WO2016175554A1 - 리튬 이차전지용 양극활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차전지 - Google Patents
리튬 이차전지용 양극활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차전지 Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a cathode active material for a lithium secondary battery, a method for manufacturing the same, and a lithium secondary battery including the same, and more particularly, to a cathode active material for a lithium secondary battery having lithium ion conductivity, a method for manufacturing the same, and a lithium secondary battery including the same. .
- lithium secondary batteries are mainly used as a power source for mobile IT devices such as mobile phones, and as demand for electric vehicles (plug-in vehicles) and energy storage systems (ESS) increases, The need for larger capacity is increasing.
- lithium ions (Li + ) present in an ionic state move from a cathode to a cathode when discharged and from a cathode to a cathode when charged.
- a cathode active material of a lithium secondary battery As a cathode active material of a lithium secondary battery, a layered layer (LiCoO 2 , LiNi 1 -x- y Co x Mn y O 2 There are a variety of metal oxides being used, such as (0 ⁇ x ⁇ 1,0 ⁇ y ⁇ 1), spinel (LiMn 2 O 4), and post bingye (LiFePO 4).
- the surface modification technology of the positive electrode active material can effectively improve the deterioration of battery characteristics and thermal stability caused by side reactions due to the direct contact between the positive electrode active material and the electrolyte, and has been reported as an important technology for developing high capacity / high energy materials. .
- the surface modifying material used for the surface modification of the positive electrode active material is chemically stable, but since a metal oxide having low electrical or ionic conductivity is mainly used, the movement of lithium ions is limited, thereby reducing the capacity. This may cause problems.
- the first technical problem of the present invention is to provide a positive electrode active material for a secondary battery comprising lithium metal phosphate nanoparticles that can increase the structural stability of the positive electrode active material, while giving a high lithium ion conductivity.
- a second technical problem of the present invention is to provide a method for producing the positive electrode active material.
- the third technical problem of the present invention is to provide a positive electrode for a secondary battery having improved capacity, thermal safety, and high temperature lifetime by including the surface-modified cathode active material.
- a fourth technical problem of the present invention is to provide a secondary battery having the secondary battery positive electrode.
- Lithium transition metal oxide particles represented by Formula 1 Lithium transition metal oxide particles represented by Formula 1;
- cathode active material for a secondary battery comprising a; lithium metal phosphate nanoparticles represented by the following formula (2) disposed on the surface of the lithium transition metal oxide particles.
- M is at least one metal selected from the group consisting of Mn, Al, Cu, Fe, Mg, Cr, Sr, V, Sc and Y, 0 ⁇ a ⁇ 0.2, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1.
- M ' is Al, Y, Cr or Ca
- M' ' is Ge, Ti, Sn, Hf, Zn or Zr, where 0 ⁇ x ⁇ 0.5.
- the method may further include a heat treatment step after the coating step according to the crystal state of the lithium metal phosphate nanoparticles disposed on the lithium transition metal oxide particle surface.
- the present invention also provides a secondary battery including a positive electrode including the surface-modified positive electrode active material of the present invention, a negative electrode including the negative electrode active material, a separator interposed between the positive electrode and the negative electrode, and a nonaqueous electrolyte.
- a cathode active material having increased structural stability and lithium ion conductivity may be manufactured.
- the side-modification of the electrolyte and the positive electrode active material may be prevented by the surface-modified positive electrode active material, and thus, a lithium secondary battery having improved rate rate characteristics, high temperature, high voltage stability, and cycle life characteristics may be manufactured.
- FIG. 2 is an XRD graph of lithium metal phosphate nanoparticles prepared in Preparation Example 1.
- FIG. 4 is an XRD graph of lithium metal phosphate nanoparticles prepared in Preparation Example 2.
- Example 5 is an electron micrograph of the surface of the positive electrode active material including lithium metal phosphate nanoparticles prepared according to Example 1 of the present invention.
- Example 6 is an electron micrograph of the surface of the positive electrode active material including lithium metal phosphate nanoparticles prepared according to Example 2 of the present invention.
- Example 7 is an electron micrograph of the surface of the cathode active material including lithium metal phosphate nanoparticles prepared according to Example 3 of the present invention.
- Example 8 is an electron micrograph of the surface of the positive electrode active material including lithium metal phosphate nanoparticles prepared according to Example 4 of the present invention.
- FIG. 11 is a graph showing the capacity change according to the charge and discharge cycle of the cell according to Experimental Example 2 of the present invention.
- FIG. 13 is a graph showing the capacity change according to the charge and discharge cycle of the cell according to Experimental Example 3 of the present invention.
- ionic conductivity should be understood to have the same meaning as the terms “ion conductivity”, “ion conductivity” and the like.
- the conventional cathode active material can improve the structural safety of the secondary battery by freeing the flow of electrons by the surface modification and by acting as a protective shell mechanically and chemically to improve the efficiency for the high rate.
- Chemically stable carbonaceous materials or metal oxides having low electrical and ionic conductivity such as Al 2 O 3 or ZrO 2 , were used as materials used for the surface modification.
- a material having low electrical and ionic conductivity such as a metal oxide, the movement of lithium ions between the electrolyte and the positive electrode active material is limited, and the interface resistance may increase.
- the present invention is to provide a surface modification material that can increase the structural stability of the positive electrode active material while giving a high lithium ion conductivity.
- Lithium transition metal oxide particles represented by Formula 1 Lithium transition metal oxide particles represented by Formula 1;
- cathode active material for a secondary battery comprising a; lithium metal phosphate nanoparticles represented by the following formula (2) disposed on the surface of the lithium transition metal oxide particles.
