CN114975912B - Ternary positive electrode material and application thereof - Google Patents
Ternary positive electrode material and application thereof Download PDFInfo
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- CN114975912B CN114975912B CN202210474535.7A CN202210474535A CN114975912B CN 114975912 B CN114975912 B CN 114975912B CN 202210474535 A CN202210474535 A CN 202210474535A CN 114975912 B CN114975912 B CN 114975912B
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 70
- 239000011164 primary particle Substances 0.000 claims abstract description 38
- 239000011163 secondary particle Substances 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 31
- 239000010406 cathode material Substances 0.000 claims description 12
- 229910052810 boron oxide Inorganic materials 0.000 claims description 11
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 7
- 230000010287 polarization Effects 0.000 abstract description 6
- 238000005336 cracking Methods 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 description 20
- 238000002156 mixing Methods 0.000 description 11
- 238000005245 sintering Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 239000004327 boric acid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910016722 Ni0.5Co0.2Mn0.3 Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/50—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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a ternary positive electrode material and application thereof, wherein the ternary positive electrode material comprises primary particles and secondary particles composed of the primary particles; the primary particles have an average particle diameter of 200nm to 800nm; particle diameter D of the secondary particles 50 From 2.2 μm to 2.8 μm. According to the invention, by controlling the granularity of the primary particles and the secondary particles of the ternary positive electrode material, the problem of secondary particle breakage caused by grain boundary cracking of the ternary positive electrode material in the battery charging and discharging process is solved, the multiplying power and the power performance of the material are greatly improved, and the polarization and the ohmic internal resistance of the battery are reduced.
Description
Technical Field
The invention belongs to the technical field of batteries, and relates to a ternary positive electrode material, in particular to a ternary positive electrode material and application thereof.
Background
In the current battery anode material, no grain boundary exists in the single crystal ternary material, so that the problems of grain boundary breakage and performance degradation caused by the grain boundary breakage can be effectively solved, but the ohmic internal resistance of the single crystal material is obviously increased due to larger particles and longer lithium ion migration channels, and the multiplying power is limited, so that the power performance is poor. The common polycrystal ternary anode material is in a secondary spherical state of about 5 microns formed by agglomeration of nanoscale primary particles.
Although the smaller primary particles of the ternary material can shorten the lithium ion diffusion channel, reduce the lithium ion diffusion resistance and greatly improve the power performance. However, since a large number of crystal boundaries exist in the polycrystalline ternary material, in the charge and discharge process of the battery, the crystal boundaries are easy to crack due to anisotropic lattice change, secondary particles are easy to crush, the specific surface area and interface side reaction are rapidly increased, the impedance of the battery is increased, and the performance is rapidly reduced.
Based on the above research, it is necessary to provide a ternary positive electrode material, which can avoid the breakage of secondary particles in the polycrystalline ternary positive electrode material, reduce polarization and resistance, and greatly improve power and cycle performance.
Disclosure of Invention
The invention aims to provide a ternary positive electrode material and application thereof, wherein the granularity of primary particles and secondary particles of the ternary positive electrode material is adjusted, so that cracking of the secondary particles is avoided, polarization is obviously reduced, resistance is reduced, and the power performance of the material is greatly improved.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a ternary positive electrode material comprising primary particles, and secondary particles consisting of the primary particles;
the primary particles have an average particle diameter of 200nm to 800nm;
particle diameter D of the secondary particles 50 From 2.2 μm to 2.8 μm.
According to the invention, the granularity of the primary particles and the secondary particles of the ternary positive electrode material is controlled, so that the sphericity of the ternary positive electrode material is improved, the problem of secondary particle breakage caused by grain boundary cracking of the ternary positive electrode material in the battery charging and discharging process is avoided, the multiplying power and the power performance of the material are greatly improved, and the polarization and the ohmic internal resistance of the battery are reduced.
