WO2019059654A1 - Précurseur de matériau actif de cathode pour batterie secondaire, matériau actif de cathode, et batterie secondaire au lithium le comprenant - Google Patents

Précurseur de matériau actif de cathode pour batterie secondaire, matériau actif de cathode, et batterie secondaire au lithium le comprenant Download PDF

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WO2019059654A1
WO2019059654A1 PCT/KR2018/011081 KR2018011081W WO2019059654A1 WO 2019059654 A1 WO2019059654 A1 WO 2019059654A1 KR 2018011081 W KR2018011081 W KR 2018011081W WO 2019059654 A1 WO2019059654 A1 WO 2019059654A1
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Prior art keywords
active material
doping element
precursor
cathode active
lithium
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PCT/KR2018/011081
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English (en)
Korean (ko)
Inventor
유민규
조치호
박성빈
허혁
황진태
정왕모
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주식회사 엘지화학
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Priority claimed from KR1020180111642A external-priority patent/KR102217105B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US16/480,832 priority Critical patent/US11611076B2/en
Priority to EP18857652.4A priority patent/EP3560894A4/fr
Priority to JP2020516365A priority patent/JP7047203B2/ja
Priority to CN201880008449.9A priority patent/CN110225886A/zh
Publication of WO2019059654A1 publication Critical patent/WO2019059654A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides; Hydroxides
    • 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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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 precursor for a secondary battery, a cathode active material, and a lithium secondary battery comprising the same.
  • the lithium secondary battery includes a cathode including a cathode active material capable of intercalating / deintercalating lithium ions, a cathode including a cathode active material capable of intercalating / deintercalating lithium ions, an electrode including a microporous separator interposed between the cathode and the anode, Means a battery in which an electrolyte containing lithium ions is contained in an assembly.
  • a lithium transition metal oxide is used as the positive electrode active material of the lithium secondary battery, and lithium metal, lithium alloy, crystalline or amorphous carbon or carbon composite is used as the negative electrode active material.
  • the active material is coated on the electrode current collector with an appropriate thickness and length, or the active material itself is coated in a film form and wrapped or laminated with a separator as an insulator to form an electrode group. The electrode group is then placed in a can or similar container, Thereby manufacturing a secondary battery.
  • Lithium cobalt oxide (LiCoO 2 ) has a layered structure as a cathode active material of a lithium secondary battery that has been actively researched and used at present.
  • Lithium cobalt oxide (LiCoO 2 ) has an advantage of high operating voltage and excellent capacity characteristics, but its thermal characteristics are poor due to the destabilization of the crystal structure due to lithium remnants and the structure becomes unstable under high voltage.
  • lithium cobalt oxide (LiCoO 2 ) has been increasingly required for a high capacity lithium secondary battery. Unlike a tin oxide cathode active material, the capacity can be increased only by raising the voltage. Therefore, It is necessary to develop lithium cobalt oxide (LiCoO 2 ) capable of securing the structural stability even at 4.5 V or more.
  • An object of the present invention is to provide a cathode active material of lithium cobalt oxide which is an acceptor having an average particle diameter (D 50 ) of 15 ⁇ m or more by solving the problem of obstructing grain growth by a doping element while having structural stability under high voltage by excessively doping a doping element will be.
  • the present invention relates to a secondary battery comprising a primary particle of Co 3 O 4 or CoOOH, wherein the primary particle contains 3,000 ppm or more of a doping element and the average particle diameter (D 50 ) of the primary particle is 15 ⁇ m or more Precursor.
  • the present invention also provides a lithium secondary battery comprising a primary particle of a lithium cobalt oxide, wherein the primary particle contains a doping element in an amount of 2,500 ppm or more, and the primary particle has an average particle diameter (D 50 ) .
  • the present invention also provides a method of forming a precursor, comprising: providing a precursor forming solution comprising a cobalt-containing starting material and a doping element source; And forming a precursor of Co 3 O 4 or CoOOH having an average particle diameter (D 50 ) of the primary particles of not less than 15 ⁇ m and containing the doping element in an amount of 3,000 ppm or more by coprecipitation reaction with the precursor forming solution, A method for manufacturing a positive electrode active material precursor for a battery is provided.
  • the cathode active material precursor powder and the lithium source according to the present invention are mixed and sintered to prepare a lithium cobalt oxide having an average particle size (D 50 ) of the primary particles of not less than 2,500 ppm and having a primary particle size of not less than 15 ⁇ m
  • the present invention also provides a method for producing a cathode active material for a secondary battery.
  • the present invention also provides a positive electrode and a lithium secondary battery including the positive electrode active material.
  • a cathode active material of lithium cobalt oxide which is an acceptor having an average particle diameter (D 50 ) of 15 ⁇ m or more, by solving the problem of obstructing grain growth by a doping element while having structural stability under high voltage by excessively doping the doping element can do.
