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WO2019132267A1 - Précurseur de matériau actif d'électrode positive pour batterie secondaire au lithium, matériau actif d'électrode positive l'utilisant et batterie secondaire au lithium le comprenant - Google Patents

Précurseur de matériau actif d'électrode positive pour batterie secondaire au lithium, matériau actif d'électrode positive l'utilisant et batterie secondaire au lithium le comprenant Download PDF

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Publication number
WO2019132267A1
WO2019132267A1 PCT/KR2018/014883 KR2018014883W WO2019132267A1 WO 2019132267 A1 WO2019132267 A1 WO 2019132267A1 KR 2018014883 W KR2018014883 W KR 2018014883W WO 2019132267 A1 WO2019132267 A1 WO 2019132267A1
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Prior art keywords
active material
secondary battery
cathode active
positive electrode
precursor
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English (en)
Korean (ko)
Inventor
김재한
김득수
손승용
김정한
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Posco Future M Co Ltd
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Posco ES Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • 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
    • 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 positive electrode active material precursor for a lithium secondary battery, a positive electrode active material using the same, and a lithium secondary battery comprising the same.
  • the lithium secondary battery has high energy density, excellent output characteristics, and light weight, and is widely used as an energy storage device for mobile phones and hybrid electric vehicles.
  • the lithium secondary battery is composed of a cathode, a cathode, and an electrolyte, and uses a material capable of intercalating / deintercalating lithium ions in the anode as a cathode active material.
  • cathode active material examples include lithium nickel oxide (LiNiO 2 ), lithium cobalt oxide (LiCoO 2 ), lithium manganese oxide (LiMnO 2 ), and the like.
  • Lithium nickel oxide (LiNiO 2 ) has high electric capacity, but has problems such as charge / discharge characteristics, stability, and the like.
  • Lithium cobalt oxide (LiCoO 2 ) has an advantage of being excellent in cycle life and rate capability as well as capacity, and being easy to synthesize. However, it has a high cost of Co, a human hazard, a thermal instability at high temperature It has disadvantages.
  • Mn-based cathode active materials such as LiMn 2 O 4 and LiMnO 2 are easy to synthesize and have a relatively low cost and are superior in thermal stability to other active materials and have a low environmental pollution when overcharged, It has disadvantages.
  • the NCM is a material that has advantages of each of LiCoO 2 , LiNiO 2 and LiMnO 2 as a single component and has been actively studied since it has many advantages in terms of safety, life and cost.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2007-0083384 discloses a lithium metal composite oxide having a composition of LiNi 1-xy Co x Mn y O 2 , wherein the content of Ni is 75 mol% or more, and the molar content of Mn is not less than the molar amount of Co is used as the cathode active material, the average discharge voltage, the high rate characteristic, and the discharge capacity of the battery are improved. Particularly, when compared to the conventional commercial LiCoO 2 The density is improved.
  • the cathode active material using NCM metal oxide is one of high energy candidate materials because the reversible capacity increases according to the Ni content.
  • shortening the lifetime due to increase in structural instability during repetitive charging / discharging is a problem. Doping techniques for replacing some of the transition metal components with other elements have been attempted.
  • the present invention aims to provide a positive electrode active material precursor having a novel structure having excellent capacity characteristics, rate characteristics and life characteristics, a positive electrode active material using the same, and a lithium secondary battery comprising the same.
  • the precursor of the cathode active material for a secondary battery includes Ni, Mn, Co, M1 and M2, and M1 is at least one element selected from the group consisting of Mg, Al, Si, Ca, Ti, V, Mn, Co, Wherein at least one of Fe, Zn, Ga, Zr, Nb, Mo, Ru, Rh and W is at least one selected from the group consisting of Mg, Al, Si, Ca, Ti, V, Mn, Co, Ni, Cr, Ga, Zr, Nb, Mo, Ru, Rh and W, and M1 and M2 are different from each other.
  • the cathode active material precursor for a secondary battery may include a core and a shell disposed to surround the center portion.
  • the center portion may include M1 as a doping element
  • the surface portion may include M2 as a doping element.
