CN109786732B - Multimodal powder based on lithium transition metal oxides and use in rechargeable batteries - Google Patents
Multimodal powder based on lithium transition metal oxides and use in rechargeable batteries Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 141
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 title claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 117
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 238000005245 sintering Methods 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 24
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 17
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 73
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 71
- 239000000203 mixture Substances 0.000 claims description 41
- 230000002950 deficient Effects 0.000 claims description 38
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 35
- 229910052723 transition metal Inorganic materials 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- 150000003624 transition metals Chemical class 0.000 claims description 16
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- 229910052726 zirconium Inorganic materials 0.000 claims description 15
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 14
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 229910052727 yttrium Inorganic materials 0.000 claims description 13
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- 229910052787 antimony Inorganic materials 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 5
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910020910 Co1-xMx Inorganic materials 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 2
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 2
- 238000011049 filling Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 239000010405 anode material Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000005056 compaction Methods 0.000 description 25
- 239000010410 layer Substances 0.000 description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 11
- 239000000395 magnesium oxide Substances 0.000 description 11
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000010936 titanium Substances 0.000 description 11
- 239000010406 cathode material Substances 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- 230000005611 electricity Effects 0.000 description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 239000008188 pellet Substances 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000007771 core particle Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Images
Classifications
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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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a multimodal powder based on lithium transition metal oxide and application thereof in a rechargeable battery, wherein the preparation method comprises the steps of mixing a primary product or a secondary product of powder A with a secondary product of powder B and/or a primary product of powder C, adding transition metal oxide or hydroxide for mixing, and sintering at a temperature of at least 500 ℃ in an oxygen-containing atmosphere to obtain a finished product of multimodal powder based on lithium transition metal oxide. The invention forms the multimodal structure powder by a plurality of particles to form the anode material with high filling rate and stable structure applied under high voltage. The method is simple, and the prepared multimodal material consists of various particles, so that the filling requirement is better met, the filling effect is improved, the porosity is reduced, the material obtains higher volume energy density, and the material has better cycle performance.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to multimodal powder based on a lithium transition metal oxide and application of the multimodal powder in a rechargeable battery.
Background
The rechargeable lithium ion battery has the characteristics of high power density, high energy and long service life, and is widely applied to the field of 3C. As the amount of lithium cobaltate material used increases, the safety and energy density of the rechargeable battery are two related problems.
For lithium cobaltate powders, factors that affect density include particle shape, primary particle size, and particle size distribution. Increasing the compaction density and decreasing the porosity can increase the electrode density. The positive electrode of the lithium cobaltate full-cell is compacted generally at 3.9-4.2g/cm3The compaction density is improved by 0.1g/cm3The energy density of the battery can be greatly improved. When the full-electric charging cut-off voltage of the lithium cobaltate is increased by 0.1V, the specific capacity is increased by 10 percent.
Mixing multiple different particle size cathode material powders with each other fills large particle voids, reducing porosity, which can increase the energy density of a lithium battery because more active material fits into the limited volume of the battery.
Currently, Li metal cannot be used as an anode due to insufficient safety of a rechargeable battery. As a result, the lithium needs to be provided by the cathode, which limits the choice of cathode materials. The cathode material is a typical layered lithium-containing intercalation material. Lithium in and out of the material can be reversibly stored. Each delithiated transition metal oxide is in good contact with the organic electrolyte during charging, which fills the pores between the particles. The cut-off voltage is increased, the lithium cobaltate loses Li and undergoes phase change under the high-voltage charging state, so that the structure is unstable, oxygen is easily released under the action of an electrolyte, the cobalt dissolution phenomenon is caused, the safety is reduced, and in the circulation process, the discharge capacity is reduced due to the existence of the cobalt dissolution phenomenon, so that the circulation performance is deteriorated; the contact between the surface of the lithium cobaltate positive electrode material and the electrolyte is reduced by a doping and coating method, and the safety performance is improved.
High bulk density is readily achieved using relatively large and dense particles. Increasing the material compaction density, decreasing the porosity, and slowing the Li diffusion rate in lithium cobaltate requires shortening the diffusion paths within the particles, which can reduce the particle size, or increasing the material porosity, which can increase the BET of the material, which is very difficult to achieve with nano-sized cathode materials. It is very important to fill the gaps between large particles with micro and small particles, to reduce porosity, to increase compacted density, and to increase the lithium diffusion rate.
Disclosure of Invention
The primary object of the present invention is to provide a method for the preparation of multimodal powders based on lithium transition metal oxides.
