CN114864923B - Boron-doped nickel-cobalt-manganese positive electrode material and preparation method thereof - Google Patents
Boron-doped nickel-cobalt-manganese positive electrode material and preparation method thereof Download PDFInfo
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- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000007774 positive electrode material Substances 0.000 title claims description 27
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 31
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052796 boron Inorganic materials 0.000 claims abstract description 28
- 239000010405 anode material Substances 0.000 claims abstract description 22
- 239000011159 matrix material Substances 0.000 claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000011572 manganese Substances 0.000 claims abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 8
- 239000011163 secondary particle Substances 0.000 claims description 8
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910011255 B2O3 Inorganic materials 0.000 claims description 2
- 238000002441 X-ray diffraction Methods 0.000 claims description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 2
- 238000009766 low-temperature sintering Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 2
- 150000003624 transition metals Chemical group 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 21
- 239000002245 particle Substances 0.000 description 9
- 238000007873 sieving Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
Abstract
The invention provides a boron-doped nickel-cobalt-manganese anode material and a preparation method thereof. The general formula of the matrix of the boron doped nickel cobalt manganese anode material is Li a Ni b Co c Mn d M e M’ f B z O 2 M is one or more of Mg, al, zr or Ti, M' Sn, Y, mo, W, nb, ta, and a, b, c, d, e, f, z meets the following requirements: a is more than or equal to 0.95 and less than or equal to 1.2,0.7, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 0.2, d is more than or equal to 0 and less than or equal to 0.2, e is more than or equal to 0 and less than or equal to 0.02,0, f is more than or equal to 0.01,0, and z is more than or equal to 0.02. The preparation method comprises the following steps: according to the stoichiometric ratio, a lithium source, a nickel cobalt manganese ternary precursor and MB 2 Mixing the M' compounds, sintering at high temperature, washing with deionized water, drying, and sintering with a coating agent at low temperature to obtain the boron doped nickel-cobalt-manganese anode material. The invention is doped with metal element and boron element in the matrix, the boron element can enter the lattice more easily, and can replace transition metal atoms in the lattice to form B-O bond with larger bond energy, stabilize the crystal structure, improve high-temperature storage performance and reduce gas production of the battery.
Description
Technical Field
The invention belongs to ternary anode materials, and particularly relates to a boron-doped nickel-cobalt-manganese anode material and a preparation method thereof.
Background
The lithium ion battery can be used in the fields of 3C products, electric tools, new energy automobiles and the like, and the demand of the lithium ion battery is also increased sharply along with the rapid development of the new energy automobiles recently. In order to solve the demands of the market for batteries with high energy density, low cost and high cost performance, the high-nickel ternary positive electrode material is pushed to the front of research.
Researchers find that, in addition to the commonly used cationic metal modification, the use of boron compounds such as boron oxide or boric acid, or boron-doped compounds as a coating layer, can act as an insulating electrolyte, which is beneficial to improving the cycle performance of the cathode material. For example, chinese patent publication No. CN108899502a discloses a "high capacity nickel cobalt lithium manganate based composite positive electrode material and a preparation method thereof", and the method is that after washing in water by first firing, boron is coated on the surface of the positive electrode material by second firing, so that the surface structure of the material can be improved, and the interface stability can be improved, thereby improving the cycle performance. However, boron coats the surface of the material, and the generation of microcracks and the breakage of particles during high-temperature storage and circulation cannot be avoided. Particle breakage can aggravate gas production of the lithium ion battery, and the gas production can lead to gas expansion of the soft package lithium ion battery; the generated bubbles accumulate inside the battery cells and can also cause lithium precipitation at the edges of the bubbles.
Disclosure of Invention
The invention aims to solve the technical problems and overcome the defects and shortcomings in the background art, and provides the boron-doped nickel-cobalt-manganese anode material with high safety and good high-temperature storage performance.