  • Example 1 is a scanning electron microscope (SEM) photograph of a precursor of a cathode active material prepared according to Example 1 of the present invention.
  • a precursor is doped with an excessive amount of a doping element, and a precursor particle size is increased up to an average particle diameter (D 50 ) of 15 ⁇ m or more to prepare a precursor of an acceptor.
  • D 50 average particle diameter
  • the cathode active material precursor for a secondary battery according to the present invention comprises primary particles of Co 3 O 4 or CoOOH, wherein the primary particles contain 3,000 ppm or more of a doping element, and the average particle diameter of the primary particles (D 50 ) Is not smaller than 15 mu m.
  • the cathode active material precursor of the present invention is composed of primary particles of Co 3 O 4 or CoOOH.
  • the positive electrode active material precursor of the present invention is preferably a primary particle that is not a secondary particle formed by aggregation of primary particles but is not physically separated.
  • the average particle diameter (D 50 ) of the primary particles is 15 ⁇ m or more, and more preferably the average particle diameter (D 50 ) of the primary particles is 17 ⁇ m or more.
  • the average particle diameter (D 50 ) of the primary particles of the cathode active material precursor is less than 15 ⁇ , when the cathode active material is produced through a firing process using a precursor of less than 15 ⁇ , the doping element interferes with the particle growth, There arises a problem that it is difficult to produce a cathode active material having a thickness (D 50 ) of 15 ⁇ m or more. If the positive electrode active material can not be made into an average particle diameter (D 50 ) of 15 ⁇ m or more, there is a limit to increase the compression density of the positive electrode and it is difficult to increase the battery capacity.
  • the cathode active material precursor of the present invention may contain not less than 3,000 ppm of the doping element and more preferably not less than 4,000 ppm of the doping element.
  • the primary particles of the cathode active material precursor may contain less than 3,000 ppm of the doping element, it is difficult to secure the structural stability of the lithium cobalt oxide cathode active material.
  • the primary particles of the cathode active material precursor have low structural stability at a high voltage of 4.5 V or higher, There may be a problem of deterioration of battery characteristics.
  • a doping element is further added to the precursor when the undoped precursor is formed as a substituent, Doping element having a uniform concentration can not be doped and there is a limit to improvement in cell characteristics such as battery capacity, rate characteristics, and life characteristics.
  • the doping element may be at least one or more selected from the group consisting of Al, Ti, Mn, Zr, Mg, Nb, Ca, F and Ni, and more preferably Al.
  • the doping element Al since the grain growth inhibiting effect is particularly large as compared with other doping elements (for example, Mg), the precursor which is a substituent is produced with a high content of doping as in the present invention, May be more preferable.
  • the precursor of the cathode active material doped with the doping element in the preparation of the precursor may have a certain concentration in the primary particle of the precursor.
  • the cathode active material precursor of the present invention comprises a precursor forming solution including a cobalt-containing starting material and a doping element source; And forming a precursor of Co 3 O 4 or CoOOH having an average particle diameter (D 50 ) of the primary particles of not less than 15 ⁇ m by containing at least 3,000 ppm of a doping element by coprecipitation reaction of the precursor forming solution do.
  • the doping element source is subjected to coprecipitation to perform precursor doping.
  • the doping element can be doped at a uniform concentration by doping the precursor by adding the doping element source together in the precursor coprecipitation step and the particle size of the doping precursor can be easily controlled by controlling the coprecipitation reaction time, But the precursor size can be easily increased.
  • the precursor preparation first provides a precursor forming solution comprising a cobalt-containing starting material and a doping element source.
  • the cobalt-containing starting material may be a sulfate, halide, acetate, sulfide, hydroxide, oxide, or oxyhydroxide containing cobalt, and is not particularly limited as long as it is soluble in water.
  • the cobalt-containing starting material is a Co (SO 4) 2 and 7H 2 O, CoCl 2, Co (OH) 2, Co (OCOCH 3) 2 and 4H 2 O or Co (NO 3) 2 and 6H 2 O, etc., and any one or a mixture of two or more of them may be used.
  • the doping element source may be a sulfate, nitrate, acetate, halide, hydroxide or oxyhydroxide containing a doping element, and any one or a mixture of two or more of them may be used.
  • the doping element may be at least one or more selected from the group consisting of Al, Ti, Mn, Zr, Mg, Nb, Ca, F and Ni, and more preferably Al as the doping element.
  • the precursor forming solution may be prepared by adding the cobalt-containing starting material and the doping element source to a solvent, specifically water or a mixture of water and an organic solvent (specifically, an alcohol or the like) which can be uniformly mixed with water, or A solution containing each of the cobalt-containing starting materials and a solution containing the doping element source may be prepared and then mixed and used.
