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CN-115207300-B - Composite positive electrode active material, positive electrode comprising same, lithium battery and preparation method of composite positive electrode active material

CN115207300BCN 115207300 BCN115207300 BCN 115207300BCN-115207300-B

Abstract

A composite positive electrode active material, a positive electrode including the same, a lithium battery, and a method of preparing the same are provided, wherein the composite positive electrode active material includes a core including a lithium transition metal oxide, and a shell disposed on and conforming to a surface of the core, wherein the shell includes at least one first metal oxide, a carbonaceous material, and a doped fluorine (F) element, the first metal oxide is represented by formula M a O b (0<a≤3 and 0< b <4, and b is not an integer if a is 1,2, or 3), and the first metal oxide is disposed in a carbonaceous material matrix, and M is at least one metal selected from groups 2 to 13, 15, and 16 of the periodic table of elements.

Inventors

  • Andre kopilov
  • Wen Zhongshuo
  • SUN YINHE
  • JIN GUICHENG
  • The Denis Qie Ernei husband that continues
  • MA XIANGGUO
  • Zhao Shengren

Assignees

  • 三星SDI株式会社

Dates

Publication Date
20260512
Application Date
20220401
Priority Date
20210401

Claims (16)

  1. 1. A composite positive electrode active material, the composite positive electrode active material comprising: a core comprising a lithium transition metal oxide, and A shell disposed on a surface of the core and conforming to the surface of the core, Wherein the shell comprises at least one first metal oxide, A carbonaceous material and a doped fluorine element, the first metal oxide being selected from at least one of Al 2 O z , wherein 0< z <3 >, nbo x , wherein 0< x <2.5 >, mgo x , wherein 0< x < 1>, sc 2 O z , wherein 0< z <3 >, tio y , wherein 0< y <2 >, zro y , wherein 0< y <2 >, v 2 O z , wherein 0< z <3 >, wo y , wherein 0< y <2 >, fe 2 O z , wherein 0< z <3 >, co 3 O w , wherein 0< w <4 >, pdo 2, wherein 0< x < 1>, cuo x , wherein 0< x < 1>, zno 92, wherein 0< x < 1>, sb < 26 >, and wherein 0< z <2, and 585, and wherein 0< 2 Wherein the first metal oxide is disposed in a carbonaceous material matrix, and Wherein the carbonaceous material is a carbonaceous two-dimensional nanostructure.
  2. 2. The composite positive electrode active material according to claim 1, wherein an amount of the doped fluorine element included in the shell is 1at% to 10at%, relative to a total atomic number of the shell.
  3. 3. The composite positive electrode active material according to claim 1, wherein an amount of metal included in the first metal oxide in the shell is 1at% to 10at% with respect to a total atomic number of the shell, an amount of oxygen included in the shell is 1at% to 20at% with respect to the total atomic number of the shell, an amount of nitrogen included in the shell is 1at% to 12at% with respect to the total atomic number of the shell, and an amount of boron included in the shell is more than 0at% and less than or equal to 5at% with respect to the total atomic number of the shell.
  4. 4. The composite positive electrode active material according to claim 1, wherein an amount of carbon included in the shell is 65at% to 99at%, relative to a total atomic number of the shell.
  5. 5. The composite positive electrode active material according to claim 1, wherein the shell has a thickness of 1nm to 5 μm.
  6. 6. The composite positive electrode active material according to claim 1, wherein the carbonaceous material is graphene.
  7. 7. The composite positive electrode active material according to claim 1, wherein the shell comprises at least one selected from a composite and an abrasive article of the composite, wherein the composite comprises the first metal oxide, the carbonaceous material, and the doped fluorine element, and an amount of the at least one selected from the composite and the abrasive article of the composite is 3wt% or less relative to a total weight of the composite positive electrode active material.
  8. 8. The composite positive electrode active material according to claim 7, wherein the carbonaceous material has a branched structure within which the first metal oxide is distributed, and the branched structure includes a plurality of carbonaceous material particles in contact with each other.