It is another object of the present invention to provide multimodal powders prepared by the above process having at least three number of particle size peaks, high packing density, high rate capability, improved discharge capacity with better cycling stability at higher voltages.
It is a further object of the present invention to provide the use of the multimodal powder as described above as a positive electrode material for rechargeable batteries.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a multimodal powder based on lithium transition metal oxide comprising the steps of:
(1) mixing a lithium source, a cobalt source and transition metal oxide or hydroxide powder, wherein the molar ratio of Li to Co in the mixture is 0.98-1.08, and sintering in air or oxygen atmosphere to obtain a primary product of powder A; the particle size of the obtained powder A is 15-30 μm, preferably 17-26 μm;
in the step (1), the molar ratio of Li/Co in the mixture is preferably 1.05; the transition metal in the transition metal oxide or hydroxide is more than one of Ni, Mn, Al, Ti, V, Mg, Y, Ce, Zr, Sb or La, and the total content of the transition metal in the mixture in the step (1) is 1000-10000 ppm;
sintering in the step (1), and preferably, preserving heat for more than 10 hours at the temperature of not less than 950 ℃;
(2) mixing a lithium source, a cobalt source and transition metal oxide or hydroxide powder, wherein the molar ratio of Li to Co in the mixture is more than 1, and sintering the mixture in air or oxygen-containing atmosphere at the temperature of at least 850 ℃ to obtain a primary product of powder B; the grain diameter of the obtained powder B is 4-12 μm, preferably 4-6 μm;
in the step (2), the molar ratio of Li/Co in the mixture is preferably 1.02; the transition metal in the transition metal oxide or hydroxide is more than one of Y, Al, Mg, Ti, La, F, Ga, Sn, Zr, Fe or Si, and the total content of the transition metal in the mixture in the step (2) is 1000-10000 ppm;
sintering in the step (2), and preferably, preserving heat for more than 8 hours at the temperature of not less than 940 ℃;
(3) mixing a lithium source, a cobalt source and transition metal oxide or hydroxide powder, wherein the molar ratio of L/Co in the mixture is 1.00-1.08, and sintering the mixture at a temperature of at least 800 ℃ in an oxygen-containing atmosphere, wherein the oxygen concentration in the atmosphere is not less than 15% by volume fraction to obtain a primary powder C; the grain diameter of the obtained powder C is 0.5-4.0 μm, preferably 1-2 μm;
in the step (3), the molar ratio of Li/Co in the mixture is preferably 1.01; the transition metal in the transition metal oxide or hydroxide is more than one of Ni, Mn, Mg, Al, Y, Yb, Nb, Sn, Cr or Zr, and the total content of the transition metal in the mixture in the step (3) is 1000-3000 ppm;
sintering in the step (3), and preferably, preserving heat for more than 6 hours at the temperature of not less than 880 ℃;
(4) mixing the powder A-defective product with the powder B-defective product and/or the powder C primary product, adding a transition metal oxide or hydroxide for mixing, and sintering at a temperature of at least 800 ℃ in an oxygen-containing atmosphere to obtain multimodal powder based on a lithium transition metal oxide;
or, preserving the temperature of the primary powder A at 980 ℃ for more than 10h at 800-; after sintering, obtaining multimodal powder based on lithium transition metal oxide;
the transition metal in the transition metal oxide or hydroxide in the step (4) is more than one of Ni, Mn, Mg, Al, Ti, Yb, Nb, Sn, Cr or Zr, and the total content of the transition metal in the mixture in the step (4) is 1000-10000 ppm;
the multimodal powder of the lithium transition metal oxide in the step (4), wherein the weight ratio of the powder A, the defective powder A, the powder B, the defective powder and/or the powder C is (12-15): (0-5): 0-2);
wherein the powder A and the powder B are mixed with the powder C, and the weight ratio of the powder A to the powder B is (12-15): (0-5): 0-2);
in the above method, the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate or lithium oxide, preferably lithium carbonate or lithium hydroxide; the cobalt source is more than one of cobaltosic oxide, cobaltous hydroxide, cobalt chloride, cobalt nitrate or cobalt oxalate, and preferably cobaltosic oxide.
In the method, the ratio of the D50 value of the primary or secondary powder A to the D50 value of the first defective powder B is more than 2:1, and the ratio of the D50 value of the first defective powder B to the D50 value of the first defective powder C is more than 4: 3; meanwhile, the specific surface area of the powder A once or two defective products is less than 0.2 square meter/g, the specific surface area of the powder B one defective product is 0.25-0.9 square meter/g, and the specific surface area of the powder C is more than 0.8 square meter/g; the specific surface area is obtained by BET measurement.