- M is at least one metal selected from the group consisting of Mn, Al, Cu, Fe, Mg, Cr, Sr, V, Sc and Y, 0 ⁇ a ⁇ 0.2, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1.
- M ' is Al, Y, Cr or Ca
- M' ' is Ge, Ti, Sn, Hf, Zn or Zr, where 0 ⁇ x ⁇ 0.5.
- the LiNi 1 -x- y Co x Mn y O 2 (NMC) lithium transition metal oxide is a three-component material represented by Formula 1 (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1), for example, LiNi 0.6 Mn 0.2 Co 0.2 O 2 , and the like.
- the lithium transition metal oxide may further include at least one compound having a spinel structure or an olivine structure together with the lithium transition metal oxide particles represented by Chemical Formula 1.
- the lithium metal phosphate nanoparticles represented by Chemical Formula 2 refers to a lithium ion conductor material that provides high lithium ion conductivity of a NASICON structure.
- nanocon is an abbreviation of Na Super Ion Conductor, and examples thereof include Na 3 Zr 2 Si 2 PO 12 , NaZr 2 (PO 4 ) 3 , and the like.
- the lithium metal phosphate-based nanoparticles of the present invention have the same or similar crystal structure as that of the nacicon compound, wherein Na is substituted with lithium and Zr is partially or entirely substituted with other metals.
- the lithium metal phosphate nanoparticles represented by Chemical Formula 2 may be LiTi 2 (PO 4 ) 3 , LiZr 2 (PO 4 ) 3 , or Li 1 + x Al x Ti in which Li is partially substituted with Al or Y. 2-x (PO 4 ) 3 (0 ⁇ x ⁇ 0.5, referred to as “LATP”), Li 1 + x Al x Zr 2 -x (PO 4 ) 3 (0 ⁇ x ⁇ 0.5) and Li 1 + x Y x Zr 2-x (PO 4 ) 3 (0 ⁇ x ⁇ 0.5, referred to as “LYZP”).
- the lithium metal phosphate nanoparticles represented by Chemical Formula 2 are representative examples of Li 1 . 4 Al 0 . 4 Ti 1 .6 (PO 4) 3, Li 1. 15 Al 0 . 15 Zr 1 .85 (PO 4) 3, or Li 1.15 Y 0.15 Zr 1.85 (PO 4) 3 Can be mentioned.
- the LiTi 2 (PO 4 ) 3 , and LiZr 2 (PO 4 ) 3 shows a lithium ion conductivity of 1 ⁇ 10 -6 S / cm at room temperature, while Li is partially substituted with Al or Y Li 1 + x Al x Ti 2 -x (PO 4 ) 3 , Li 1 + x Al x Zr 2 -x (PO 4 ) 3 (0 ⁇ x ⁇ 0.5) and Li 1 + x Y x Zr 2 -x ( PO 4 ) 3 is 1 ⁇ 10 -3 S / cm at room temperature Higher lithium ion conductivity may be exhibited, from 1 ⁇ 10 ⁇ 5 S / cm.
- the lithium metal phosphate nanoparticles may have an average particle diameter (D50) of 200 nm or less, specifically, 10 nm to 200 nm, more specifically, 10 nm to 100 nm, based on a long axis.
- D50 average particle diameter
- the lithium metal phosphate nanoparticles may be included in 0.1 wt% to 2 wt%, specifically 0.3 wt% to 1 wt% based on the total weight of the cathode active material. If the content of the lithium metal phosphate nanoparticles is less than 0.1% by weight, the effect of the coating may be insignificant. When the content of the lithium metal phosphate is less than 2% by weight, the amount of the cathode active material is relatively reduced, so that the capacity per gram decreases. There is.
- the lithium ion conductivity of the cathode active material including the lithium metal phosphate nanoparticles of the present invention is 1 ⁇ 10 -3 S / cm to 1 ⁇ 10 -6 S / cm, specifically 1 ⁇ 10 -4 S / cm to 1 ⁇ It can be 10 -5 S / cm.
- the lithium metal phosphate nanoparticles disposed on the transition metal oxide particle surface have a very stable structure by strong PO bonds.
- the thermal stability is increased on the surface of the transition metal oxide particles, and the lithium metal phosphate nanoparticles are very stable even in the reaction with the electrolyte. Can be placed.
- the lithium metal phosphate nanoparticles may serve as a protective layer along with surface modification on the surface of the lithium transition metal oxide particle.
- a nanoparticle-lithiated lithium metal phosphate compound having a size of 200 nm or less on the surface of the lithium transition metal oxide particle, the surface of the transition metal oxide particle reacts with an electrolyte based on LiPF 6 during charge and discharge.
- Forming a thin film of "Co-Al-OF" form in the to increase the structural stability it is possible to prevent the side reaction with the electrolyte solution to prevent the dissolution of the transition metal such as cobalt (Co dissolution).
- Co dissolution Co dissolution
- It provides a method for producing a cathode active material for a secondary battery comprising a; (c) mixing the coating solution and the lithium transition metal oxide particles, coating the lithium metal phosphate nanoparticles on the surface of the lithium transition metal oxide particles.
- lithium metal phosphate nanoparticles having a uniform size with an average particle diameter of 200 nm or less are first synthesized, and then coated on the surface of the transition metal oxide particles to form lithium metal phosphate nanoparticles on the surface of the transition metal oxide particles. Can be placed.
- the method may further include or omit the heat treatment step after the coating step according to the crystal state of the lithium metal phosphate nanoparticles.