  • a solvent specifically water or a mixture of water and an organic solvent (specifically, an alcohol or the like) which can be uniformly mixed with water, or
  • a solution containing each of the cobalt-containing starting materials and a solution containing the doping element source may be prepared and then mixed and used.
  • the precursor forming solution is coprecipitated to form a Co 3 O 4 or CoOOH precursor having an average particle size (D 50 ) of the primary particles of 3,000 ppm or more and a primary particle size of 15 ⁇ m or more.
  • the precursor solution was added to the reactor and form, doped with the co-precipitation reaction by adding a chelating agent and aqueous base element is doped more than 3,000ppm, 1 average particle diameter of primary particles (D 50) is less than 15 ⁇ m Co 3 O 4 Or a CoOOH precursor can be prepared.
  • the chelating agent examples include NH 4 OH, (NH 4 ) 2 SO 4 , NH 4 NO 3 , NH 4 Cl, CH 3 COONH 4 , and NH 4 CO 3 .
  • the above mixture may be used.
  • the chelating agent may be used in the form of an aqueous solution.
  • As the solvent water or a mixture of water and an organic solvent (specifically, alcohol or the like) that can be mixed with water and water may be used.
  • the basic compound may be a hydroxide of an alkali metal or an alkaline earth metal such as NaOH, KOH or Ca (OH) 2 , or a hydrate thereof, and either one of them or a mixture of two or more of them may be used.
  • the basic compound may also be used in the form of an aqueous solution.
  • As the solvent water or a mixture of water and an organic solvent (specifically, alcohol or the like) which can be uniformly mixed with water may be used. At this time, the concentration of the basic aqueous solution may be 2M to 10M.
  • the coprecipitation reaction for the production of the cathode active material precursor may be carried out at a pH of from 10 to 12. If the pH is out of the above range, there is a possibility that the size of the cathode active material precursor to be produced is changed or the particle cleavage is caused. More specifically, at a pH of 11 to a pH of 12. Such pH control can be controlled through the addition of a basic aqueous solution.
  • the coprecipitation reaction for the production of the cathode active material precursor may be performed in an inert atmosphere such as nitrogen at a temperature ranging from 30 ° C to 80 ° C.
  • a stirring process may be selectively performed, wherein the stirring speed may be from 100 rpm to 2000 rpm.
  • the Co 3 O 4 or CoOOH precursor of the primary particles in which the doping element is excessively doped is precipitated.
  • the content of the doping element doped in the precursor may be 3,000 ppm or more, more preferably 4,000 ppm or more.
  • the doping element can be doped with a high content.
  • the precursor thus prepared can be uniformly doped with the doping element without any concentration gradient from the center of the precursor particle of the cathode active material to the surface thereof.
  • the particle size of the doping precursor can be easily controlled by controlling the coprecipitation reaction time in the production of the precursor, the size of the precursor can easily be raised while doping with a high content.
  • the coprecipitation reaction time may be 10 to 40 hours, more preferably 10 to 30 hours.
  • the Co 3 O 4 or CoOOH precursor having an average particle size (D 50 ) of the primary particles of 15 ⁇ m or more can be formed by adjusting the coprecipitation time.
  • the precipitated Co 3 O 4 or CoOOH precursor may be selectively subjected to separation and drying processes according to a conventional method, and the drying process may be performed at 110 ° C. to 400 ° C. for 15 to 30 hours.
  • the present invention provides a cathode active material prepared using a precursor of an overdoped bulk as described above.
  • a cathode active material prepared using a precursor of an overdoped bulk as described above.
  • the cathode active material for secondary prevention of the present invention contains primary particles of lithium cobalt oxide, the primary particles contain 2,500 ppm or more of the doping element, the average particle diameter (D 50 ) of the primary particles is 15 mu m or more.
  • a precursor in the form of a secondary particle in which primary particles are aggregated is used, it is difficult to prepare a cathode active material having primary particles of 15 mu m or more due to the grain growth inhibition action of the high-dose doping element during the firing process.
  • the doping element Al since the particle growth inhibiting action is particularly large as compared with other doping elements (for example, Mg), the precursor which is a substituent is produced by doping with a high content as in the present invention, It may be more preferable to produce it.
  • the present invention is produced by using a precursor containing 3,000 ppm or more of the doping element and having an average particle diameter (D 50 ) of the primary particles of 15 ⁇ m or more as described above, the doping element is 2,500 ppm or more and an average particle diameter (D 50 ) of the primary particles of 15 ⁇ or more can be produced.
  • the cathode active material of the present invention is composed of primary particles of lithium cobalt oxide.
  • the average particle diameter (D 50 ) of the primary particles is 15 ⁇ m or more, and more preferably the average particle diameter (D 50 ) of the primary particles is 17 ⁇ m or more. It is possible to improve the battery capacity, energy density and lifetime characteristics by satisfying the average particle size (D 50 ) of the primary particles of the cathode active material of 15 ⁇ or more. In particular, when the average particle diameter (D 50 ) The capacity of the battery can be increased by significantly increasing the compression density of the anode by mixing the active material with the cathode active material of the small particle at a certain ratio.