The invention also provides a preparation method of the boron-doped nickel-cobalt-manganese anode material.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the general formula of the boron doped nickel cobalt manganese positive electrode material matrix is Li a Ni b Co c Mn d M e M’ f B z O 2 M is Mg, al, zr or Ti, M' is one or more of Sn, Y, mo, W, nb, ta, and a, b, c, d, e, f, z meets the following requirements: a is more than or equal to 0.95 and less than or equal to 1.2,0.7, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 0.2, d is more than or equal to 0 and less than or equal to 0.2, e is more than or equal to 0 and less than or equal to 0.02,0, f is more than or equal to 0.01,0, and z is more than or equal to 0.04.
The boron-doped nickel-cobalt-manganese anode material is a secondary sphere particle, and the primary particles on the surface and in the surface of the secondary sphere particle show preferential growth, and the secondary sphere particle is characterized in that: the crystallite size of the (104) crystal plane calculated by using an X-ray diffraction method and a Scherrer formula is 48.0nm or more and 66.5nm or less.
Preferably, the ratio of f to z is in the range of 1:4 to 1:20, more preferably, the ratio of f to z is in the range of 1:4 to 1:10, and in this ratio range, the preferred directional growth of primary particles in the secondary spherical particles is more favored.
Preferably, the secondary particle size D10 of the boron doped nickel cobalt manganese positive electrode material is 8-12 mu m, D50 is 10-15 mu m, and D90 is 15-25 mu m.
The preparation method of the boron-doped nickel-cobalt-manganese anode material comprises the following steps:
(1) According to the stoichiometric ratio, a lithium source, a nickel cobalt manganese ternary precursor and MB 2 Mixing the compounds of M' and sintering at high temperature to obtain a matrix;
(2) And washing and drying the matrix by deionized water, and sintering the matrix and the coating agent at low temperature to obtain the boron-doped nickel-cobalt-manganese anode material.
Preferably, in the step (1), the lithium source is selected from one or more of anhydrous lithium hydroxide, lithium hydroxide monohydrate and lithium carbonate.
Preferably, in step (1), the compound of M' is selected from SnO 2 、Y 2 O 3 、MoO 3 、WO 3 、Nb 2 O 5 、Ta 2 O 5 One or more of them.
Preferably, in step (1), the high temperature sintering process is: heating to 450-550 ℃ at a speed of 1-5 ℃/min under the air or oxygen atmosphere, preserving heat and sintering for 3-5h, then heating to 700-850 ℃ at a temperature of 1-3 ℃ and preserving heat for 8-15h, and then naturally cooling to room temperature.
Preferably, in the step (2), the low-temperature sintering process is as follows: heating to 300-400 ℃ at 1-5 ℃ in air or oxygen atmosphere, preserving heat for 3-6h, and naturally cooling to room temperature.
Preferably, the specific steps of washing and drying are: washing a burned substrate with deionized water at 4-15 ℃ for 10-20min according to the solid-liquid ratio of 1:1-2:1, and then placing the burned substrate in a vacuum oven for vacuum drying for 5-15h.
Preferably, the coating agent is one or more of boric acid and boric oxide.
Compared with the prior art, the invention has the advantages that:
(1) Compared with the traditional oxide cladding doping, the boron doped nickel-cobalt-manganese anode material is doped with metal elements and boron elements simultaneously, the boron elements can enter the lattice more easily, transition metal atoms in the lattice can be replaced, a B-O bond with larger bond energy is formed, the crystal structure is stabilized, the high-temperature storage performance is improved, and the gas production of the battery is reduced.
(2) The boron doped nickel cobalt manganese anode material is doped with Sn, Y, mo, W, nb or Ta, the elements are doped into the lattice structure of the anode material through high-temperature sintering, the effect of changing the growth orientation of primary particles in the secondary sphere material is achieved, after the boron doped nickel cobalt manganese anode material is co-doped with B, the growth of the primary particles shows the characteristic of orientation preferred orientation, the result is that the size range of microcrystals of a 104 crystal face is 48.0-66.5nm, the morphology is similar to single crystals, the occurrence of cracks in the secondary sphere particles in the circulation process can be effectively reduced, the high-temperature mechanical property of the material is improved, and the high-temperature circulation stability of the material is improved.