The primary particles have an average particle diameter of 200nm to 800nm, and may be, for example, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, 650nm, 700nm, 750nm or 800nm, but are not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Particle diameter D of the secondary particles 50 From 2.2 μm to 2.8 μm, for example, 2.2 μm, 2.25 μm, 2.3 μm, 2.35 μm, 2.4 μm, 2.45 μm, 2.5 μm, 2.55 μm, 2.6 μm, 2.65 μm, 2.7 μm, 2.75 μm or 2.8 μm, but not limited to the values recited, within the range of valuesThe values not listed apply equally well.
Preferably, the surface of the ternary positive electrode material is coated with boron oxide.
Preferably, the boron oxide is in a glassy state.
The surface of the ternary positive electrode material is also coated with the glassy boron oxide, and the coated glassy boron oxide can improve the sphericity of the ternary positive electrode material and enable the surface of the ternary positive electrode material to be smoother and more round, so that the ternary positive electrode material has good fluidity and stable structure, unstable structure caused by uneven lithium deintercalation in the charging and discharging process of the material is relieved, accumulation of stress areas is greatly reduced, crushing tendency of the material is delayed, and the cycle performance is improved.
Preferably, the ternary cathode material is doped with a transition metal element.
Preferably, the ternary cathode material is doped with an Al element.
Preferably, the ternary positive electrode material has the chemical formula of Li a Ni x Co y Mn 1-x-y Al b B c O 2 Wherein x is more than 0 and less than 1, y is more than 0 and less than 1, a is more than or equal to 1 and less than or equal to 1.1, b is more than or equal to 0.005 and less than or equal to 0.1,0.001, and c is more than or equal to 0.01.
The chemical formula of the ternary positive electrode material is Li a Ni x Co y Mn 1-x-y Al b B c O 2 Where 0 < x < 1, for example, may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9, but are not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The chemical formula of the ternary positive electrode material is Li a Ni x Co y Mn 1-x-y Al b B c O 2 Where 0 < y < 1, for example, may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9, but are not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The chemical formula of the ternary positive electrode material is Li a Ni x Co y Mn 1-x-y Al b B c O 2 Wherein a is more than or equal to 1 and less than or equal to 1.1,for example, 1, 1.02, 1.04, 1.06, 1.08, or 1.1, but is not limited to the recited values, as are other non-recited values within the range of values.
The chemical formula of the ternary positive electrode material is Li a Ni x Co y Mn 1-x-y Al b B c O 2 Wherein, b is 0.005.ltoreq.b.ltoreq.0.1, which may be, for example, 0.005, 0.008, 0.01, 0.03, 0.05, 0.08 or 0.1, but is not limited to the values recited, other non-recited values within the numerical range are equally applicable.
The chemical formula of the ternary positive electrode material is Li a Ni x Co y Mn 1-x-y Al b B c O 2 Wherein, c is 0.001.ltoreq.0.01, for example, 0.001, 0.003, 0.005, 0.008 or 0.01 can be used, but the present invention is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
The preparation method of the ternary positive electrode material comprises the following steps:
mixing lithium salt, a ternary positive electrode material precursor and an oxide of a doping element according to the formula amount, and mixing the obtained co-doped mixture with boric acid after primary sintering, and carrying out secondary sintering to obtain the ternary positive electrode material.
The ternary positive electrode material with the target primary particle size and the target secondary particle size is obtained by controlling the sintering process and the like.
Preferably, the primary sintering includes heating to 430 ℃ to 470 ℃ at a first heating rate and then heating to 860 ℃ to 880 ℃ at a second heating rate.
