio of lithium / metal may be 1 or less.
  • the growth of particles is suppressed, and small particles having a particle size of 2 m or less (but greater than 0 // m) are formed even at a normal firing temperature, as described above.
  • the mixture including the small particle metal oxide feed material and the lithium feed material may further include any one of a Ti feed material and an Mg feed material, or may further include both the Ti feed material and the Mg feed material.
  • the molar ratio of lithium / metal is 1 or more
  • the particle size of 2 ⁇ M or less is achieved even at a normal firing temperature.
  • the branched particles are formed as described above.
  • doping of Ti may be applied when the molar ratio of lithium / metal is less than one.
  • the small oxide metal oxide supply material may be particles containing Co as an essential component. Co has been described above as an element capable of alleviating the phase shift caused by the detachment and insertion of lithium ions. Small particle precursor firing process (small particle powder manufacturing process)
  • the firing temperature may be 750 to 1, 050 ° C. This is a conventional calcined silver for crystallization, and detailed description thereof is omitted as it is generally known.
  • the minimum particle size is greater than 0.5 / 1 / m or less 0.5
  • the D50 particle diameter is greater than 0.5 ⁇ 1 / an or less
  • the maximum particle size is greater than 4 7 ⁇ Powders consisting of lithium metal oxide particles below can be prepared.
  • the large particle diameter metal oxide feed material may be particles having a size of 3 to 15.
  • Large particle precursor firing process large particle powder manufacturing process
  • the firing temperature may be 750 to 1,050 ° C. This is the usual firing temperature for crystallization, the details of which are omitted as they are generally known.
  • Large particle powder and small particle powder mixing process
  • the coating process is performed on the small particle powder, the large particle powder, the black silver, the large particle powder and the small particle powder mixed powder.
  • the coating layer may be formed on the surface of some or all of the particles included in the powder to be coated.
  • the coating raw material may be a phosphate coating raw material.
  • it may be phosphoric acid (H 3 P0 4 ), ammonium dihydrogen phosphate (NH 4 H 2 P0 4 ), diammonium hydrogen phosphate ((NH 4 ) 2 HP0 4 ), or a combination thereof.
  • firing silver may be 650 to 95CTC.
  • a coating layer containing phosphate, lithium phosphate, or a combination thereof may be formed.
  • a composite coating layer further comprising an oxide selected from the group consisting of lithium metal phosphate, metal phosphate, lithium metal oxide, metal oxide and combinations thereof may be formed.
  • Lithium metal oxide powder obtained by heat-treating the mixture at 900 to 1000 ° C. for 10 hours was prepared as Preparation Example 1.
  • Manufacture example 2 small particle size powder
  • Li 2 C0 3 , C03O4 (D50 14 // m), Ti0 2 500 ppm, and MgC0 3 100 ppm were dry mixed but the Li / Me ratio in the mixture was 1.024.
  • FIG. 5 is a SEM photograph of one particle of Preparation Example 3 at a high magnification (more than 10,000 magnification), and from this, it can be seen that the particle size is smaller than 2 and the particle shape is equilateral.
  • Preparation Example 7 0.13 17.55 62.23 Preparation Example 1 and Preparation Example 6 Mixed Powder Preparation Example 8 0. 13 17.43 62.23 Preparation Example 3 and Preparation Example 6 Mixed Powder Preparation Example 9 0.78 18.26 62.23 Preparation Example 4 and Preparation Example 6 Preparation of Mixed Powder Example 10 1.50 17.76 62.23 Preparation Example 3 and Preparation Example 6 Mixed Powder Coating
  • the minimum particle size was recorded in Dmin and the maximum particle size in Dmax, and the D50 particle size according to the general definition. Recorded.
  • Ti is more than 500ppm and can be doped with 300ppm or more, for example, to form a particle size "as appropriate.
  • it is necessary to control the Mg so as not to be doped or less than 2000ppm when doping.
  • Preparation Examples 7 and 8 have large particle size powders, but particles having a size smaller than Dmin of Preparation Example 6 at least in the PSD of Preparation Example 8 exhibit the characteristics of the particles of Preparation Examples 1 and 3. It can be seen from having.
  • a battery was fabricated by using Preparation Example 8 in which large and small particle powders were mixed and Preparation Example 10 in which surface coating after large and small particle powders were mixed as positive electrode active materials, respectively.
  • 95% by weight of the positive electrode active material, 2.5% by weight of carbon black as a conductive agent, and 2.5% by weight of PVDF as a binder were added to 5.0% by weight of N-methyl-2 pyridone (NMP) as a solvent (solvent).
  • NMP N-methyl-2 pyridone
  • the positive electrode slurry was applied to a thin film of aluminum (A1), which is a positive electrode current collector having a thickness of 20 to 40, and vacuum dried, followed by roll press to prepare a positive electrode.
  • A1 a thin film of aluminum
  • Li-metal was used as the negative electrode.
  • a coin cell type half cell was manufactured using 1.15M LiPF6EC: DMC (l: lvol%) as an electrolyte and a cathode prepared as described above.
  • the cycle capacity retention rate was evaluated for the battery produced using Preparation Example 8 in which large and small particle powders were mixed, and Preparation Example 10 in which surface coating after large and small particle powder mixing were used as the positive electrode active material, respectively.
  • particles smaller than the Dmin of the large particle size before mixing may have similar characteristics to the small particle size before mixing have.
  • the particles occupied at least 10.17 vol% of the particles smaller than the Dmin of the large particle size powder before mixing, and among them, those particles having a particle size of 2 im or less (but 1.5; mi or more)
  • the volume occupied was 0.78 vol%, it was confirmed that the pellet density when pressed at 200 MPa at room temperature is at least 3.9 g / cc or more.
  • the chemical conversion efficiency may be more than 97%.
  • the capacity retention rate may be more than 97%.
  • the surface-coated positive electrode active material after mixing the large particle size powder has a volume occupied by particles smaller than Dmin of the large particle size powder before mixing, at least 10.17 vol%, and in particular, has a particle size of 2 M or less (but 1.5 or more).
  • the eggplants have a volume of 0.78 vol% and have a Pel let Dens i ty of at least 3.9 g / cc when pressed to 200 MPa at room temperature. Dose retention may be expressed at greater than 97%.
  • the small particle powder used for the preparation can be used by reducing the Li / Me ratio in the small particle powder to less than 1 or by appropriately doping Ti expressing the grain growth inhibiting function.
  • the Li / Me molar ratio is less than 1 and the Ti content is 300ppm, small particles having a particle size of D50 of 2 m or less (but 0.5 or more) may be formed.
  • the Li / Me molar ratio is 1 or more, in accordance with the increased content of Li If the content of Ti is also increased, small particles having a particle size of 2 or less (but 0.5 or more) may be formed.
  • the Ti content is increased in the range of 300 ppm or more, the distribution of the particle size may appear evenly.
  • the Mg content is more than 3000 ppra, particle uniformity may decrease. Therefore, when the Li / Me ratio is less than 1, or the Li / Me ratio is 1 or more, the Ti content is 300ppm or more, and the Mg content is controlled to be less than 4000ppm, it is necessary to use the small particle size powder prepared as a raw material.
  • the present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person of ordinary skill in the art to which the present invention pertains does not change the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Battery Electrode And Active Subsutance (AREA)