(3) After the primary sintered substrate is washed, the content of residual lithium on the surface of the material can be effectively reduced, then the secondary sintered coating B can generate a fast ion conductor coating layer through reaction with the residual lithium on the surface, so that the surface structure damage caused by water washing is repaired, the surface impedance of the material is reduced, and the lithium ion conductivity is improved.
(4) According to the preparation method of the boron-doped nickel-cobalt-manganese positive electrode material, the sectional sintering is beneficial to improving the crystallinity of the positive electrode material and the formation of a pure phase structure, reducing the occurrence of cation mixed discharge phenomenon and improving the electrochemical performance of the positive electrode material.
Drawings
FIG. 1 is an electron microscope image of a boron doped nickel cobalt manganese positive electrode material of example 1;
FIG. 2 is an electron microscope image of the boron doped nickel cobalt manganese positive electrode material of example 2;
FIG. 3 is an electron micrograph of the boron doped nickel cobalt manganese positive electrode material of comparative example 1;
FIG. 4 is a gas production line graph of a full cell of boron doped nickel cobalt manganese positive electrode material of example 1 and comparative example 1 stored at 60℃for 3 weeks;
FIG. 5 is a cross-sectional view of an electron microscope of the boron doped nickel cobalt manganese anode material of example 1 after 100 weeks of high temperature cycling;
fig. 6 is a cross-sectional view of an electron microscope of the boron-doped nickel cobalt manganese positive electrode material of comparative example 1 after 100 weeks of high temperature cycle.
Detailed Description
The invention will be described more fully hereinafter with reference to the preferred embodiments for the purpose of facilitating an understanding of the invention, but the scope of the invention is not limited to the specific embodiments described below.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1:
boron doped nickel cobalt manganese positive electrode material, and the general formula of matrix is Li 1.00 Ni 0.845 Co 0.07 Mn 0.05 Mg 0.01 Sn 0.005 B 0.0 2 O 2.00 Secondary particle size d10=9.15 μm, d50=13.04 μm, d90=15.40 μm, and the numerical value of the secondary particle size was measured by a malvern 3000 laser particle sizer. According to the Scherrer formula: d=kγ/Bcos θ (K is Scherrer constant, k=0.89, γ is X-ray wavelength=0.15418 nm, b is width of half-width of crystallite size, θ is bragg angle), and the boron-doped cathode material was analyzed by XRD, and the crystallite size d=52.4 nm was calculated from the analysis result (peak of 104 crystal plane) by Scherrer formula.
The method for preparing the boron doped nickel cobalt manganese anode material comprises the following steps:
(1) Ni is a precursor of a high nickel positive electrode material 0.88 Co 0.07 Mn 0.05 (OH) 2 、LiOH·H 2 O、MgB 2 、SnO 2 Mixing in a high-speed mixer at a molar ratio of 1:1.05:0.01:0.005, mixing at a rotating speed of 1500rpm/min for 30min at a high speed to obtain a mixed material, placing the mixed material in a sintering furnace, heating to 500 ℃ at a heating rate of 3 ℃/min under an oxygen atmosphere, carrying out heat preservation and sintering for 5h, heating to 750 ℃ at a heating rate of 1.5 ℃/min, carrying out heat preservation and sintering for 10h, naturally cooling to room temperature, crushing and sieving (300 meshes) to obtain the boron-doped one-step sintered base material.
(2) Washing the primary burned matrix with deionized water for 15min, wherein the solid-to-liquid ratio is 1:1, controlling the temperature of the deionized water to be 10 ℃, placing the sample in a vacuum oven for vacuum drying at 160 ℃ for 8h after washing, naturally cooling to room temperature, and sieving with 300 meshes to obtain the washed sample.
(3) And (3) putting the washed sample and boric acid into a high-speed mixer according to the mass ratio of 1:0.001, mixing at the rotating speed of 1500rpm/min, mixing at a high speed for 30min to obtain a mixed material, placing the mixed material into a sintering furnace, heating to 350 ℃ at the heating rate of 2 ℃/min under the oxygen atmosphere, preserving heat and sintering for 5h, naturally cooling to room temperature, and sieving by 300 meshes to obtain the boron-doped nickel-cobalt-manganese anode material with the boron coating layer.