  • the primary particles may contain a doping element in an amount of 2,500 ppm or more, more preferably 3,000 ppm or more in a doping element. Since the lithium source is further added in the production of the cathode active material, the content ratio (ppm) of the doping element of the cathode active material may be somewhat reduced compared with the content ratio (ppm) of the doping element contained in the cathode active material.
  • the primary particles of the cathode active material contain less than 2,500 ppm of the doping element, it is difficult to secure the structural stability of the lithium cobalt oxide cathode active material. In particular, the structural stability is lowered at a high voltage of 4.5 V or more, There is a problem that battery characteristics of the battery are deteriorated.
  • the doping element may be at least one or more selected from the group consisting of Al, Ti, Mn, Zr, Mg, Nb, Ca, F and Ni, and more preferably Al.
  • the doping element Al since the grain growth inhibiting effect is particularly large as compared with other doping elements (for example, Mg), the precursor which is a substituent is produced with a high content of doping as in the present invention, May be more preferable.
  • the doping element may have a constant concentration in the primary particles of the cathode active material particle.
  • the primary particles of the positive electrode active material may contain 50% or more of the entire content of the doping element in the central portion corresponding to 50% of the center of the radius of the particle from the center to the surface.
  • the lithium cobalt oxide may have a molar ratio (molar ratio of lithium / metal element (Co, M, etc.)) of metal elements (Co, M, etc.) other than lithium to lithium of 0.98 to 1.1.
  • the cathode active material according to an embodiment of the present invention may further include a surface layer on the particle surface of the lithium cobalt oxide and the surface layer may include Mg, Ti, Fe, Cu, Ca, Ba, Sn, Sb, At least one selected from the group consisting of Si, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Sc, Ce, Pr, Nd, Gd, Dy, Yb, Er, Co, One or more oxides.
  • the cathode active material of the present invention is obtained by mixing and firing a cathode active material precursor and a lithium source of the present invention to prepare a lithium cobalt-based compound having a doping element content of 2,500 ppm or more and having an average particle diameter (D 50 ) To form oxides.
  • the lithium source a lithium-containing sulfate, nitrate, acetate, carbonate, oxalate, citrate, halide, hydroxide or oxyhydroxide may be used, and it is not particularly limited as long as it can be dissolved in water.
  • the lithium source material may be Li 2 CO 3 , LiNO 3 , LiNO 2 , LiOH, LiOH ⁇ H 2 O, LiH, LiF, LiCl, LiBr, LiI, CH 3 COOLi, Li 2 O, Li 2 SO 4 , CH 3 COOLi, or Li 3 C 6 H 5 O 7 Etc., and any one or a mixture of two or more of them may be used.
  • the amount of the lithium source to be used may be determined depending on the content of lithium (Li) and the metal element (Co, etc.) other than lithium in the finally produced lithium cobalt oxide. Specifically, the lithium cobalt- And the molar ratio of the metal element other than lithium (molar ratio of lithium / metal element) is from 0.98 to 1.1.
  • a sintering agent when the precursor and the lithium source are mixed, a sintering agent may be optionally added.
  • the sintering agent specifically includes a compound containing an ammonium ion such as NH 4 F, NH 4 NO 3 , or (NH 4 ) 2 SO 4 ; Metal oxides such as B 2 O 3 or Bi 2 O 3 ; Or metal halides such as NiCl 2 or CaCl 2, and any one or a mixture of two or more of them may be used.
  • the sintering may be used in an amount of 0.01 to 0.2 mol based on 1 mol of the precursor.
  • the effect of improving the sintering property of the cathode active material precursor may be insignificant. If the content of the sintering agent is excessively high, the excessive sintering agent may deteriorate the performance of the cathode active material And there is a possibility that the initial capacity of the battery is lowered during the charge / discharge process.
  • a moisture removing agent may be optionally added.
  • the moisture removing agent include citric acid, tartaric acid, glycolic acid, and maleic acid, and any one or a mixture of two or more thereof may be used.
  • the moisture scavenger may be used in an amount of 0.01 to 0.2 mol based on 1 mol of the precursor.
  • the firing may be performed at 900 ° C to 1,100 ° C, and more preferably 1,000 to 1,050 ° C. If the calcination temperature is less than 900 ° C., there is a fear that the discharge capacity per unit weight, the cycle characteristics, and the operating voltage may decrease due to the residual unreacted raw material. If the calcination temperature is more than 1,100 ° C., There is a fear of lowering the discharge capacity per unit time, lowering the cycle characteristics, and lowering the operating voltage.