  • the precursor and the cathode active material may contain one or more dissimilar metals, if necessary, (Central portion) or an outer frame portion (surface portion), or by arranging dissimilar metals different from each other in the central portion and the outer frame portion, thereby enhancing performance.
  • the center portion may include a material represented by the following Formula 1, and the surface portion may include a material represented by Formula 2 below.
  • the cathode active material precursor for a secondary battery according to an embodiment of the present invention may be represented by the following chemical formula 3.
  • the cathode active material according to an embodiment of the present invention is divided into a center portion and a surface portion arranged to surround the center portion, the center portion includes M1, and the surface portion may include M2.
  • the positive electrode active material for a secondary battery includes Ni, Mn, Co, M 1 and M 2 and M 1 is at least one element selected from the group consisting of Mg, Al, Si, Ca, Ti, V, Mn, Co, Ni, Wherein at least one of Zn, Ga, Zr, Nb, Mo, Ru, Rh and W is at least one selected from the group consisting of Mg, Al, Si, Ca, Ti, V, Mn, Co, Ni, Cr, Fe, Zr, Nb, Mo, Ru, Rh and W, and M1 and M2 may be different from each other.
  • the cathode active material according to an embodiment of the present invention can be represented by the following chemical formula (4).
  • M1 and M2 are combinations of at least one of Mg, Al, Si, Ca, Ti, V, Mn, Co, Ni, Cr, Fe, Zn, Ga, Zr, Nb, Mo, Ru, Rh,
  • the cathode active material according to an embodiment of the present invention is composed of a plurality of primary particles, and the ratio of the major axis to the minor axis of the primary particles (long axis: short axis) . ≪ / RTI >
  • the ratio (major axis: minor axis) of the major axis to minor axis of the primary particles constituting the central portion is a ratio of the major axis to the minor axis of the primary particles constituting the surface portion Long axis: short axis).
  • the cathode active material according to the embodiment of the present invention includes primary particles in the form of a rod having a major axis to minor axis ratio (major axis: minor axis) of primary particles constituting the surface portion exceeding 1, And may be arranged in a direction toward the center.
  • the rod-shaped primary particles can be arranged in a direction in which the long axis is oriented toward the center of the positive electrode active material.
  • the ratio of the intensity of the 003 peak to the intensity of the 104 peak may be larger than that of the undoped cathode active material.
  • the ratio of the intensity at the peak of 003 to the intensity at the peak of 104 may be 1.75 or more and 1.80 or less.
  • the secondary battery according to an embodiment of the present invention includes a cathode including the cathode active material for the secondary battery, a cathode including the anode active material, a separator interposed between the anode and the cathode, And an electrolyte supported between the anode and the cathode.
  • the precursor according to the embodiment of the present invention is characterized in that one or more dissimilar metals are intensively arranged in the central part or the surface part as required or the dissimilar metals different from each other are arranged in the center or outer part,
  • the electrochemical performance of the cathode active material and the secondary battery including the cathode active material can be enhanced.
  • FIG. 1 schematically illustrates the step of synthesizing a partially doped Li a Ni b Co c Mn d M1 e M2 f O 2 cathode active material by sequentially subjecting M1 and M2 to a partial doping in a precursor step.
  • FIG. 2 is a structural view of a partially doped cathode active material made from a precursor partially doped with a central portion M1 and a surface portion M2.
  • FIG. 3 is a graph showing the growth of a precursor including the precursor diameter D1 during the time of application of M1 and the precursor partial diameter D2 according to the time of application of M2 during synthesis of the precursor of FIG. 2;
  • FIG. 4 (a) is a partially doped precursor section
  • FIG. 4 (b) is a SEM image of a cross-section of a cathode active material.
  • Figure 5 shows the results of SEM images of undoped precursor and partially doped precursors according to Examples 1-3.
  • FIG. 6 is a SEM image of a partially doped precursor section according to Examples 1 to 3.
  • FIG. 6 is a SEM image of a partially doped precursor section according to Examples 1 to 3.