The specific surface area is the surface area/volume ratio, the ratio of 4 Π r2 to 3/4 Π r3 is (3/r), the larger the particles, the smaller the value of 3/r, the size range of the particles is determined by the specific surface area, and the size of the particles is in hook with the compaction density, and the compaction density is in hook with the energy density.
Three groups of powder need to have certain proportion to improve the compaction density, and the proper proportion is selected to better fill large-particle gaps. Because the large-particle gap space is limited and has a size range, when the number of medium-sized particles is too large or the particle size is too large, the medium-sized particles can exceed the large-particle gap, and the medium-sized particles cannot be well filled at the moment, so that the pressure density is reduced; similarly, the medium size particles are too small or too small to fill well, so that voids cannot be filled and the compacted density is reduced. Meanwhile, the fine particles also need to be controlled within a certain particle size range, because the gaps between the medium-sized particles and the large particles need to be filled with small particles, which also has a certain particle size requirement on the fine particles.
The finished product of the powder A consists of an inner core and an outer layer or the inner core, an impurity-containing layer and the outer layer, and has at least one peak, and the particle size of D50 is at least 18 mu m;
the inner core is composed of lithium cobalt oxide doped with transition metal ions, has a layered structure, and has a molecular formula of Li1+a(Co1-xMx)1-aO2Wherein M is more than one of Ni, Mn, Al, Ti, V, Mg, Y, Ce, Zr, Sb or La, a is more than or equal to-0.02 and less than or equal to 0.035, x is more than 0 and less than 0.2;
the outer layer is composed of lithium transition metal oxide with molecular formula of Li (Co)1-zM“z)O2Wherein M' is more than one of Ni, Mn, Al, Ti, V, Mg, Y, Ce, Zr, Sr, Cu, Sb or La, and z is more than or equal to 0.005;
the inclusion layer is positioned between the inner core and the outer layer, and the molecular formula of the inclusion layer is Li1+b(Co1-yM‘y)1-bO2Wherein M' is more than one of Ni, Mn, Al, Ti, V, Mg, Y, Ce, Zr, Sr, Cu, Sb or La, b is more than or equal to-0.01 and less than or equal to 0.025, and Y is more than 0 and less than 0.06.
The powder A finished product has two combination modes, wherein the first mode is an inner layer and an outer layer, and the second mode is an inner layer, an inclusion layer and an outer layer.
When one sample is two layers, core particles are generally obtained by primary sintering, a coating layer grows on the surface of the core particles by secondary sintering, the particles are changed into a two-layer structure, and the inner layer particles and the surface layer are different in composition and have different functions in the application of lithium ion batteries; in both examples 1 and 2, the process was a two-shot process.
One sample is subjected to primary sintering to form inner-layer particles, secondary sintering to form a layer growing on the surfaces of the inner-layer particles, namely an additive layer is formed, and tertiary sintering is to form a layer growing on the surfaces of the particle additive layers, namely an outer layer, wherein the finished product of the powder A in the example 3 is tertiary sintering; the transition metal element does not volatilize, and more or less of the transition metal element remains in the particle, and the approximate range of the element in the formula can be calculated from the amount of the transition metal oxide doped when the particles A in example 3 are sintered. One sample is sintered for three times, the temperature of the three times is different, and the coating of the transition metal oxide is different, so that the obtained powder has 3 layers.
Generally, when the first burning is a double-peak structure, the second burning will also be a double-peak structure.
Preferably, when the powder a primary or secondary product comprises double peaks, the ratio of the D50 value of the powder a primary or secondary product to the D50 value of the powder C secondary product is greater than 6:1, in order to increase the compaction density, the powder a secondary product is large particles, the powder C primary product is micro particles, and the ratio of D50 between them must be greater than a certain value to achieve good filling.
Preferably, when the powder a primary or secondary product comprises a double peak, the ratio of the weight fraction of the powder a-substandard product in the multimodal powder of the invention to the weight fraction of the powder C-substandard product is greater than 8:1, and the ratio of the weight fraction of the powder B-substandard product to the weight fraction of the powder C-substandard product is not less than 3: 1.
Preferably, when the powder a primary or secondary product comprises a single peak, the ratio of the weight fraction of powder a in the multimodal powder of the invention to the weight fraction of powder C secondary product is greater than 6: 1.