- the synthesized lithium metal phosphate nanoparticles are in a crystallized NASICON state, it is not necessary to perform a subsequent heat treatment step, but when the synthesized lithium metal phosphate nanoparticles are in an amorphous state, additionally perform a subsequent heat treatment step. Can be crystallized.
- Preparing a mixed solution by adding a reaction solvent, a lithium precursor, a phosphorus precursor, and at least two or more metal precursors together in an atmospheric pressure reactor;
- lithium metal phosphate nanoparticles may include.
- the size of the crystallized lithium metal phosphate nanoparticles may have an average particle diameter (D50) of 200 nm or less, specifically 10 nm to 200 nm, more specifically 10 nm to 100 nm on the basis of a long axis.
- D50 average particle diameter
- the atmospheric pressure reactor used in the method of the present invention may use a reactor commonly used in the art for producing a cathode active material, the type is not particularly limited.
- a reactor commonly used in the art for producing a cathode active material the type is not particularly limited.
- it may be an open reactor or a closed reactor.
- a solvent containing a diol, a polyol, or a glycol having at least two hydroxyl groups in a molecule may be used, and specific examples thereof include ethylene glycol, 1,2- Propylene glycol, 1,3-propylene glycol, glycerin, glycerol, diethyl glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 2,3-butanediol or Mixtures of two or more of these can be used.
- lithium metal phosphate particles of several tens of nm in size since a simple grinding method is used, it is difficult to produce lithium metal phosphate particles of several tens of nm in size.
- the present invention by performing a polyol synthesis reaction using a solvent containing a diol, a polyol, or a glycol having at least two hydroxyl groups, lithium metal phosphate nanoparticles of several to several tens of nm in size can be prepared. have. Furthermore, by increasing the temperature during the polyol reaction or lengthening the reaction time, the particles can be crystallized or the particle size can be controlled.
- reaction solvent may be used 100 parts by weight to 10,000 parts by weight, specifically 100 parts by weight to 1,000 parts by weight based on 100 parts by weight of the total content of the precursor.
- the lithium precursor may be, for example, lithium acetate dihydrate (CH 3 COOLi ⁇ 2H 2 O), lithium hydroxide monohydrate (LiOH.H 2 O), lithium hydroxide (LiOH), Selected from the group consisting of lithium carbonate (Li 2 CO 3 ), lithium phosphate (Li 3 PO 4 ), lithium phosphate dodecahydrate (Li 3 PO 4 12H 2 O) and lithium oxalate (Li 2 C 2 O 4 ) It may be one or a mixture of two or more.
- the phosphorus precursors also include ammonium phosphate ((NH 4 ) 2 HPO 4 ), phosphoric acid, tri-ammonium phosphate trihydrate ((NH 4 ) 3 PO 4 .3H 2 O), and ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ) may be a mixture of one or two or more selected from the group consisting of.
- the two or more metal precursors may include an aluminum precursor, a titanium precursor, a yttrium precursor, a zirconium precursor, or the like.
- the aluminum precursor may be aluminum acetate and aluminum nitrate and aluminum oxide (Al 2 O 3 ).
- the titanium precursor is titanium (IV) butoxide (Ti (OCH 2 CH 2 CH 2 CH 3 ) 4 ), titanium (IV) isopropoxide (Ti [OCH (CH 3 ) 2 ] 4 ), titanium chloride (TiCl 4 ), titanium fluoride (TiF 4 ) and tetrakis dimethylamino titanium (TDMAT, Ti [N (CH 3 ) 2 ] 4 ), or a mixture of two or more thereof.
- the yttrium precursors also include yttrium nitrate hexahydrate (Y (NO 3 ) 3 .6H 2 O), yttrium acetate hydrate ((CH 3 CO 2 ) 3 YH 2 O), and yttrium chloride hexahydrate (Cl 3 Y. 6H 2 O), yttrium oxide (Y 2 O 3 ) or a mixture of two or more selected from the group consisting of.
- the zirconium precursor is zirconium (IV) oxy-nitrate hydrate (ZrO (NO 3) 2 ⁇ xH 2 O), zirconium propoxide (C 12 H 28 O 4 Zr ), zirconium oxychloride octa-hydrate (Cl 2 OZr ⁇ 8H 2 O), or zirconium (IV) acetylacetonate (Zr (C 5 H 7 O 2 ) 4 ) It may be a single or a mixture of two or more selected from the group consisting of.
- the molar ratio of the lithium precursor: phosphorus precursor: two or more metal precursors may be 1.1 to 1.5: 3: 0.6 to 2.5, specifically, lithium precursor:
- the molar ratio of phosphorus precursor: first metal precursor: second metal precursor is 1.1 to 1.5: 3: 0.1 to 0.55: 0.5 to 1.95, more specifically 1.15 to 1.4: 3: 0.15 to 0.4: 1.6 to 1.85, more specifically 1.4 3: 3: 0.4: 1.6.
- a NASICON structural material having an ion conductivity of 1 ⁇ 10 ⁇ 6 S / cm or more may be prepared, If the range is over or below the range, the nanoparticle compound of the NASICON structure having the above ion conductivity cannot be prepared.
- the mixed solution may be stirred while raising the temperature to 200 ° C, thereby preparing a lithium metal phosphate compound.
- the mixing and stirring step may be carried out while heating to 190 °C to 220 °C, specifically 200 °C, stirring for 3 to 24 hours.
- the mixed solution was cooled to room temperature and then filtered to obtain lithium metal phosphate nanoparticles.
- the obtained lithium phosphate nanoparticles can be washed sequentially using acetone and methanol.