  • FIG. 7 shows SEM images of a non-doped cathode active material and a partially doped cathode active material according to Examples 1 to 3.
  • FIG. 7 shows SEM images of a non-doped cathode active material and a partially doped cathode active material according to Examples 1 to 3.
  • FIG. 9 (a) is a schematic view of a cross-section of a cathode active material doped with W
  • FIG. 9 (b) is a result of SEM image measurement.
  • FIG. 10 (a) is a cross-sectional view of a cathode active material according to Example 1, and FIG. 10 (b) is a result of SEM image measurement.
  • Fig. 11 (a) is a cross-sectional view of a cathode active material according to Example 2
  • Fig. 12 (b) is a SEM image.
  • FIG. 12 (a) is a cross-sectional view of a cathode active material according to Example 3, and FIG. 12 (b) is a result of SEM image measurement.
  • FIG. 13 is a graph showing the results of analysis of DSC peak temperature and calorific value of a non-doped cathode active material, a cathode active material wholly doped with W, and a cathode active material according to Examples 1 to 4.
  • Fig. 14 (a) is a graph showing the relationship between the total amount of NCM metal oxide and the voltage of the positive electrode active material containing 90% Ni according to the capacity of the undoped positive electrode active material, the fully doped positive active material of W and the positive active material of Examples 1 to 3 (B) is a graph showing a change in capacity retention rate according to the number of charge / discharge cycles.
  • FIG. 16 is a graph showing the XRD measurement results of the undoped positive electrode active material and the positive electrode active material according to Examples 1 to 3.
  • FIG. 16 is a graph showing the XRD measurement results of the undoped positive electrode active material and the positive electrode active material according to Examples 1 to 3.
  • FIGS. 1 and 2 are schematic views of a precursor and a cathode active material according to the present invention.
  • the precursor and the cathode active material according to the embodiment of the present invention may be prepared by concentrating one or more different kinds of metals to the center (center part) or the outer part (surface part) of the precursor in the precursor step, Place different dissimilar metals to improve performance.
  • the positive electrode active material precursor for a high nickel-based secondary battery according to an embodiment of the present invention may include a metal hydroxide containing Ni and Co and Mn in an amount of 50 mol% or more, preferably 90 mol% or more.
  • the precursor of the cathode active material includes M1 and M2 as doping elements and M1 is at least one element selected from the group consisting of Mg, Al, Si, Ca, Ti, V, Mn, Co, Ni, Cr, Fe, Zn, Ga, Zr, Wherein at least one of Ru, Rh, and W is at least one selected from the group consisting of Mg, Al, Si, Ca, Ti, V, Mn, Co, Ni, Cr, Fe, Zn, Ga, Zr, W, and M1 and M2 are different from each other.
  • the cathode active material precursor may include a center portion and a surface portion arranged to surround the center portion, and the center portion may include a doping element M1, and the surface portion may include a doping element M2, and M1 ⁇ M2.
  • the cathode active material precursor according to the present invention generally includes a center portion represented by Formula 1 and a surface portion represented by Formula 2, and may be represented by Formula 3 below.
  • M1 or M2 is preferably W.
  • M1 or M2 when M1 or M2 is W, the diffusion of Li ions in the inside of the positive electrode active material is facilitated, and as a result, Can be improved.
  • the W raw material examples include oxides such as tungsten trioxide (WO 3 ), halides (such as tungsten hexafluoride (WF 6 )), and ammonium salts (ammonium paratungstate [(NH 4 ) 10 H 2 (W 2 O 7 ) 6 ] or ammonium metatungstate [(NH 4 ) 6 H 2 W 12 O 40 ]], and the like.
  • oxides such as tungsten trioxide (WO 3 ), halides (such as tungsten hexafluoride (WF 6 )), and ammonium salts (ammonium paratungstate [(NH 4 ) 10 H 2 (W 2 O 7 ) 6 ] or ammonium metatungstate [(NH 4 ) 6 H 2 W 12 O 40 ]]
  • WO 3 tungsten trioxide
  • halides such as tungsten hexafluoride (WF 6 )
  • ammonium salts ammonium paratungstate [(NH 4 ) 10 H 2
  • the cathode active material for a secondary battery according to an embodiment of the present invention includes Li, Ni, Mn, Co, M1 and M2.