  • the calcination may be performed in an oxidizing atmosphere such as air or oxygen or a reducing atmosphere containing nitrogen or hydrogen for 5 to 30 hours.
  • a surface layer containing an inorganic oxide may be further formed on the surface of the lithium co-based oxide thus produced.
  • the surface layer may include at least one of Mg, Ti, Fe, Cu, Ca, Ba, Sn, Sb, Na, Z, Si, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, And at least one kind of oxide selected from the group consisting of Gd, Dy, Yb, Er, Co, Al, Ga and B is mixed with the coating material containing the element forming the surface layer, Can be formed.
  • the cathode active material of lithium cobalt oxide prepared as described above over-doped the doping element to solve the grain growth inhibition problem caused by the doping element while having the structural stability under high voltage, so that the average particle diameter (D 50 ) of the primary particles was 15 ⁇ Or more. Therefore, the cathode active material can be used for a high-voltage secondary battery of 4.5V or higher, and can realize a high capacity and significantly improve lifetime characteristics.
  • a positive electrode and a lithium secondary battery for a lithium secondary battery including the positive electrode active material.
  • the positive electrode includes a positive electrode collector and a positive electrode active material layer formed on the positive electrode collector and including the positive electrode active material.
  • the cathode current collector is not particularly limited as long as it has conductivity without causing a chemical change in the battery, and for example, a metal such as stainless steel, aluminum, nickel, titanium, sintered carbon, , Nickel, titanium, silver, or the like may be used.
  • the cathode current collector may have a thickness of 3 to 500 ⁇ , and fine unevenness may be formed on the surface of the cathode current collector to increase the adhesive force of the cathode active material.
  • it can be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the cathode active material layer may include a conductive material and a binder together with the cathode active material described above.
  • the conductive material is used for imparting conductivity to the electrode.
  • the conductive material can be used without particular limitation as long as it has electron conductivity without causing chemical change. Specific examples thereof include graphite such as natural graphite and artificial graphite; Carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, summer black and carbon fiber; Metal powder or metal fibers such as copper, nickel, aluminum and silver; Conductive whiskey such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; And polyphenylene derivatives. These may be used alone or in admixture of two or more.
  • the conductive material may be typically contained in an amount of 1 to 30% by weight based on the total weight of the cathode active material layer.
  • the binder serves to improve adhesion between the positive electrode active material particles and adhesion between the positive electrode active material and the positive electrode collector.
  • specific examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethylcellulose ), Starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene butadiene rubber (SBR), fluororubber, and various copolymers thereof.
  • the binder may be included in an amount of 1 to 30% by weight based on the total weight of the cathode active material layer.
  • the positive electrode may be manufactured according to a conventional positive electrode manufacturing method, except that the positive electrode active material described above is used. Specifically, the composition for forming a cathode active material layer containing the above-mentioned cathode active material and optionally a binder and a conductive material may be coated on the cathode current collector, followed by drying and rolling. At this time, the types and contents of the cathode active material, the binder, and the conductive material are as described above.
  • the solvent examples include dimethyl sulfoxide (DMSO), isopropyl alcohol, N-methylpyrrolidone (NMP), acetone, and the like. Water and the like, and one kind or a mixture of two or more kinds can be used.
  • the amount of the solvent to be used is sufficient to dissolve or disperse the cathode active material, the conductive material and the binder in consideration of the coating thickness of the slurry and the yield of the slurry, and then to have a viscosity capable of exhibiting excellent thickness uniformity Do.
  • the positive electrode may be produced by casting the composition for forming the positive electrode active material layer on a separate support, then peeling off the support from the support, and laminating the obtained film on the positive electrode current collector.
  • an electrochemical device including the anode.
  • the electrochemical device may be specifically a battery or a capacitor, and more specifically, may be a lithium secondary battery.
  • the lithium secondary battery includes a positive electrode, a negative electrode disposed opposite to the positive electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte, as described above.
  • the lithium secondary battery may further include a battery container for storing the positive electrode, the negative electrode and the electrode assembly of the separator, and a sealing member for sealing the battery container.
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer disposed on the negative electrode current collector.
  • the negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery.
  • the negative electrode current collector may be formed on the surface of copper, stainless steel, aluminum, nickel, titanium, sintered carbon, Carbon, nickel, titanium, silver or the like, aluminum-cadmium alloy, or the like may be used.
  • the negative electrode collector may have a thickness of 3 to 500 ⁇ , and similarly to the positive electrode collector, fine unevenness may be formed on the surface of the collector to enhance the binding force of the negative electrode active material.
  • it can be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the anode active material layer optionally includes a binder and a conductive material together with the anode active material.
  • the negative electrode active material layer may be formed by applying and drying a composition for forming a negative electrode including a negative electrode active material on the negative electrode collector and, optionally, a binder and a conductive material, or by casting the composition for forming a negative electrode on a separate support , And a film obtained by peeling from the support may be laminated on the negative electrode collector.