- the lithium metal phosphate nanoparticles are dispersed in (b) a dispersion solvent to prepare a coating solution.
- the solvent used may be an alcohol solvent such as ethanol or methanol.
- the coating solution and the lithium transition metal oxide particles may be mixed to place lithium metal phosphate nanoparticles on the surface of the transition metal oxide particles.
- the wet method may prepare a coating solution by dispersing the nanoparticles lithium phosphate compound in a dispersion solvent, and then mixed and immersed lithium transition metal oxide particles in the coating solution, it can be carried out while stirring at 80 °C temperature. .
- the heat treatment step may be further included or omitted depending on the crystal state of the lithium metal phosphate nanoparticles formed after the coating step. That is, when the lithium metal phosphate nanoparticles are in the crystallized nasicon state, it is not necessary to perform the subsequent heat treatment step, but when the lithium metal phosphate nanoparticles are in the amorphous state, the subsequent heat treatment step is further performed to crystallize It is desirable to convert to state.
- the heat treatment step may be carried out by heating to a temperature range of 400 to 900 °C under an atmospheric pressure of 10 bar or less in an oxygen atmosphere or an air atmosphere, heat treatment time is not particularly limited, for example, to be carried out within 0.5 to 5 hours desirable.
- lithium metal phosphate nanoparticles may be disposed or coated on the surface of the lithium transition metal oxide particle of the present invention based on the total weight of the positive electrode active material.
- an embodiment of the present invention provides a positive electrode including the positive electrode active material.
- the positive electrode may be manufactured as follows.
- the cathode active material composition After preparing at least one of a cathode active material, a solvent, optionally a conductive material, a binder and a filler of the present invention to prepare a cathode active material composition, the cathode active material composition is coated and dried on a cathode current collector to form a cathode active material layer A positive electrode plate can be manufactured.
- the cathode active material composition may be cast on a separate support, and then a film obtained by peeling from the support may be laminated on the aluminum current collector to prepare a cathode electrode plate having a cathode active material layer formed thereon.
- the conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and 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 and thermal black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
- 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 and thermal black
- Conductive fibers such as carbon fibers and metal fibers
- Metal powders such as carbon fluoride powder, aluminum powder and nickel powder
- Conductive whiskeys such as zinc oxide and potassium titanate
- Conductive metal oxides
- the conductive material may typically be included in an amount of 1 to 30% by weight based on the total weight of the mixture including the positive electrode active material.
- the binder is not particularly limited as long as the component assists in bonding the active material and the conductive material and bonding to the current collector, and is not particularly limited.
- the binder may be typically included in an amount of 1 to 30% by weight based on the total weight of the mixture including the positive electrode active material.
- the filler may be optionally used as a component for inhibiting the expansion of the electrode, and is not particularly limited as long as it is a fibrous material that does not cause chemical change in the battery, for example, an olefin polymer such as polyethylene, polypropylene; Fibrous materials, such as glass fiber and carbon fiber, can be used.
- an olefin polymer such as polyethylene, polypropylene
- Fibrous materials such as glass fiber and carbon fiber, can be used.
- the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery.
- carbon, nickel, titanium on the surface of stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel Surface treated with silver, silver or the like can be used.
- the current collector may have a thickness of 3 to 500 ⁇ m typically, may form a fine concavo-convex on the surface of the current collector to increase the adhesion of the positive 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, a nonwoven body.
- a cathode comprising a cathode active material of the present invention
- a negative electrode comprising a negative electrode active material
- a separator interposed between the positive electrode and the negative electrode, and
- a lithium secondary battery including a nonaqueous electrolyte.
- the negative electrode is manufactured by applying a negative electrode mixture containing a negative electrode active material on a negative electrode current collector and then drying the negative electrode mixture.
- the negative electrode mixture may include components such as a conductive material, a binder, and a filler as described above, if necessary. May be included.
- the negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
- the negative electrode current collector may be formed on a surface of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper, or stainless steel. Surface-treated with carbon, nickel, titanium, silver, and the like, aluminum-cadmium alloy and the like can be used.
- the current collector may have a thickness of typically 3 to 500 ⁇ m, and like the positive electrode current collector, it is also possible to form a fine concavo-convex on the surface of the current collector to enhance the bonding strength 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, a nonwoven body.
- the separator is interposed between the anode and the cathode, and an insulating thin film having high ion permeability and mechanical strength may be used.
- the pore diameter of the separator is generally 0.01 to 10 ⁇ m, the thickness may be generally 5 to 300 ⁇ m.
- the separator may be, for example, an olefin polymer such as polypropylene having chemical resistance and hydrophobicity; Sheets or non-woven fabrics made of glass fibers or polyethylene, etc. may be used.
- the solid electrolyte may also serve as a separator.
- the lithium salt-containing non-aqueous electrolyte solution consists of an electrolyte solution and a lithium salt, and a non-aqueous organic solvent or an organic solid electrolyte is used as the electrolyte solution.
- non-aqueous organic solvent for example, N-methyl-2-pyrrolidone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyrolactone, 1,2-dime Methoxyethane, tetrahydroxyfuran, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolon, formamide, dimethylformamide, dioxolon, acetonitrile, nitromethane, methyl formate, methyl acetate, Phosphate triester, trimethoxy methane, dioxoron derivative, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivative, tetrahydrofuran derivative, ether, methyl propionate, ethyl propionate
- An aprotic organic solvent such as may be used.
- organic solid electrolyte examples include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, polyedgetion lysine, polyester sulfides, polyvinyl alcohols, polyvinylidene fluorides, and ions. Polymers including sex dissociating groups and the like can be used.