  • the method for producing a cathode active material may include synthesizing an NCM metal oxide precursor, mixing the metal oxide precursor and a Li source, and then subjecting the mixture to a primary heat treatment to produce a cathode active material.
  • the NCM metal oxide precursor for the synthesis of the NCM metal oxide precursor, one species selected from the group consisting of nickel sulfate, nickel nitrate and nickel carbonate; Cobalt sulfate, cobalt nitrate and cobalt carbonate;
  • the SO 4 2- , NH 4 + , NO 3 - , Na + , K + adsorbed on the surface of the precipitated powder is washed several times with distilled water to synthesize a high purity metal oxide precursor.
  • the thus synthesized metal oxide precursor And then dried in an oven at 100 to 200 ° C, preferably 150 ° C for at least 24 hours so that the moisture content is 0.1 wt% or less.
  • the cathode active material may be obtained by homogeneously mixing the dried metal oxide precursor and the Li source and then performing heat treatment for 5 to 30 hours.
  • lithium hydroxide may be lithium hydroxide (LiOH) or the like,
  • lithium salt examples include LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , LiSbF 6 , LiAlO 4 , LiAlCl 4 , LiCl, and LiI can be used.
  • the heat treatment temperature is preferably 600 to 1000 ° C. If the heat treatment temperature is lower than 600 ° C., there is a fear that the reaction between the Li source and the transition metal hydroxide precursor or the NCM and the transition metal source may not be performed well, The particle size of the active material may be excessively increased and the battery characteristics may be deteriorated.
  • the positive electrode active material includes M1 and M2 doped therein and M1 is at least one element selected from the group consisting of Mg, Al, Si, Ca, Ti, V, Mn, Co, Ni, Cr, Fe, Zn, Ga, Zr, At least one of Ru, Rh, and W, and M2 is at least one of Mg, Al, Si, Ca, Ti, V, Mn, Co, Ni, Cr, Fe, Zn, Ga, Zr, And W, and M1 and M2 are different from each other.
  • M1 or M2 is W is as described above.
  • the cathode active material may be represented by the following general formula (4).
  • M1 and M2 are combinations of at least one of Mg, Al, Si, Ca, Ti, V, Mn, Co, Ni, Cr, Fe, Zn, Ga, Zr, Nb, Mo, Ru, Rh,
  • the cathode active material for the secondary battery is composed of a plurality of primary particles, and the ratio of the major axis to the minor axis of the primary particles (long axis: short axis) is larger than that of the primary particles of the undoped cathode active material or the entirely doped cathode active material (Fig. 8).
  • the ratio (major axis: minor axis) of the major axis to minor axis of the primary particles constituting the central portion is a ratio of the major axis to the minor axis of the primary particles constituting the surface portion Long axis: short axis).
  • the cathode active material for a secondary battery may include primary particles of a rod shape having a major axis to minor axis ratio (major axis: minor axis) of primary particles constituting the surface portion of more than 1, As shown in FIG.
  • the rod-shaped primary particles may have a ratio of major axis to minor axis greater than 1, greater than 1.5, greater than 2, greater than 2.5, greater than 3, greater than 3.5, or greater than 4.
  • the ratio of the intensity at the peak of 003 to the intensity at the peak of 104 may be larger than that in the case of the undoped cathode active material. ).
  • the ratio of the intensity at the peak of 003 to the intensity at the peak of 104 may be 1.75 or more and 1.80 or less (Fig. 16).
  • the center portion and the surface portion of the cathode active material may include different types of primary particles.
  • the center portion includes primary particles in a bulk form
  • the surface portion includes a plurality of primary particles in the form of a rod
  • the rod form can be arranged in a direction toward the center of the center portion. More specifically, the primary particles of the rod-like form can be arranged in a direction in which the long axis is oriented toward the center of the cathode active material (FIG. 10)
  • a secondary battery includes: a positive electrode including the positive electrode active material; A negative electrode comprising a negative electrode active material; A separation membrane interposed between the anode and the cathode; And an electrolyte supported between the anode and the cathode.