  9. 9. The composite positive electrode active material according to claim 7, wherein the carbonaceous material has at least one structure selected from the group consisting of a spherical structure, a spiro structure in which the spherical structures are connected to each other, and a cluster structure in which the spherical structures are aggregated with each other, Wherein the first metal oxide is distributed within the spherical structure, the spherical structure has a size of 50nm to 300nm, the spiro structure has a size of 500nm to 100 μm, the cluster structure has a size of 0.5mm to 10mm, the composite has a pleated polyhedral or planar structure, at least one selected from the first metal oxide and the second metal oxide is distributed within the pleated polyhedral or planar structure or on a surface of the pleated polyhedral or planar structure, the carbonaceous material extends from the first metal oxide by a distance of 10nm or less and includes 1 to 20 carbonaceous material layers, and the total thickness of the carbonaceous material is 0.6nm to 12nm, and Wherein the second metal oxide is represented by M a O c , wherein 0<a≤3 and 0<c≤4, c is an integer if a is 1,2 or 3, and M is at least one metal selected from groups 2 to 6, groups 8 to 13, groups 15 and group 16 of the periodic Table of the elements, and Wherein the first metal oxide is a reduction product of the second metal oxide.
  10. 10. The composite positive electrode active material according to claim 1, wherein the lithium transition metal oxide is represented by formula 1 or formula 5: < 1> Li a Ni x Co y M z O 2-b A b In formula 1, 0.9≤a≤1.2, 0≤b≤0.2, 0.8≤x <1, 0≤y≤0.3, 0< z≤0.3, and x+y+z=1, M is Mn, nb, V, mg, ga, si, W, mo, fe, cr, cu, zn, ti, al or a combination thereof, and A is F, S, cl, br or a combination thereof, < 5> Li a Co x M y O 2-b A b In formula 5, 1.0≤a≤1.2, 0≤b≤ 0.2,0.9≤x≤1, 0≤y≤0.1, and x+y=1, m is Mn, nb, V, mg, ga, si, W, mo, fe, cr, cu, zn, ti, al or a combination thereof, and a is F, S, cl, br or a combination thereof.
  11. 11. The composite positive electrode active material according to claim 1, wherein the lithium transition metal oxide is represented by at least one of formulas 2 to 4: < 2> LiNi x Co y Mn z O 2 < 3> LiNi x Co y Al z O 2 In the formulae 2 to 3, 0.8≤x≤0.95, 0< y≤0.2, 0< z≤0.2, and x+y+z=1, < 4> LiNi x Co y Mn v Al w O 2 In formula 4, 0.8≤x≤0.95, 0< y≤0.2, 0< v≤0.2, 0< w≤0.2, and x+y+v+w=1.
  12. 12. A positive electrode comprising the composite positive electrode active material according to any one of claims 1 to 11.
  13. 13. A lithium battery comprising the positive electrode of claim 12, a negative electrode, and an electrolyte disposed between the positive electrode and the negative electrode.
  14. 14. A method of preparing a composite positive electrode active material, the method comprising the steps of: providing a lithium transition metal oxide; providing a composite, and Mechanically milling the lithium transition metal oxide and the composite, Wherein the composite comprises at least one first metal oxide, A carbonaceous material and a doped fluorine element, the first metal oxide being selected from at least one of Al 2 O z , wherein 0< z <3; nbO x , wherein 0< x <2.5; mgO x , wherein 0< x <1; sc 2 O z , wherein 0< z <3; tiO y , wherein 0< y <2; zrO y , wherein 0< y <2; V 2 O z , wherein 0< z <3; WO y , wherein 0< y <2; fe 2 O z , wherein 0< z <3 >, co 3 O w , wherein 0< w <4 >, pdO x , wherein 0< x < 1>, cuO x , wherein 0< x < 1>, agO x , wherein 0< x < 1>, znO x , wherein 0< x < 1>, sb 2 O z , wherein 0< z <3 >, and SeO y , wherein 0< y <2, Wherein the first metal oxide is disposed within a carbonaceous material matrix, an Wherein the carbonaceous material is a carbonaceous two-dimensional nanostructure.
  15. 15. The method of claim 14, wherein providing the composite comprises providing an undoped composite by supplying a reaction gas composed of a carbon source gas to at least one second metal oxide represented by M a O c , wherein 0<a≤3 and 0<c≤4, and if a is 1,2 or 3, c is an integer, and performing a heat treatment to reduce the second metal oxide to the first metal oxide, and Preparing the undoped composite by contacting the composite with a fluorine-containing compound, wherein M is at least one metal selected from groups 2 to 6, groups 8 to 13, groups 15 and groups 16 of the periodic table of elements.
  16. 16. The method of claim 15, wherein the fluorine-containing compound is at least one selected from the group consisting of hydrogen fluoride, [ NO 2 ]BF 4 、[Et 2 NSF 2 ]BF 4 、HPF 6 、XeF 2 、F 2 gas, F 2 /Ar plasma, CF 4 plasma, and SF 6 plasma.