- the lithium salt is a good material to be dissolved in the non-aqueous electrolyte, for example, LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, 4-phenyl lithium borate, and imide Can be.
- pyridine triethyl phosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitro Benzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrroles, 2-methoxy ethanol, aluminum trichloride and the like may be added. .
- halogen-containing solvents such as carbon tetrachloride and ethylene trifluoride may be further included, and carbon dioxide gas may be further included to improve high temperature storage characteristics.
- Li 1 of the crystalline phase . 4 Al 0 . 4 Ti 1 .6 (PO 4) 3 is the generation can be confirmed as compared with the XRD graph of the LiTi 2 (PO 4) 3 crystalline phases.
- FIG, LiTi 2 (PO 4) as shown is of a similar intensity to a similar position and the crystal phase XRD graph of peak 3 Li 1 as shown in Fig. 4 Al 0 . 4 Ti 1 .6 (PO 4) it can be seen that the 3 is generated.
- Al is partially substituted.
- Li 1 obtained above . 15 Y 0 . 15 to 1 .85 Zr (PO 4) 3 added to the nanoparticles at a temperature above 750 °C heat treatment to prepare a Li 1.4 Y 0.4 Ti 1.6 (PO 4) 3 crystal phase (see Fig. 3).
- Li 1 of the crystalline phase . 4 Y 0 . 4 Ti 1 .6 (PO 4) 3 is the generation can be confirmed as compared with the XRD graph of the LiZr 2 (PO 4) 3 crystalline phases.
- LiZr 2 (PO 4) as Li 1 may appear similar to that of a similar intensity to the crystalline phase locations and XRD graph of the third peak.
- 4 Y 0 . 4 Ti 1 .6 (PO 4) it can be seen that the 3 is generated.
- Y is partially substituted.
- Preparation Example 1 the lithium metal phosphate (LATP) and distributed to the appropriate concentration of nanoparticles in ethanol to prepare a coating solution, the lithium-transition metal oxide particles in the coating solution of (LiNi 0. 85 Co 0. 10 Al 0. 05 O 2 , NCA) (20 g) were mixed, followed by stirring until the solvent evaporated at a temperature of 80 ° C. to prepare a cathode active material in which lithium metal phosphate nanoparticles were disposed on the surface of the transition metal oxide particle.
- LATP lithium metal phosphate
- NCA NCA
- the cathode active material slurry was prepared by mixing the cathode active material, the conductive material (SC65), and the binder (polyvinylidene fluoride) in a weight ratio of 93: 4: 3.
- the prepared positive electrode slurry was coated on Al foil and then rolled to prepare a positive electrode plate for a coin cell.
- the prepared positive electrode plate was punched to 1.6 cm, used as a counter electrode, and placed in a glove box containing an electrolyte solution (a mixed solution of ethylene carbonate and dimethyl carbonate (1: 1 volume ratio) in which 1M LiPF 6 was dissolved).
- Coin cells were prepared.
- LATP lithium metal phosphate
- a coin cell was manufactured in the same manner as in Example 1, except that the NMC cathode active material was used instead of the cathode active material (NCA) of Example 1.
- NMC cathode active material was used instead of the cathode active material (NCA) of Example 1.
- the positive electrode active material LiCoO 2 ) (20g) is added to the coating solution and then the solvent is evaporated at a temperature of 80 °C By stirring until the positive electrode active material in which the phosphate nanoparticles are disposed on the surface of the lithium transition metal oxide particles.
- Example 2 instead of the positive electrode active material (NCA) of Example 1, the LiCoO 2 positive electrode active material was used, and a positive electrode active material, a conductive material (SC65), and a binder (polyvinylidene fluoride) were used in a weight ratio of 96: 2: 2.
- a coin cell was manufactured in the same manner as in Example 1 except for using the same.
- Preparative Example 2 a lithium metal phosphate nanoparticles (LYZP) having an average particle size of several tens nm dispersed in a suitable concentration in ethanol to prepare a coating solution, and then, the positive electrode active material in the coating solution (LiCoO 2) the incorporation of (20g) and then After stirring, the solvent was evaporated at a temperature of 80 ° C. to prepare a cathode active material in which phosphate nanoparticles were disposed on the surface of the lithium transition metal oxide particle.
- LYZP lithium metal phosphate nanoparticles
- the positive electrode active material coated with the lithium metal phosphate nanoparticles of Preparation Example 2 a conductive material (SC65), and a binder (polyvinylidene fluoride) were used in a weight ratio of 96: 2: 2.
- a coin cell was manufactured in the same manner as in Example 1, except that.
- Example 2 A coin cell and in the same manner as Example 1 except for using the lithium metal phosphate (LATP) positive electrode active material (LiNi 0.85 Co 0.10 Al 0. 05 O 2, NCA) are not coated nanoparticles were prepared.
- LATP lithium metal phosphate
- NCA negative electrode active material
- Coin cells were prepared in the same manner as in Example 2, except that lithium metal phosphate (LATP) nanoparticles were not coated with a cathode active material (LiNi 0.6 Mn 0.2 Co 0.2 O 2 , NMC).
- LATP lithium metal phosphate
- a coin cell was prepared in the same manner as in Example 3 except for using a cathode active material (LiCoO 2 ) not coated with lithium metal phosphate (LATP) nanoparticles.
- LiCoO 2 cathode active material
- LiATP lithium metal phosphate
- LiOH.H 2 O, (NH 4 ) 2 HPO 4 was dissolved in water at a molar ratio of 3: 1, and then the dry powder was ground using a ball mill.