  • the anode can be prepared by coating directly on an aluminum current collector and drying. Or by casting the positive electrode active material composition on a separate support, then peeling the support from the support, and laminating the resulting film on an aluminum current collector.
  • the anode may further include a conductive material and a binder.
  • the conductive material is used for imparting conductivity to the electrode, and can be used without particular limitation as long as it does not cause chemical change and has electronic conductivity.
  • Specific examples include 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 binder serves to improve the adhesion between the positive electrode active material particles or between the positive electrode active material and the current collector.
  • Specific examples include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, There may be mentioned polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene-butadiene rubber, fluorine rubber or various copolymers thereof. Can be used.
  • the negative electrode can be manufactured by coating the negative electrode active material directly on the copper current collector as in the case of the positive electrode, or by casting on a separate support and laminating the negative electrode active material film peeled off from the support on the copper current collector.
  • the negative electrode active material a material capable of intercalating / deintercalating lithium may be used.
  • a material capable of intercalating / deintercalating lithium may be used.
  • lithium metal, a lithium alloy, coke, artificial graphite, natural graphite, an organic polymer combustible material have.
  • a conductive material and a binder used for the positive electrode may be used for the negative electrode.
  • polyethylene, polypropylene, polyvinylidene fluoride or a multilayer film of two or more thereof may be used.
  • the separator may be a polyethylene / polypropylene double-layer separator , A polyethylene / polypropylene / polyethylene three-layer separator, a polypropylene / polyethylene / polypropylene three-layer separator, etc. may be used.
  • a non-aqueous electrolyte or a known solid electrolyte can be used, and a lithium salt dissolved therein is used.
  • the solvent of the non-aqueous electrolyte is not particularly limited, but cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and vinylene carbonate; Chain carbonates such as dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate; Esters such as methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate and?
  • Example 1 Cathode active material precursor in which W is a central portion and Mn is partially doped on a surface portion
  • composition of the precursor was determined by measuring NiSO 4 * 6H 2 O, CoSO 4 * 7H 2 O, and MnSO 4 * H 2 O according to the composition ratios of Ni, Co and Mn shown in Table 1 below and dissolving in distilled water.
  • the dissolved metal hydroxide solution was divided into 50% portions and stored in the respective reservoirs so that the ratios of Formulas 1 and 2 were 1: 1.
  • Each metal aqueous solution was introduced into the reactor using a hose type metering pump. At this time, the metal aqueous solution of the formula (1) was put into the reactor for a certain period of time, and the aqueous metal solution of the formula (2) was introduced into the metal aqueous solution storage tank of the formula (1). The aqueous solution composition of the central metal aqueous solution reservoir containing the M1 raw material was changed to the aqueous metal solution composition of the formula (2) containing the M2 raw material.
  • the ratio of the input flow rate of the chemical formula (2) to the input flow rate of the metal solution of the chemical formula (1) introduced into the reactor is set to 1.0 or more, the reaction is carried out from the metal aqueous solution of the chemical formula (1) A precursor with different M1 and M2 distribution was synthesized. At this time, the reactor reacted with ammonia and caustic soda to precipitate.
  • the precipitated slurry was subjected to washing with water and solid-liquid separation using a filter press, and residual water was removed using a high-pressure fresh air.
  • the solid-liquid separated precursor was dried at 100 to 200 ° C using a fluid bed drier.
  • the dried precursor was mixed with LiOH as a raw material of Li so as to have a Li: metal ratio (based on molar number) of 1.03, and then calcined at a temperature of 700 ° C to 800 ° C under an oxygen (O 2 ) atmosphere at a temperature raising rate of 1.5 ° C / min.
  • the sintered material was pulverized and classified to obtain a cathode active material.
  • the cathode active material of Example 1 is shown in Table 1 below.