  • a compound capable of reversible intercalation and deintercalation of lithium may be used.
  • Specific examples thereof include carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fiber and amorphous carbon;
  • Metal compounds capable of alloying with lithium such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloys, Sn alloys or Al alloys;
  • Metal oxides capable of doping and dedoping lithium such as SiO x (0 ⁇ x ⁇ 2), SnO 2 , vanadium oxide, and lithium vanadium oxide;
  • a composite containing the metallic compound and the carbonaceous material such as Si-C composite or Sn-C composite, and any one or a mixture of two or more thereof may be used.
  • a metal lithium thin film may be used as the negative electrode active material.
  • the carbon material may be both low-crystalline carbon and high-crystallinity carbon.
  • Examples of the low-crystalline carbon include soft carbon and hard carbon.
  • Examples of the highly crystalline carbon include natural graphite, artificial graphite, artificial graphite or artificial graphite, Kish graphite graphite, pyrolytic carbon, mesophase pitch based carbon fiber, meso-carbon microbeads, mesophase pitches and petroleum or coal tar coke derived cokes).
  • binder and the conductive material may be the same as those described above for the anode.
  • the separator separates the negative electrode and the positive electrode and provides a moving path of lithium ions.
  • the separator can be used without any particular limitation as long as it is used as a separator in a lithium secondary battery. Particularly, It is preferable to have a low resistance and an excellent ability to impregnate the electrolyte.
  • porous polymer films such as porous polymer films made of polyolefin-based polymers such as ethylene homopolymers, propylene homopolymers, ethylene / butene copolymers, ethylene / hexene copolymers and ethylene / methacrylate copolymers, May be used.
  • a nonwoven fabric made of a conventional porous nonwoven fabric for example, glass fiber of high melting point, polyethylene terephthalate fiber, or the like may be used.
  • a coated separator containing a ceramic component or a polymer material may be used, and may be optionally used as a single layer or a multilayer structure.
  • Examples of the electrolyte used in the present invention include an organic-based liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel-type polymer electrolyte, a solid inorganic electrolyte, and a molten inorganic electrolyte that can be used in the production of a lithium secondary battery. It is not.
  • the electrolyte may include an organic solvent and a lithium salt.
  • the organic solvent may be used without limitation as long as it can act as a medium through which ions involved in the electrochemical reaction of the battery can move.
  • examples of the organic solvent include ester solvents such as methyl acetate, ethyl acetate,? -Butyrolactone and?
  • Ether solvents such as dibutyl ether or tetrahydrofuran; Ketone solvents such as cyclohexanone; Aromatic hydrocarbon solvents such as benzene and fluorobenzene; Dimethyl carbonate (DMC), diethylcarbonate (DEC), methylethylcarbonate (MEC), ethylmethylcarbonate (EMC), ethylene carbonate (EC), propylene carbonate PC) and the like; Alcohol solvents such as ethyl alcohol and isopropyl alcohol; R-CN (R is a straight, branched or cyclic hydrocarbon group of C2 to C20, which may contain a double bond aromatic ring or an ether bond); Amides such as dimethylformamide; Dioxolanes such as 1,3-dioxolane; Or sulfolane may be used.
  • Ether solvents such as dibutyl ether or tetrahydrofuran
  • Ketone solvents such as cyclohexanone
  • a carbonate-based solvent is preferable, and a cyclic carbonate (for example, ethylene carbonate or propylene carbonate) having a high ionic conductivity and a high dielectric constant, for example, such as ethylene carbonate or propylene carbonate, For example, ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate) is more preferable.
  • a cyclic carbonate for example, ethylene carbonate or propylene carbonate
  • ethylene carbonate or propylene carbonate for example, ethylene carbonate or propylene carbonate
  • ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate
  • the lithium salt can be used without particular limitation as long as it is a compound capable of providing lithium ions used in a lithium secondary battery.
  • the lithium salt LiPF 6, LiClO 4, LiAsF 6, LiBF 4, LiSbF 6, LiAl0 4, LiAlCl 4, LiCF 3 SO 3, LiC 4 F 9 SO 3, LiN (C 2 F 5 SO 3) 2 , LiN (C 2 F 5 SO 2) 2, LiN (CF 3 SO 2) 2.
  • LiCl, LiI, or LiB (C 2 O 4 ) 2 may be used.
  • the concentration of the lithium salt is preferably in the range of 0.1 to 2.0 M. When the concentration of the lithium salt is within the above range, the electrolyte has an appropriate conductivity and viscosity, so that it can exhibit excellent electrolyte performance and the lithium ion can effectively move.