Abstract

Les modes de réalisation de la présente invention concernent un matériau actif de cathode qui présente une excellente efficacité coulombienne et un taux de rétention de capacité de cycle d'une batterie et qui peut réaliser une densité d'énergie élevée, son procédé de fabrication, et une batterie secondaire au lithium le comprenant.
PCT/KR2016/014474 2016-12-09 2016-12-09 Matériau actif de cathode destiné à une batterie secondaire au lithium, son procédé de fabrication, et batterie secondaire au lithium le comprenant Ceased WO2018105791A1 (fr)

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Cited By (1)

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US11053602B2 (en) 2018-09-17 2021-07-06 Co-Tech Development Corp. Micro-roughened electrodeposited copper foil and copper foil substrate

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KR20120029441A (ko) * 2009-06-05 2012-03-26 유미코르 안정한 리튬 캐소드 물질용 나노입자 도핑된 전구체
US20120156566A1 (en) * 2009-06-24 2012-06-21 Reminex Sa Particles of doped lithium cobalt oxide, method for preparing the same and their use in lithium ion batteries
KR101400593B1 (ko) * 2012-12-06 2014-05-27 삼성정밀화학 주식회사 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차 전지
KR20160075196A (ko) * 2014-12-19 2016-06-29 주식회사 엘지화학 혼합 양극활물질, 이를 포함하는 양극 및 이차전지

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KR20120029441A (ko) * 2009-06-05 2012-03-26 유미코르 안정한 리튬 캐소드 물질용 나노입자 도핑된 전구체
US20120156566A1 (en) * 2009-06-24 2012-06-21 Reminex Sa Particles of doped lithium cobalt oxide, method for preparing the same and their use in lithium ion batteries
KR20110132287A (ko) * 2010-06-01 2011-12-07 주식회사 엘앤에프신소재 전이금속 화합물 전구체, 이를 이용한 리튬 전이금속 화합물, 상기 리튬 전이금속 화합물을 포함하는 양극 활물질 및 상기 양극 활물질을 포함하는 리튬 이온 이차전지
KR101400593B1 (ko) * 2012-12-06 2014-05-27 삼성정밀화학 주식회사 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차 전지
KR20160075196A (ko) * 2014-12-19 2016-06-29 주식회사 엘지화학 혼합 양극활물질, 이를 포함하는 양극 및 이차전지

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11053602B2 (en) 2018-09-17 2021-07-06 Co-Tech Development Corp. Micro-roughened electrodeposited copper foil and copper foil substrate

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