  • Example 1 Example 2
  • Example 3 Example 4 Bulk W doping W Core W Shell Zr CoreW Shell W CoreAl Shell Casting Li 1.03 Ni 0.90 Co 0.07 Mn d M1 e1 M2 f1 O 2 M1 Mn W W Mn Zr, W M2 Mn W Mn W W Al
  • Example 2 Cathode active material precursor in which Mn is the central portion and W is partially doped on the surface portion
  • Example 1 was followed except that 0.5 mol% of Mn was used as M1 in the formula (1) and 0.5 mol% of W was used as M2 in the formula (2).
  • Example 3 A positive electrode active material precursor in which (Mn + Zr) was the center portion and W was partially doped on the surface portion
  • Example 1 The procedure of Example 1 is followed except that 0.5 mol% of the combination of (Mn + Zr) as M1 in Formula (1) and 0.5 mol% of W as M2 in Formula (2) are applied.
  • Example 4 Cathode active material precursor in which W is the center part, (Mn + Al) is partially doped on the surface part
  • Example 5 A positive electrode active material precursor in which W is the center portion and (Zr + Mg) is doped on the surface portion
  • Example 1 is followed except that 0.5 mol% of W is used as M1 in the formula (1) and 0.5 mol% of the combination of (Zr + Mg) is used as M2 in the formula (2).
  • Example 6 Cathode active material precursor in which W is the central portion and Ti is doped on the surface portion
  • Example 1 The procedure of Example 1 is followed except that 0.5 mol% of W is used as M1 of Formula 1 and 0.5 mol% of Ti is used as M2 of Formula 2 and the metal aqueous solution ratio of Formulas 1 and 2 is 9: 1.
  • Example 7 Cathode active material precursor in which W is a central portion and V is partially doped on a surface portion
  • Example 1 is followed except that 0.5 mol% of W as M1 in Formula 1 and 0.5 mol% of V as M2 in Formula 2 are applied and the metal aqueous solution ratio of Formulas 1 and 2 is 9: 1.
  • Example 8 Cathode active material precursor in which Zr was the center portion and Al was partially doped on the surface portion
  • Example 1 is followed except that 0.5 mol% of Zr is used as M1 of Formula 1 and 0.5 mol% of Al is used as M2 of Formula 2 and the ratio of the metal aqueous solution of Formulas 1 and 2 is 9: 1.
  • Example 1 is followed except that Mn is applied as M1 and M2 in formulas (1) and (2).
  • Example 1 is followed except that 0.5 mol% of W is applied as M1 and M2 in the formulas (1) and (2).
  • the growth of the precursor was measured according to the treatment time while changing the dopant of the central part and the surface part, and the result is shown in FIG.
  • M1 was applied to form the initial center portion and grown to the precursor diameter (D1). It was confirmed that the size of the precursor was gradually increased by growing the precursor part diameter (D2) while applying M2.
  • the center portion is in a bulk form, and a plurality of surface rods (not shown) are formed on the surface of the cathode active material.
  • rod type primary particles and it was confirmed that the rod shape had a central orientation.
  • FIG. 5 shows SEM images of undoped precursors (Bulk, Comparative Example 1) and partially doped precursors according to Examples 1 to 3, and FIG. 6 shows SEM images of the cross- Respectively.
  • a high-nickel precursor containing 90% of Ni (based on molar amount) based on the total amount of NCM metal oxides was mixed with Li source so that the ratio of Li and NCM metal oxides exceeded 1.0 (based on molar number)
  • the surface reaction proceeded with the aqueous metal solution corresponding to the surface residual Li (PLM mixer application).
  • Comparative Example 1 (Bulk) was Li 1.03 Ni 0.90 Co 0.07 Mn 0.03 O 2 ,
  • Comparative Example 2 (W doping) was performed using Li 1.03 Ni 0.90 Co 0.07 Mn 0.025 W 0.005 O 2 ,
  • Example 1 is Li 1.03 Ni 0.90 Co 0.07 Mn 0.027 W 0.003 O 2
  • Example 2 is Li 1.03 Ni 0.90 Co 0.07 Mn 0.027 W 0.003 O 2
  • Example 3 (ZrC-WS) is represented by Li 1.03 Ni 0.90 Co 0.07 Mn 0.026 Zr 0.001 W 0.003 O 2 .