  • the electrolyte may contain, for example, a haloalkylene carbonate-based compound such as difluoroethylene carbonate or the like, pyridine, triethanolamine, or the like for the purpose of improving lifetime characteristics of the battery, Ethyl phosphite, triethanol amine, cyclic ether, ethylenediamine, glyme, hexametriamide, nitrobenzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, At least one additive such as benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, The additive may be included in an amount of 0.1 to 5% by weight based on the total weight of the electrolyte.
  • the lithium secondary battery including the cathode active material according to the present invention stably exhibits excellent discharge capacity, output characteristics, and capacity retention rate, it can be used in portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles hybrid electric vehicle (HEV)).
  • portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles hybrid electric vehicle (HEV)).
  • HEV hybrid electric vehicles hybrid electric vehicle
  • a battery module including the lithium secondary battery as a unit cell and a battery pack including the same.
  • the battery module or the battery pack may include a power tool; An electric vehicle including an electric vehicle (EV), a hybrid electric vehicle, and a plug-in hybrid electric vehicle (PHEV); Or a power storage system, as shown in FIG.
  • a power tool including an electric vehicle (EV), a hybrid electric vehicle, and a plug-in hybrid electric vehicle (PHEV); Or a power storage system, as shown in FIG.
  • EV electric vehicle
  • PHEV plug-in hybrid electric vehicle
  • the cathode active material precursor (5,000 ppm Al-doped Co 3 O 4 ) prepared as in Example 1 and Li 2 CO 3 as a lithium source were mixed at a molar ratio of Li / Co of 1.035 and calcined at 1,000 ° C. for 17 hours to obtain 4,500 ppm Al-doped lithium cobalt oxide was prepared.
  • the cathode active material precursor (3,000 ppm Al-doped Co 3 O 4 ) prepared as in Example 2 and Li 2 CO 3 as a lithium source were mixed at a molar ratio of Li / Co of 1.035 and calcined at 1,000 ° C. for 17 hours to give 2,500 ppm Al-doped lithium cobalt oxide was prepared.
  • the cathode active material precursor (3,000 ppm Al-doped Co 3 O 4 ) prepared as in Comparative Example 1 and Li 2 CO 3 as a lithium source were mixed at a Li / Co 1.045 molar ratio and calcined at 1,020 ° C. for 20 hours to obtain 2,500 ppm Al-doped lithium cobalt oxide was prepared.
  • the thus prepared cathode active material was doped with a concentration gradient gradually decreasing from the surface to the inside of Al.
  • the thus prepared cathode active material was grown up to 12 ⁇ in primary particle size, but no abnormal growth was caused due to interference of grain growth of Al.
  • FIG. 1 (Example 1) and FIG. 2 (Comparative Example 1) show photographs of the cathode active material precursor powder prepared in Example 1 and Comparative Example 1 magnified with a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the cathode active material precursor of Co 3 O 4 prepared in Example 1 and Comparative Example 1 is composed of primary particles, and Example 1 (FIG. 1) , And Comparative Example 1 (Fig. 2) formed small particles with a primary particle size of about 7 mu m.
  • the average particle diameters of the primary particles of the cathode active material precursor and the cathode active material prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were measured by Particle Size Distribution (PSD), and the results are shown in Table 1 below .
  • Example 1 Example 2 Example 3
  • Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 4
  • the average particle diameter (D 50 ) of the primary particles of the precursor was 15 ⁇ m or more in Example 1 and Example 2, and the precursors of Example 1 and Example 2 were used,
  • Al was doped with a high content of not less than 2,500 ppm without increasing the firing temperature and the amount of lithium input, and the cathode active material having a primary particle average particle diameter (D 50 ) .
  • Comparative Example 1 it was confirmed that the average particle diameter (D 50 ) of the primary particles of the precursor was 7 ⁇ m, and in Comparative Example 2 in which the cathode active material was prepared using the precursor of Comparative Example 1, The average particle diameter (D 50 ) of the primary particles was only 12 ⁇ , and the cathode active material could not be prepared.
  • Comparative Example 4 produced using the secondary particle type precursor in which the primary particles aggregated, the primary particles were grown up to 12 ⁇ , but no abnormal growth was caused due to the grain growth inhibiting action of Al .
  • lithium metal was used for the cathode.
  • a lithium secondary battery was prepared by preparing an electrode assembly between a positive electrode and a negative electrode manufactured as described above through a separator of porous polyethylene, positioning the electrode assembly inside a case, and then injecting an electrolyte into the case.
  • Each lithium secondary battery cell thus prepared was charged at 0.5 C and 4.55 V in a CCCV mode at 25 ⁇ and 45 ⁇ , cut off at a temperature of 0.05 C, (Capacity Retention [%]) was measured while discharging at a constant current of 3.0 V and performing charge / discharge 50 times. The results are shown in Table 2.