The powder B-defective product is a layered crystal structure consisting of Li and a material N and has at least one peak, and the particle size of D50 is 4-12 mu m;
the molecular formula of the material N is Co1-mM“‘mWherein M is more than 0 and less than or equal to 0.07, wherein M' is more than or equal to one of Y, Al, Mg, Ti, La, F, Ga, Sn, Zr, Fe or Si;
in the powder B, the molar ratio of Li to N is 0.99-1.02;
when the primary powder B product contains double peaks, the ratio of the D50 value of the first defective powder B product to the D50 value of the first defective powder C product is greater than 2: 1; when bimodal is included, it is indicated that the particles consist essentially of particles in the 2 particle size range, each peak representing the particle concentration point.
The defective powder C contains lithium cobalt transition metal oxide and has not less than one peak, and the grain diameter of D50 is not more than 3 mu m.
In the present invention, the increase in the compacted density of lithium cobaltate is mainly achieved by increasing the particle compactness and controlling the particle size distribution of lithium cobaltate. For large particle lithium cobaltate, such as particle a, the larger the particle, the greater the packing per volume and the greater the compacted density, but there are many gaps between the large particles, the presence of which affects the compacted density of the material. Increased volumetric energy density is achieved by increased compaction through a + B particle combination, a + B + C particle combination, or a + C particle combination.
Compared with the prior art, the invention has the following advantages and effects:
the prior art generally uses two types of particles with different sizes to fill the lithium cobaltate particles to increase the compaction density, such as Chinese patents CN1665052A and CN 105051945B, because the two types of particles are filled, the filling space is limited, the filling effect is limited, and the optimal filling effect is difficult to obtain.
Compared with the prior art, the invention has the advantages that: the invention forms the multimodal structure powder by a plurality of particles to form the anode material with high filling rate and stable structure applied under high voltage. The method is simple, and the prepared multimodal material consists of various particles, so that the filling requirement is better met, the filling effect is improved, the porosity is reduced, the material obtains higher volume energy density, and the material has better cycle performance.
Drawings
FIG. 1 is a particle size number distribution curve for a multimodal powder in example 1 of the invention.
FIG. 2 is an SEM image of a multimodal powder in example 1 of the invention.
FIG. 3 is a particle size number distribution curve for a multimodal powder in example 2 of the invention.
FIG. 4 is an SEM image of a multimodal powder in example 2 of the invention.
FIG. 5 is a particle size number distribution curve for a multimodal powder in example 3 of the invention.
FIG. 6 is an SEM image of a multimodal powder in example 3 of the invention.
FIG. 7 is a particle size number distribution curve for a multimodal powder in example 4 of the invention.
FIG. 8 is an SEM image of a multimodal powder in example 4 of the invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
A method for preparing a multimodal powder based on lithium transition metal oxide comprising the steps of:
(1) according to the Li/Co ratio of 1.06, mixing the four materials of magnesium oxide (containing Mg2000ppm), aluminum oxide (containing Al 2000ppm), lithium carbonate and cobaltosic oxide in a ball mill for 6h, putting the mixture into a sagger, putting the sagger into a furnace for sintering, raising the temperature at the rate of 5 ℃/min, and preserving the temperature at 1020 ℃ for 10h to obtain the lithium cobaltate. Crushing the lithium cobaltate to obtain large-particle lithium cobaltate D50 of 22 microns, namely a defective powder A, wherein only one peak is 22 microns in a particle size test, and the BET is 0.13 square meter/g;
(2) in the continuous type Co3O4(D50 is 5 mu m), when the mixture Li/Co is 1.015, mixing the four materials of magnesium oxide (containing Mg2000ppm), alumina (containing Al1000ppm), lithium carbonate and cobaltosic oxide in a ball mill for 6h, putting the mixture into a sagger, putting the sagger into a furnace for sintering, raising the temperature at the rate of 5 ℃/min, and preserving the temperature at 970 ℃ for 10h to obtain the lithium cobaltate. Crushing the lithium cobaltate to obtain medium-particle lithium cobaltate D50 with the particle size of 6.5 microns, namely a defective powder B, wherein only one peak is at the position of 6.5 microns in a particle size test;
(3) in the continuous type Co3O4(D50 is 2 μm), when the mixture Li/Co is 1.01, mixing the magnesium oxide (containing Mg2000ppm), alumina (containing Al 500ppm), lithium carbonate and cobaltosic oxide in a ball mill for 6h, putting the mixture into a sagger, putting the sagger into a furnace for sintering, raising the temperature at the rate of 5 ℃/min, and keeping the temperature at 900 ℃ for 8h to obtain the lithium cobaltate. Crushing the lithium cobaltate to obtain a small-particle lithium cobaltate first defective product D50 which is 2.5 micrometers, namely a powder C first defective product, wherein only one peak is at a position of 2.5 micrometers in a particle size test;
(4) mixing the large, medium and small particles according to a weight ratio of 13:5:2, adding alumina (containing 1000ppm of Al), titanium dioxide (containing 500ppm of Ti) and zirconium oxide (containing 500ppm of Zr), mixing the three particles in a high-speed mixer for 30 minutes, firing at 850 ℃ for 8 hours, and finally synthesizing a finished product of the cathode material, wherein the finished product of the cathode material is finally producedThe chemical formula is estimated as Li1.005Co0.949Mg0.017Al0.024Ti0.005Zr0.005O2And (3) a high-pressure stable lithium cobaltate cathode material finished product. The lithium cobaltate powder has three number distribution peaks as shown in fig. 1, and the SEM is shown in fig. 2.