The primary sintering includes heating to 430 c to 470 c at a first rate of heating, which may be, for example, 430 c, 440 c, 450 c, 460 c or 470 c, but is not limited to the recited values, other non-recited values within the range of values are equally applicable,
the temperature is raised to 860 ℃ to 880 ℃ at the second temperature raising rate, and may be 860 ℃, 865 ℃, 870 ℃, 875 ℃, or 880 ℃, for example, but not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the first heating rate is 2.5 ℃/min to 3.5 ℃/min, for example, 2.5 ℃/min, 3.0 ℃/min or 3.5 ℃/min, but is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the second heating rate is 5.5 ℃/min to 6.5 ℃/min, for example, may be 5.5 ℃/min, 6.0 ℃/min or 6.5 ℃/min, but is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the atmosphere of the primary sintering is an air atmosphere.
Preferably, the secondary sintering temperature is 250 ℃ to 350 ℃, for example, 250 ℃,300 ℃ or 350 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the atmosphere of the secondary sintering is an air atmosphere.
Preferably, the molar ratio of the doping mixture to boric acid is 1 (0.005 to 0.015), for example, 1:0.005, 1:0.01 or 1:0.015, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the particle size of the doped element oxide is nano-scale.
Preferably, the particle size of the boric acid is nano-scale.
The ternary positive electrode material precursor is doped with carbonate ions and is prepared by a coprecipitation method.
In a second aspect, the present invention provides an electrochemical device comprising a ternary positive electrode material as described in the first aspect.
Preferably, the negative electrode material of the electrochemical device includes graphite.
Preferably, the electrolyte of the electrochemical device includes lithium hexafluorophosphate.
In a third aspect, the present invention provides an electronic device comprising an electrochemical apparatus as described in the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, by controlling the granularity of the primary particles and the secondary particles of the ternary positive electrode material, the problem of breakage of the secondary particles caused by the occurrence of crystal boundary cracking of the ternary positive electrode material is avoided, the multiplying power and the power performance of the material are greatly improved, and the polarization and the ohmic internal resistance of the battery are reduced; meanwhile, the glassy boron oxide coated on the surface of the ternary positive electrode material ensures that the ternary positive electrode material has good fluidity and stable structure, relieves the unstable structure caused by uneven lithium intercalation and deintercalation of the material in the charge and discharge process, greatly reduces the accumulation of stress areas, delays the crushing tendency of the material, and improves the cycle performance.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a ternary positive electrode material comprising primary particles and secondary particles composed of the primary particles, wherein the average particle diameter of the primary particles is 500nm, and the particle diameter D of the secondary particles 50 2.5 μm;
the surface of the ternary positive electrode material is coated with glassy boron oxide and doped with Al element;
the chemical formula of the ternary positive electrode material is Li 1.06 Ni 0.5 Co 0.2 Mn 0.3 Al 0.01 B 0.005 O 2 ；
The preparation method of the ternary positive electrode material comprises the following steps:
(a) Mixing LiOH, a ternary positive electrode material precursor and aluminum oxide at a mixing molar ratio of 1.06:1 at a rotating speed of 800r/min to obtain a co-doped mixture;
(b) Heating the co-doped mixture in the step (a) to 450 ℃ at a heating rate of 3.0 ℃/min in an air atmosphere, preserving heat for 3 hours, heating to 870 ℃ at a heating rate of 6.5 ℃/min, and preserving heat for 10 hours to obtain a co-doped ternary material;
(c) Mixing nanoscale boric acid with the molar ratio of 0.01:1 with the co-doped ternary material in the step (b) at the rotating speed of 500r/min for 20min, and then performing secondary sintering for 5h at the temperature of 300 ℃ in an air atmosphere to obtain the ternary positive electrode material.