  • FIG. 9 (a) is a graph showing a cross-section of the anode active material doped with W, and FIG. 9 (b) shows a bulk SEM image.
  • the mixture was homogeneously mixed in a N-methyl-2-pyrrolidone solvent such that the mass ratio of the cathode active material, the dengan black and the binder (PVDF) was 94: 3: 3.
  • the mixture was spread evenly on an aluminum foil, compressed by a roll press, and vacuum dried in a vacuum oven at 100-200 ⁇ for 12 hours to prepare a positive electrode.
  • the cells using the cathode active materials of the examples and comparative examples were charged and discharged twice in the 2.50 to 4.25 V dislocation range, and only the positive electrodes were separated and washed in the cells charged at 4.25 V. Thereafter, it was dried in a 100 ° C drying oven for 10 minutes.
  • the cathode active material was scraped off from the dried anode, and 3 mg was added to the pressure pan. 2 ⁇ of electrolyte was injected, and the temperature was raised to 5 ⁇ / min and the temperature was monitored at 30 ⁇ to 400 ⁇ .
  • Example 2 Example 3
  • Example 4 Bulk W doping W Core W Shell Zr CoreW Shell W CoreAl Shell Casting Li 1.03 Ni 0.90 Co 0.07 Mn d M1 e1 M2 f1 O 2 M1 source, e1 Mn W W Mn Zr, W M2 source, f1 Mn W Mn W W Al DSC Onset Temp. °C 208.3 212.5 210.9 211.6 211.0 216.2 1 st Peak Temp. 220.1 220.5 221.2 221.9 220.5 224.9 Calorific value J / g 1358.1 1276.5 1097.6 1040.9 1161.9 1012.7
  • Example 1 Example 2
  • Example 3 Example 4 Bulk W doping W Core W Shell Zr CoreW Shell W CoreAl Shell Casting Li 1.03 Ni 0.90 Co 0.07 Mn d M1 e1 M2 f1 O 2 M1 source, e1 Mn W W Mn Mn + Zr W M2 source, f1 Mn W Mn W W Al Metal cont.
  • FIG. 16 shows the XRD measurement results of the non-doped cathode active material (Comparative Example 1) and the cathode active material according to Examples 1 to 3 in the case of the cathode active material containing 90% Ni relative to the total amount of NCM metal oxides.

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Abstract

La présente invention concerne un précurseur de matériau actif d'électrode positive pour batterie secondaire au lithium, un matériau actif d'électrode positive l'utilisant, et une batterie secondaire au lithium le comprenant. L'invention concerne : un précurseur de matériau actif d'électrode positive pour une batterie secondaire, le précurseur contenant Ni, Mn, Co, M1, et M2, M1 étant au moins l'un de Mg, Al, Si, Ca, Ti, V, Mn, Co, Ni, Cr, Fe, Zn, Ga, Zr, Nb, Mo, Ru, Rh, et W et M2 étant au moins un élément de Mg, Al, Si, Ca, Ti, V, Mn, Co, Ni, Cr, Fe, Zn, Ga, Zr, Nb, Mo, Ru, Rh, et W, M1 et M2 étant différents l'un de l'autre ; et un matériau actif d'électrode positive l'utilisant.
PCT/KR2018/014883 2017-12-29 2018-11-28 Précurseur de matériau actif d'électrode positive pour batterie secondaire au lithium, matériau actif d'électrode positive l'utilisant et batterie secondaire au lithium le comprenant Ceased WO2019132267A1 (fr)

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KR20170183291 2017-12-29
KR10-2017-0183291 2017-12-29
KR1020180060952A KR102006244B1 (ko) 2017-12-29 2018-05-29 리튬 이차전지용 양극활물질 전구체, 이를 이용한 양극활물질 및 이를 포함하는 리튬 이차전지
KR10-2018-0060952 2018-05-29

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Publication number Priority date Publication date Assignee Title
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