- the positive electrode active material (LiCoO 2 ) (20g) was mixed and mixed with the coating solution, and then the solvent at 80 °C temperature After stirring until the evaporation and heat treatment at a temperature of 450 °C to prepare a cathode active material containing lithium metal phosphate nanoparticles.
- Example 1 and Comparative Example 1 were subjected to 50 charge / discharge cycles at 3.0V to 4.6V voltage and rate c-rate 0.5C to change capacity and charge / discharge according to charge / discharge cycles. The change was measured and the results are shown in FIGS. 9 and 10, respectively.
- Example 2 For the coin cells of Example 2 and Comparative Example 2, 50 charge and discharge at 3.0V to 4.6V voltage and the rate (c-rate) 0.5C to perform the capacity change and charge / discharge according to the charge and discharge cycle The change was measured and the results are shown in FIGS. 11 and 12, respectively.
- the coin cell prepared using the positive electrode active material containing the lithium phosphate (LATP) nanoparticles of Example 2 and the lithium metal phosphate nanoparticles of Comparative Example 2 When the capacity change of the coin cell containing the positive electrode active material was measured for the charge / discharge cycle, the cell of Example 2 and the cell of Comparative Example 2 showed similar capacities up to 20 cycles, and thereafter, the cell of Comparative Example 2 It can be seen that the reduction in capacity is greater than that in Example 2.
- the coin cells of Example 2 and Comparative Example 2 show similar charge / discharge graphs in the first cycle when the 4.6V cycle proceeds, but as the cycle progresses, Compared with the coin cell of Example 2, it can be seen that the cell of Example 2 has a lower voltage drop and a lower capacity, and thus has better electrochemical properties.
- the coin cells of Examples 3 and 4 and Comparative Examples 3 and 4 were charged and discharged at a voltage of 3.0 V to 4.5 V at 0.5 C when charging and rate c-rate, and 1.0 C when discharging. Capacity change and charge / discharge change according to charge / discharge cycles were measured. The results are shown in FIGS. 13 to 17, respectively.
- the coin cells of Comparative Example 3 and Comparative Example 4 were continuously subjected to the cycle. While the capacity decreased, the coin cells of Examples 3 and 4 decreased in capacity as the cycle progressed, but it was confirmed that the deceleration width was smaller than that of Comparative Examples 3 and 4. This may be determined that lithium metal phosphate nanoparticles disposed on the surface of the lithium transition metal oxide particles prevent direct contact between the positive electrode active material and the electrolyte solution, thereby preventing Co elution to decrease capacity reduction.
- the coin cell of Example 3 (see FIG. 14) and the coin cell of Example 4 (see FIG. 15) prepared using the cathode active material including lithium metal phosphate nanoparticles prevent side reactions with the electrolyte. It was confirmed that the OCV at the initial stage of discharge was maintained by improving the structural safety.
- the capacity retention ratio was calculated by dividing the discharge capacity after 30 cycles of charge and discharge measured in FIG. 13 by the discharge capacity of the initial cycle, and the values are shown in Table 1 below.
- Example 3 Example 4 Comparative Example 3 Comparative Example 4 Capacity retention after 30 cycles 95.5% 96.8% 68.6% 85.2%
- the coin cells of Examples 3 and 4 and the coin cells of Comparative Examples 3 and 4 were subjected to one-time charging and discharging at a voltage of 3.0 V to 4.5 V and an initial rate of 0.2 C, followed by the same charging rate at 0.5 C.
- the discharge rate was increased to 2 0.1C, 3 1.0C and 4 2.0C.
- Example 3 Example 4 Comparative Example 3 Comparative Example 4 Initial charge (0.2C) mAh / g 196.2 195.4 195.7 195.1 Initial discharge (0.2C) 190.6 190.6 189.6 188.8 Initial charge and discharge efficiency % 97.1 97.5 96.9 96.8 1.0C (discharge) / 0.2 (discharge) 96.1 98.6 94.9 96.2 2.0C (discharge) /0.2 (discharge) 92.0 94.9 88.6 89.7
- the coin cells of Examples 3 and 4 have a capacity of 92.0% and 94.9%, respectively, compared to 0.2C at 2C, while the capacity of the coin cells of Comparative Examples 3 and 4 is 88.6% and 89.7%, respectively. have.
- the positive electrode active material containing the lithium metal phosphate nanoparticles of the present invention improves the lithium ion conductivity of the surface of the positive electrode active material during charge and discharge, thereby increasing the rate and decreasing the rate of capacity reduction.
- Example 3 The coin cell of Example 3 and the coin cells prepared in Comparative Examples 3 and 4 after charging and discharging 30 times with 0.5C and 1.0C constant current charge at a voltage range of 3.0 to 4.5V compared to lithium metal at a high temperature of 45 °C The result was measured, and the result is shown in FIG.
- the capacity retention ratio was calculated from the discharge capacity after the charge / discharge cycle 30 measured in FIG. 18 as the discharge capacity of the initial cycle, and the values are shown in Table 3 below.
- the capacity retention rate after measuring the life of 30 cycles is 95.5%, while instead of the coin cell and nanoparticles of Comparative Example 3 made of a cathode active material containing no lithium metal phosphate nanoparticles
- the capacity retention rate is low at 81.5% and 90.2%, respectively.