Example 2
The embodiment provides a ternary positive electrode material comprising primary particles and secondary particles composed of the primary particles, wherein the average particle diameter of the primary particles is 200nm, and the particle diameter D of the secondary particles 50 2.8 μm;
the surface of the ternary positive electrode material is coated with glassy boron oxide and doped with Al element;
the chemical formula of the ternary positive electrode material is Li 1.06 Ni 0.5 Co 0.2 Mn 0.3 Al 0.01 B 0.005 O 2 ；
The preparation method of the ternary positive electrode material comprises the following steps:
(a) Mixing LiOH, a ternary positive electrode material precursor and aluminum oxide at a mixing molar ratio of 1.06:1 at a rotating speed of 800r/min to obtain a co-doped mixture;
(b) Heating the co-doped mixture in the step (a) to 430 ℃ at a heating rate of 2.5 ℃/min in an air atmosphere, preserving heat for 3h, heating to 880 ℃ at a heating rate of 6.5 ℃/min, and preserving heat for 10h to obtain a co-doped ternary material;
(c) Mixing nanoscale boric acid with the molar ratio of 0.01:1 with the co-doped ternary material in the step (b) at the rotating speed of 500r/min for 20min, and then performing secondary sintering for 5h at the temperature of 250 ℃ in an air atmosphere to obtain the ternary positive electrode material.
Example 3
The embodiment provides a ternary positive electrode material comprising primary particles and secondary particles composed of the primary particles, wherein the average particle size of the primary particles is 800nm, and the particle size D of the secondary particles 50 2.2 μm;
the surface of the ternary positive electrode material is coated with glassy boron oxide and doped with Al element;
the three partsThe chemical formula of the meta-positive electrode material is Li 1.06 Ni 0.5 Co 0.2 Mn 0.3 Al 0.01 B 0.005 O 2 ；
The preparation method of the ternary positive electrode material comprises the following steps:
(a) Mixing LiOH, a ternary positive electrode material precursor and aluminum oxide at a mixing molar ratio of 1.06:1 at a rotating speed of 800r/min to obtain a co-doped mixture;
(b) In an air atmosphere, heating the co-doped mixture in the step (a) to 470 ℃ at a heating rate of 3.5 ℃/min, preserving heat for 3 hours, heating to 860 ℃ at a heating rate of 5.5 ℃/min, and preserving heat for 10 hours to obtain a co-doped ternary material;
(c) Mixing nanoscale boric acid with the molar ratio of 0.01:1 with the co-doped ternary material in the step (b) at the rotating speed of 500r/min for 20min, and then performing secondary sintering for 5h at the temperature of 350 ℃ in an air atmosphere to obtain the ternary positive electrode material.
The ternary cathode materials provided in examples 4 and 5 are as shown in table 2, except that the average particle diameter of the primary particles is changed, which is the same as example 1.
The ternary cathode materials provided in examples 6 and 7 are shown in Table 3, except that the secondary particles have a particle size D 50 Except for the variation, the rest was the same as in example 1.
The ternary cathode material provided in example 8 is as shown in table 4, except that the glassy boron oxide is not coated, and is the same as in example 1.
The ternary positive electrode materials provided in comparative examples 1 and 2 are shown in Table 5, except that the primary particles had an average particle diameter and the secondary particles had a particle diameter D 50 Except for the variation, the rest was the same as in example 1.
The ternary positive electrode material, the conductive carbon black, the conductive carbon tube and the polyvinylidene fluoride obtained in the above examples and comparative example are added into a nitrogen methyl pyrrolidone solvent, the mass ratio of the conductive carbon black, the conductive carbon tube and the polyvinylidene fluoride is 97:1:1, the prepared slurry is coated on an aluminum foil, and the aluminum foil is dried for 12 hours at 60 ℃ under vacuum condition, so that the surface density of the ternary positive electrode material is 18g/cm 2 The pole piece of (C) is rolled to obtain the pole piece with the compaction of 3.4g/cm 3 Is a positive electrode sheet of (a); and assembling the obtained positive plate and a graphite negative plate, a polyethylene diaphragm and lithium hexafluorophosphate solution electrolyte into a 1Ah soft package battery.
The assembled soft package battery disassembled positive plate is subjected to ultrasonic dispersion of powder obtained by scraping in an NMP solvent, centrifugal separation is carried out to remove soluble matters, the binder PVDF in the powder can be removed by repeating the steps for three times, and the cleaned powder is placed in a pure oxygen environment at 300 ℃ to be sintered for 12 hours, so that the conductive agent is fully oxidized into carbon dioxide, and finally the ternary positive plate material with higher purity and unchanged particle size is obtained.