Example 2:
boron doped nickel cobalt manganese positive electrode material, and the general formula of matrix is Li 1.00 Ni 0.867 Co 0.05 Mn 0.05 Al 0.01 Sn 0.003 B 0.0 2 O 2.00 Secondary particle size d10=10.32 μm, d50=13.56 μm, d90=16.41 μm, and the numerical value of the secondary particle size was obtained by a malvern 3000 laser particle sizer test. The crystallite size was calculated using Scherrer formula to give d=54.6 nm.
The method for preparing the boron doped nickel cobalt manganese anode material comprises the following steps:
(1) Front of high nickel positive electrode materialNi as a precursor 0.90 Co 0.05 Mn 0.05 (OH) 2 、LiOH·H 2 O、AlB 2 、SnO 2 Mixing in a high-speed mixer at a mol ratio of 1:1.03:0.01:0.003, mixing at a rotating speed of 1500rpm/min for 30min at a high speed to obtain a mixed material, placing the mixed material in a sintering furnace, heating to 500 ℃ at a heating rate of 3 ℃/min under an oxygen atmosphere, carrying out heat preservation and sintering for 5h, heating to 750 ℃ at a heating rate of 1.5 ℃/min, carrying out heat preservation and sintering for 10h, naturally cooling to room temperature, crushing and sieving (300 meshes) to obtain the boron-doped one-step sintered base material.
(2) Washing the primary burned matrix with deionized water for 15min, wherein the solid-to-liquid ratio is 1:1, controlling the temperature of the deionized water to be 10 ℃, placing the sample in a vacuum oven for vacuum drying at 160 ℃ for 8h after washing, naturally cooling to room temperature, and sieving with 300 meshes to obtain the washed sample.
(3) And (3) putting the washed sample and boric acid into a high-speed mixer according to the mass ratio of 1:0.001, mixing at the rotating speed of 1500rpm/min, mixing at a high speed for 30min to obtain a mixed material, placing the mixed material into a sintering furnace, heating to 350 ℃ at the heating rate of 2 ℃/min under the oxygen atmosphere, preserving heat and sintering for 5h, naturally cooling to room temperature, and sieving by 300 meshes to obtain the boron-doped nickel-cobalt-manganese anode material with the boron coating layer.
Example 3:
boron doped nickel cobalt manganese positive electrode material, and the general formula of matrix is Li 1.00 Ni 0.848 Co 0.06 Mn 0.06 Mg 0.01 Mo 0.002 B 0.0 2 O 2.00 Secondary particle size d10=9.92 μm, d50=13.32 μm, d90=15.22 μm, and the numerical value of the secondary particle size was measured by a malvern 3000 laser particle sizer. The crystallite size was calculated using Scherrer formula to give d=62.6 nm.
The method for preparing the boron doped nickel cobalt manganese anode material comprises the following steps:
(1) Ni is a precursor of a high nickel positive electrode material 0.88 Co 0.06 Mn 0.06 (OH) 2 、LiOH·H 2 O、MgB 2 、MoO 3 In a molar ratio of 1:1.06:0.01:0.002Mixing in a high-speed mixer at 1500rpm/min for 30min to obtain a mixed material, placing the mixed material in a sintering furnace, heating to 500 ℃ at a heating rate of 3 ℃/min under an oxygen atmosphere, preserving heat and sintering for 5h, heating to 750 ℃ at a heating rate of 1.5 ℃/min and preserving heat and sintering for 10h, naturally cooling to room temperature, crushing and sieving (300 meshes) to obtain the boron-doped primary sintering matrix material.
(2) Washing the primary burned matrix with deionized water for 15min, wherein the solid-to-liquid ratio is 1:1, controlling the temperature of the deionized water to be 10 ℃, placing the sample in a vacuum oven for vacuum drying at 160 ℃ for 8h after washing, naturally cooling to room temperature, and sieving with 300 meshes to obtain the washed sample.