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Abstract
Description
실시예3 | 실시예4 | 비교예3 | 비교예4 | |
30 싸이클 후 용량 유지율 | 95.5% | 96.8% | 68.6% | 85.2% |
실시예3 | 실시예4 | 비교예3 | 비교예4 | ||
초기 충전(0.2C) | mAh/g | 196.2 | 195.4 | 195.7 | 195.1 |
초기 방전 (0.2C) | 190.6 | 190.6 | 189.6 | 188.8 | |
초기 충방전 효율 | % | 97.1 | 97.5 | 96.9 | 96.8 |
1.0C(방전)/0.2(방전) | 96.1 | 98.6 | 94.9 | 96.2 | |
2.0C(방전)/0.2(방전) | 92.0 | 94.9 | 88.6 | 89.7 |
실시예3 | 비교예3 | 비교예4 | |
30 싸이클 후 용량 유지율 | 95.5% | 81.5% | 90.2% |
Claims (24)
- 하기 화학식 1로 표시되는 리튬 전이금속 산화물 입자; 및상기 리튬 전이금속 산화물 입자 표면에 배치된 하기 화학식 2로 표시되는 리튬 금속 포스페이트 나노입자;를 포함하는 포함하는 이차전지용 양극활물질:[화학식 1]Li(1+a)(Ni1-b-cMbCoc)O2상기 식에서, M은 Mn, Al, Cu, Fe, Mg, Cr, Sr, V, Sc 및 Y로 이루어진 군으로부터 선택된 적어도 하나 이상의 금속이고, 0≤a≤0.2, 0≤b≤1, 0≤c≤1이다.[화학식 2]Li1 + xM'xM''2-x(PO4)3상기 식에서, M'는 Al, Y, Cr 또는 Ca 이고, M''는 Ge, Ti, Sn, Hf, Zn 또는 Zr 이며, 0≤x≤0.5이다.
- 청구항 1에 있어서,상기 리튬 전이금속 산화물은 LiNi0 . 85Co0 . 10Al0.05O2 (NCA), LiNi1 -x- yCoxMnyO2 (NMC) (0≤x≤1, 0≤y≤1) 및 LiCoO2로 이루어진 군으로부터 선택된 적어도 하나 이상의 물질을 포함하는 것인 이차전지용 양극활물질.
- 청구항 1에 있어서,상기 화학식 2로 표시되는 리튬 금속 포스페이트 나노입자는 나시콘(NASICON) 구조를 가지는 것인 이차전지용 양극활물질.
- 청구항 1에 있어서,상기 화학식 2로 표시되는 리튬 금속 포스페이트 나노입자는 LiTi2(PO4)3, LiZr2(PO4)3, Li1 + xAlxTi2 -x(PO4)3 (0≤x≤0.5), Li1 + xAlxZr2 -x(PO4)3 (0≤x≤0.5) 및 Li1+xYxZr2-x(PO4)3 (0≤x≤0.5)로 이루어진 군으로부터 선택된 적어도 하나를 포함하는 것인 이차전지용 양극활물질.
- 청구항 4에 있어서,상기 리튬 금속 포스페이트 나노입자는 Li1 . 4Al0 . 4Ti1 .6(PO4)3, Li1.15Al0.15Zr1.85(PO4)3, 및 Li1 . 15Y0 . 15Zr1 .85(PO4)3 로 이루어진 군으로부터 선택된 적어도 하나를 포함하는 것인 이차전지용 양극활물질.
- 청구항 5에 있어서,상기 리튬 금속 포스페이트 나노입자의 리튬 이온전도도는 상온에서 1×10-3 S/cm 내지 1×10-5 S/cm인 것인 이차전지용 양극활물질.
- 청구항 1에 있어서,상기 리튬 금속 포스페이트 나노입자의 평균입경(D50)은 200nm 이하인 것인 이차전지용 양극활물질.
- 청구항 7에 있어서,상기 리튬 금속 포스페이트 나노입자의 평균입경(D50)은 10nm 내지 200nm인 것인 이차전지용 양극활물질.
- 청구항 1에 있어서,상기 리튬 금속 포스페이트 나노입자는 양극활물질의 전체 중량을 기준으로 0.1 중량% 내지 2 중량%로 포함되는 것인 이차전지용 양극활물질.
- 청구항 9에 있어서,상기 리튬 금속 포스페이트 나노입자는 양극활물질의 전체 중량을 기준으로 0.3 중량% 내지 1 중량%로 포함되는 것인 이차전지용 양극활물질.
- 청구항 1에 있어서,상기 양극활물질의 리튬 이온 전도도는 1×10-3 S/cm 내지 1×10-6 S/cm인 것인 이차전지용 양극활물질.
- (a) 하기 화학식 2로 표시되는 리튬 금속 포스페이트 나노입자를 합성하는 단계;(b) 분산용매에 상기 리튬 금속 포스페이트 나노입자를 분산시켜 코팅 용액을 제조하는 단계; 및(c) 상기 코팅 용액과 리튬 전이금속 산화물 입자를 혼합하여, 리튬 전이금속 산화물 입자 표면에 리튬 금속 포스페이트 나노입자를 코팅하는 단계;를 포함하는 것인 청구항 1의 이차전지용 양극활물질의 제조 방법:[화학식 2]Li1 + xM'xM''2-x(PO4)3상기 식에서, M'는 Al, Y, Cr 또는 Ca 이고, M''는 Ge, Ti, Sn, Hf, Zn 또는 Zr 이며, 0≤x≤0.5이다.
- 청구항 12에 있어서,상기 방법은 코팅 단계 후에, 열처리 단계를 추가로 포함하는 것인 이차전지용 양극활물질의 제조 방법.