The obtained ternary positive electrode material adopts a laser tester to test the particle size of secondary particles; and optionally selecting SEM pictures of three groups of visual fields of the ternary positive electrode material under 2000 times of magnification, measuring the major axis and the minor axis of primary particles by using nanomeasure software by adopting a crisscross method, taking the average value of the major axis and the minor axis as the particle size of the primary particles, measuring the particle sizes of all the primary particles in the pictures by using the crisscross method, and calculating the average value of the particle sizes of the primary particles of the three pictures to obtain the primary particle size of the ternary positive electrode material.
The soft package battery performs capacity test and first efficiency test under the conditions of 0.33C and 4.25V; testing the direct current internal resistance of discharge under the conditions of 25 ℃,50% SOC and 30s 4C; testing the rate performance under the condition of 10C/0.33C; the cycle retention was tested at 25℃and 3C 4.2V.
The test results are shown in the following table:
TABLE 1
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
TABLE 5
The following points can be seen from the above table:
(1) From examples 1 to 8, it is known that the ternary cathode material of the present invention can achieve improvement of the overall electrochemical performance of the battery by adjusting the particle sizes of the primary particles and the secondary particles; as is clear from examples 1 and 4 to 7, when the particle diameter D of the secondary particles is 50 The electrochemical performance of the battery is changed when the average particle diameter of the primary particles is changed, and the particle diameter D of the secondary particles is changed when the average particle diameter of the primary particles is unchanged 50 When the composition is changed, the electrochemical performance of the battery is also influenced, and the ternary positive electrode material with excellent comprehensive performance is obtained by matching the primary particles and the secondary particles.
(2) As is apparent from example 1, comparative example 1 and comparative example 2, the conventional-sized ternary cathode material cannot avoid the breakage of the secondary particles during charge and discharge, thereby greatly reducing the overall performance as compared with example 1.
In summary, the invention provides the ternary positive electrode material, and the granularity of the primary particles and the secondary particles of the ternary positive electrode material is controlled, so that the sphericity of the ternary positive electrode material is improved, the problem of secondary particle breakage in the battery charging and discharging process is avoided, the multiplying power and the power performance of the material are greatly improved, and the polarization and the ohmic internal resistance of the battery are reduced.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.
Claims (8)
1. A ternary positive electrode material, characterized in that the ternary positive electrode material comprises primary particles and secondary particles composed of the primary particles;
the primary particles have an average particle diameter of 200nm to 800nm;
particle diameter D of the secondary particles 50 2.2 μm to 2.8 μm;
and the surface of the ternary positive electrode material is coated with boron oxide, and the boron oxide is in a glassy state.
2. The ternary cathode material of claim 1, wherein the ternary cathode material is doped with a transition metal element.
3. The ternary cathode material of claim 2, wherein the ternary cathode material is doped with elemental Al.
4. The ternary positive electrode material of claim 3, wherein the ternary positive electrode material has a chemical formula of Li a Ni x Co y Mn 1-x-y Al b B c O 2 Wherein x is more than 0 and less than 1, y is more than 0 and less than 1, a is more than or equal to 1 and less than or equal to 1.1, b is more than or equal to 0.005 and less than or equal to 0.1,0.001, and c is more than or equal to 0.01.
5. An electrochemical device comprising the ternary cathode material according to any one of claims 1 to 4.
6. The electrochemical device of claim 5, wherein the negative electrode material of the electrochemical device comprises graphite.
7. The electrochemical device of claim 5, wherein the electrolyte of the electrochemical device comprises lithium hexafluorophosphate.
8. An electronic device, characterized in that it comprises the electrochemical apparatus according to any one of claims 5-7.
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