  • Example 3 Example 4 Comparative Example 2 Comparative Example 3 Comparative Example 4 Capacity (mAh / g) 207 209 209 209 208 Rate characteristic (%) 92.8 92.5 91.7 91.8 91.5 25 C 50 Cycle Capacity Retention (%) 96 95 92 93 92 45 C 50 Cycle Capacity Retention (%) 95 95 91 91 90

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  • Organic Chemistry (AREA)
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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

La présente invention concerne : un précurseur de matériau actif de cathode pour une batterie secondaire, comprenant une particule primaire de Co3O4 ou CoOOH, la particule primaire contenant 3 000 ppm ou plus d'un élément dopant, et le diamètre moyen de particule (D50) de la particule primaire est de 15 µm ou plus ; et un matériau actif de cathode pour une batterie secondaire, comprenant une particule primaire d'un oxyde à base de lithium cobalt, la particule primaire contenant 2 500 ppm ou plus d'un élément dopant, et le diamètre moyen de particule (D50) de la particule primaire étant de 15 µm ou plus.
PCT/KR2018/011081 2017-09-19 2018-09-19 Précurseur de matériau actif de cathode pour batterie secondaire, matériau actif de cathode, et batterie secondaire au lithium le comprenant WO2019059654A1 (fr)

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US16/480,832 US11611076B2 (en) 2017-09-19 2018-09-19 Positive electrode active material precursor for secondary battery, positive electrode active material, and lithium secondary battery including the same
EP18857652.4A EP3560894A4 (fr) 2017-09-19 2018-09-19 Précurseur de matériau actif de cathode pour batterie secondaire, matériau actif de cathode, et batterie secondaire au lithium le comprenant
JP2020516365A JP7047203B2 (ja) 2017-09-19 2018-09-19 二次電池用正極活物質前駆体、正極活物質およびこれを含むリチウム二次電池
CN201880008449.9A CN110225886A (zh) 2017-09-19 2018-09-19 二次电池用正极活性材料前体、正极活性材料和包含其的锂二次电池

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WO2020232556A1 (fr) * 2019-05-22 2020-11-26 Nemaska Lithium Inc. Procédés de préparation d'hydroxydes et d'oxydes de divers métaux et de leurs dérivés
US11078583B2 (en) 2013-03-15 2021-08-03 Nemaska Lithium Inc. Processes for preparing lithium hydroxide
US11085121B2 (en) 2014-02-24 2021-08-10 Nemaska Lithium Inc. Methods for treating lithium-containing materials
US11083978B2 (en) 2016-08-26 2021-08-10 Nemaska Lithium Inc. Processes for treating aqueous compositions comprising lithium sulfate and sulfuric acid
US11142466B2 (en) 2017-11-22 2021-10-12 Nemaska Lithium Inc. Processes for preparing hydroxides and oxides of various metals and derivatives thereof
US11254582B2 (en) 2012-05-30 2022-02-22 Nemaska Lithium Inc. Processes for preparing lithium carbonate
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US11697861B2 (en) 2013-10-23 2023-07-11 Nemaska Lithium Inc. Processes for preparing lithium carbonate

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Cited By (12)

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US11254582B2 (en) 2012-05-30 2022-02-22 Nemaska Lithium Inc. Processes for preparing lithium carbonate
US11634336B2 (en) 2012-05-30 2023-04-25 Nemaska Lithium Inc. Processes for preparing lithium carbonate
US11078583B2 (en) 2013-03-15 2021-08-03 Nemaska Lithium Inc. Processes for preparing lithium hydroxide
US11697861B2 (en) 2013-10-23 2023-07-11 Nemaska Lithium Inc. Processes for preparing lithium carbonate
US11085121B2 (en) 2014-02-24 2021-08-10 Nemaska Lithium Inc. Methods for treating lithium-containing materials
US11519081B2 (en) 2014-02-24 2022-12-06 Nemaska Lithium Inc. Methods for treating lithium-containing materials
US11083978B2 (en) 2016-08-26 2021-08-10 Nemaska Lithium Inc. Processes for treating aqueous compositions comprising lithium sulfate and sulfuric acid
US11142466B2 (en) 2017-11-22 2021-10-12 Nemaska Lithium Inc. Processes for preparing hydroxides and oxides of various metals and derivatives thereof
US11542175B2 (en) 2017-11-22 2023-01-03 Nemaska Lithium Inc. Processes for preparing hydroxides and oxides of various metals and derivatives thereof
WO2020232556A1 (fr) * 2019-05-22 2020-11-26 Nemaska Lithium Inc. Procédés de préparation d'hydroxydes et d'oxydes de divers métaux et de leurs dérivés
CN114497534A (zh) * 2022-01-27 2022-05-13 蜂巢能源科技(马鞍山)有限公司 一种无钴正极材料、其制备方法和用途
CN114497534B (zh) * 2022-01-27 2023-10-31 蜂巢能源科技(马鞍山)有限公司 一种无钴正极材料、其制备方法和用途

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