- 청구항 12에 있어서,상기 (a) 리튬 금속 포스페이트 나노입자 합성 단계는상압 반응기에 반응 용매와 리튬 전구체, 인 전구체 및 적어도 2종 이상의 금속 전구체를 함께 투입하여 혼합 용액을 제조하는 단계;상기 혼합 용액을 200℃까지 승온하면서 교반하는 단계; 및반응 종결 후, 혼합 용액을 냉각하여 리튬 금속 포스페이트 나노입자를 수득하는 단계;를 포함하는 것인 이차전지용 양극활물질의 제조 방법.
- 청구항 14에 있어서,상기 반응 용매는 분자 내에 히드록시기를 적어도 2개 이상 가지는 다이올, 폴리올, 또는 글리콜 용매를 포함하는 것인 이차전지용 양극활물질의 제조 방법.
- 청구항 15에 있어서,상기 반응 용매는 에틸렌글리콜, 1,2-프로필렌글리콜, 1,3-프로필렌글리콜, 글리세린, 글리세롤, 디에틸 글리콜, 1,2-부탄디올, 1,3-부탄디올, 1,4-부탄디올, 및 2,3-부탄디올로 이루어지는 군으로 선택된 단일물 또는 이들의 2종 이상의 혼합물을 포함하는 것인 이차전지용 양극활물질의 제조 방법.
- 청구항 14에 있어서,상기 리튬 전구체는 리튬 아세테이트 디하이드레이트, 리튬 히드록사이드 모노하이드레이트, 리튬 히드록사이드, 리튬 카보네이트, 리튬 포스페이트, 리튬 포스페이트 도데카하이드레이트 및 리튬 옥살레이트(Li2C2O4)로 이루어진 군으로부터 선택된 단일물 또는 2종 이상의 혼합물인 것인 이차전지용 양극활물질 제조 방법.
- 청구항 14에 있어서,상기 인 전구체는 암모늄 포스페이트, 인산, 트리-암모늄포스페이트 트리하이드레이트 및 암모늄 디하이드로젠 포스페이트로 이루어진 군으로부터 선택된 단일물 또는 2종 이상의 혼합물인 것인 이차전지용 양극활물질 제조 방법.
- 청구항 14에 있어서,상기 2종 이상의 금속 전구체는 알루미늄 전구체, 티타늄 전구체, 이트륨 전구체, 및 지르코늄 전구체로 이루어진 군으로부터 선택된 적어도 2종 이상의 혼합물을 포함하는 것인 이차전지용 양극활물질 제조 방법.
- 청구항 14에 있어서,상기 리튬 전구체 : 인 전구체 : 2종 이상의 금속 전구체의 몰비는 1.1 내지 1.5 : 3 : 0.6 내지 2.5인 것인 이차전지용 양극활물질 제조 방법.
- 청구항 20에 있어서,상기 리튬 전구체 : 인 전구체 : 제1 금속 전구체 : 제2 금속 전구체의 몰비는 1.1 내지 1.5 : 3 : 0.1 내지 0.55 : 0.5 내지 1.95인 것인 이차전지용 양극활물질 제조 방법.
- 청구항 21에 있어서,상기 리튬 전구체 : 인 전구체 : 제1 금속 전구체 : 제2 금속 전구체의 몰비는 1.15 내지 1.4 : 3 : 0.15 내지 0.4 : 1.6 내지 1.85인 것인 이차전지용 양극활물질 제조 방법.
- 청구항 1 기재의 이차전지용 양극활물질을 포함하는 이차전지용 양극.
- 양극활물질을 포함하는 양극,음극활물질을 포함하는 음극,상기 양극과 음극 사이에 개재된 분리막, 및비수 전해질을 포함하며,상기 양극은 청구항 23의 이차전지용 양극을 포함하는 리튬 이차전지.
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CN107492643A (zh) * | 2017-07-31 | 2017-12-19 | 三峡大学 | 一种磷酸钛锂包覆LiNi1/3Co1/3Mn1/3O2正极材料及其制备方法 |
CN107591529A (zh) * | 2017-10-10 | 2018-01-16 | 中南大学 | 一种磷酸钛锂包覆镍钴锰三元正极材料及其制备方法 |
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CN106711412A (zh) * | 2016-12-13 | 2017-05-24 | 北京理工大学 | 一种复合富锂锰基正极材料及其制备方法 |
CN107492643A (zh) * | 2017-07-31 | 2017-12-19 | 三峡大学 | 一种磷酸钛锂包覆LiNi1/3Co1/3Mn1/3O2正极材料及其制备方法 |
JP2020511740A (ja) * | 2017-09-26 | 2020-04-16 | エルジー・ケム・リミテッド | リチウムマンガン系酸化物を含む高電圧用正極活物質およびその製造方法 |
JP7041798B2 (ja) | 2017-09-26 | 2022-03-25 | エルジー エナジー ソリューション リミテッド | リチウムマンガン系酸化物を含む高電圧用正極活物質およびその製造方法 |
US11600820B2 (en) | 2017-09-26 | 2023-03-07 | Lg Energy Solution, Ltd. | High voltage positive electrode active material including lithium manganese-based oxide and method for producing the same |
CN107591529A (zh) * | 2017-10-10 | 2018-01-16 | 中南大学 | 一种磷酸钛锂包覆镍钴锰三元正极材料及其制备方法 |
CN107768631A (zh) * | 2017-10-16 | 2018-03-06 | 桑顿新能源科技有限公司 | 一种包覆磷酸钛铝锂的富锂锰基材料及其制备方法 |
CN113346079A (zh) * | 2021-05-11 | 2021-09-03 | 浙江帕瓦新能源股份有限公司 | 钪体相掺杂与磷酸钛铬锂修饰正极材料前驱体及其制备方法 |
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