(3) And (3) putting the washed sample and boric acid into a high-speed mixer according to the mass ratio of 1:0.001, mixing at the rotating speed of 1500rpm/min, mixing at a high speed for 30min to obtain a mixed material, placing the mixed material into a sintering furnace, heating to 350 ℃ at the heating rate of 2 ℃/min under the oxygen atmosphere, preserving heat and sintering for 5h, naturally cooling to room temperature, and sieving by 300 meshes to obtain the boron-doped nickel-cobalt-manganese anode material with the boron coating layer.
Comparative example 1:
compared with example 1, the difference is that: no SnO is added 2 The other conditions or parameters were the same as in example 1.
Comparative example 2:
compared with example 1, the difference is that: no MgB is added 2 The other conditions or parameters were the same as in example 1.
Comparative example 3:
compared with example 1, the difference is that: boric acid is not added in the secondary sintering process, and the other conditions or parameters are the same as those of the embodiment 1.
Comparative example 4:
compared with example 1, the difference is that: mgB is not added in the primary sintering process 2 ，SnO 2 Boric acid is not added in the secondary sintering process, and the other conditions or parameters are the same as those in example 1.
TABLE 1
Claims (9)
1. A boron-doped nickel-cobalt-manganese positive electrode material is characterized in that the general formula of a matrix of the boron-doped nickel-cobalt-manganese positive electrode material is Li a Ni b Co c Mn d M e M’ f B z O 2 M is Mg, al, zr or Ti, M' is one or more of Sn, Y, mo, W, nb, ta, and a, b, c, d, e, f, z meets the following requirements: a is more than or equal to 0.95 and less than or equal to 1.2,0.7, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 0.2, d is more than or equal to 0 and less than or equal to 0.2, e is more than or equal to 0 and less than or equal to 0.02,0, f is more than or equal to 0.01,0, and z is more than or equal to 0.04;
the crystallite size of the (104) crystal face calculated by an X-ray diffraction method and a Scherrer formula of the boron-doped nickel-cobalt-manganese positive electrode material is more than 48.0nm and less than 66.5 nm.
2. The boron-doped nickel cobalt manganese positive electrode material according to claim 1, wherein the ratio of f to z ranges from 1: 4-1: 20.
3. the boron-doped nickel cobalt manganese positive electrode material according to claim 1 or 2, wherein the secondary particle diameter D10 of the boron-doped nickel cobalt manganese positive electrode material is 8-12 μm, D50 is 10-15 μm, and D90 is 15-25 μm.
4. A method for preparing the boron doped nickel cobalt manganese positive electrode material according to any one of claims 1 to 3, comprising the steps of:
(1) According to the stoichiometric ratio, a lithium source, a nickel cobalt manganese ternary precursor and MB 2 Mixing the compounds of M' and sintering at high temperature to obtain a matrix;
(2) And washing and drying the matrix by deionized water, and sintering the matrix and the coating agent at low temperature to obtain the boron-doped nickel-cobalt-manganese anode material.
5. The method of claim 4, wherein in step (1), the lithium source is selected from one or more of anhydrous lithium hydroxide, lithium hydroxide monohydrate, and lithium carbonate.
6. The process of claim 4, wherein in step (1), the compound of M' is selected from the group consisting of SnO 2 、Y 2 O 3 、MoO 3 、WO 3 、Nb 2 O 5 、Ta 2 O 5 One or more of them.
7. The method of claim 4, wherein in step (1), the high temperature sintering process is: heating to 450-550 ℃ at a speed of 1-5 ℃/min under the air or oxygen atmosphere, preserving heat and sintering for 3-5h, heating to 700-850 ℃ at a temperature of 1-3 ℃ and preserving heat for 8-15h, and naturally cooling to room temperature.
8. The method of claim 4, wherein in step (2), the low temperature sintering process is: heating to 300-400 ℃ at 1-5 ℃ in air or oxygen atmosphere, preserving heat for 3-6h, and naturally cooling to room temperature.
9. The method of claim 4, wherein the coating agent is one or more of boric acid and boric oxide.
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