Description

Composite positive electrode active material, positive electrode comprising same, lithium battery and preparation method of composite positive electrode active material The present application is based on and claims priority of korean patent application No. 10-2021-0042810 filed in the korean intellectual property office on 1 month 2021, the disclosure of which is incorporated herein by reference in its entirety. Technical Field Provided are a composite positive electrode active material, a positive electrode and a lithium battery using the same, and a method of preparing the same. Background As various devices are increasingly miniaturized and have higher performance, it is increasingly important that lithium batteries have higher energy densities in addition to miniaturization and weight saving. That is, lithium batteries having a high capacity are increasingly important. In order to achieve a lithium battery suitable for the above-mentioned purpose, a positive electrode active material having a high capacity is being studied. Conventional nickel-based positive electrode active materials exhibit reduced life characteristics and unsatisfactory thermal stability due to side reactions. Therefore, a method for preventing deterioration of battery performance while including a nickel-based positive electrode active material is required. Disclosure of Invention One aspect provides a novel composite positive electrode active material that suppresses side reactions of the composite positive electrode active material and improves reversibility of an electrode reaction, thereby preventing deterioration of performance of a lithium battery. Another aspect provides a positive electrode including the composite positive electrode active material. Another aspect provides a lithium battery employing the positive electrode. Another aspect provides a method of preparing the composite positive electrode active material. Additional aspects will be set forth in part in the description which follows, and in part will be apparent from the description, or may be learned by practice of the disclosed presented embodiments. According to one aspect, there is provided a composite positive electrode active material including a core including a lithium transition metal oxide, and a shell disposed on and conforming to a surface of the core, wherein the shell includes at least one first metal oxide, a carbonaceous material, and a doped fluorine (F) element, the first metal oxide is represented by M aOb (0<a≤3 and 0< b <4, and if a is 1,2, or 3, b is not an integer), and the first metal oxide is disposed in a carbonaceous material matrix, and M is at least one metal selected from groups 2 to 13, 15, and 16 of the periodic table of elements. According to another aspect, a positive electrode including a composite positive electrode active material is provided. According to another aspect, a lithium battery is provided that includes a positive electrode, a negative electrode, and an electrolyte disposed between the positive electrode and the negative electrode. According to another aspect, there is provided a method of preparing a composite positive electrode active material, the method comprising the steps of providing a lithium transition metal oxide, providing a composite, and mechanically milling the lithium transition metal oxide and the composite, wherein the composite comprises at least one first metal oxide, a carbonaceous material, and a doped fluorine (F) element, the first metal oxide being represented by the formula M aOb (0<a≤3 and 0< b <4, and if a is 1, 2, or 3, then b is not an integer), wherein the first metal oxide is disposed within the carbonaceous material matrix, and M is at least one metal selected from groups 2 to 13, 15, and 16 of the periodic Table of the elements. Drawings The above and other aspects, features and advantages of some embodiments of the disclosure will become more apparent from the following description when taken in conjunction with the accompanying drawings in which: Fig. 1 shows XPS spectra of the undoped compound prepared in reference preparation example 1 and the fluorine (F) -doped compound prepared in preparation example 1. Fig. 2 is a schematic diagram of a lithium battery according to an example. < Description of reference numerals in the drawings > 1 Lithium cell 2 negative electrode 3 Positive electrode 4 separator 5 Battery case 6 cover Assembly Detailed Description Reference will now be made in detail to the embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the like elements throughout. In this regard, the embodiments presented may take different forms and should not be construed as limited to the descriptions set forth herein. Accordingly, the embodiments are described below merely by referring to the drawings to explain aspects of the present description. As used herein, the term "and/or (and/or)" includes any and all co