The positive electrode material based on lithium cobaltate has the specific surface area of 0.17 square meter/g and the compaction density of 4.11g/cm3. The silver coin type electricity deduction is carried out at 3.0-4.5V and the multiplying power of 0.1C, the activation cycle N is 1, the electricity deduction is firstly charged with 197.2mAh/g, the electricity deduction is firstly discharged with 190.5mAh/g, and the first effect is 96.6%; the silver coin type is electrified for 50 weeks for circulation, and the capacity retention rate is 90.6%.
The electrical properties and the compacted density of the large, medium and small mixed calcined pellets were compared to those of one of the calcined pellets alone as shown in table 1 below: after the large, medium and small particles are mixed and twice burned, the 50-week cycle performance is better than that of a single particle; the compacted density is higher than that of a single granule; the reasonable control of the weight ratio of the large, medium and small particles can improve the cycle performance and the compaction density under high pressure.
| Numbering | Head placing device | CE％ | Capacity retention at 50 weeks | Density of compaction |
| Big + medium + small | 190.5mAh/g | 96.6％ | 90.6％ | 4.11g/cm3 |
| Big (a) | 188.1mAh/g | 94.6％ | 82.1％ | 4.03g/cm3 |
| In | 189.2mAh/g | 95.2％ | 73.4％ | 3.92g/cm3 |
| Small | 190mAh/g | 95.9％ | 52.6％ | 3.70g/cm3 |
Example 2
A method for preparing a multimodal powder based on lithium transition metal oxide comprising the steps of:
(1) mixing the four materials of magnesium oxide (containing Mg2000ppm), aluminum oxide (containing Al 3000ppm), lithium carbonate and cobaltosic oxide for 6 hours in a ball mill according to the Li/Co ratio of 1.04, putting the mixture into a sagger, putting the sagger into a furnace for sintering, raising the temperature at a rate of 5 ℃/min, keeping the temperature at 750 ℃ for 1 hour, continuing to raise the temperature to 1010 ℃, and keeping the temperature for 10 hours to obtain the lithium cobaltate. Crushing the lithium cobaltate to obtain large-particle lithium cobaltate D50 ═ 18 micrometers, namely a defective powder A, wherein the particle size test has two number peaks, one peak is at 7 micrometers, the other peak is at 20 micrometers, and the BET is 0.144 square meter/g;
(2) in the continuous type Co3O4(D50 ═ 3 μm) and when the blend L/C was 1.015, magnesium oxide (containing Mg2500ppm), aluminum oxide (containing Al1000ppm), lithium carbonate andand mixing the cobaltosic oxide and the four materials in a ball mill for 6 hours, putting the mixture into a sagger, putting the sagger into a furnace for sintering, raising the temperature at a speed of 5 ℃/min, and preserving the heat at 940 ℃ for 12 hours to obtain the lithium cobaltate. Crushing the lithium cobaltate to obtain medium-particle lithium cobaltate D50 with the particle size of 3.5 micrometers, namely a defective powder B, wherein the particle size test has two peaks, the first peak is at 1.2 micrometers, and the second peak is at 4.0 micrometers;
(3) mixing the large and medium particles according to a weight ratio of 3:1, adding alumina (containing Al1000ppm), titanium dioxide (containing Ti 600ppm) and zirconium oxide (containing Zr 800ppm), mixing the three particles in a high-speed mixer for 30 minutes, firing at 880 ℃ for 8 hours and finally synthesizing a finished product of the high-pressure stable lithium cobaltate cathode material. The lithium cobaltate powder has four number distribution peaks as shown in fig. 3, and the SEM is shown in fig. 4.
The specific surface area of the positive electrode material based on the lithium cobaltate is 0.2 square meter/g, and the compaction density is 4.05g/cm3. The silver coin type electricity deduction is carried out at 3.0-4.5V and the multiplying power of 0.1C, the activation cycle N is 1, the electricity deduction is firstly charged with 197.6mAh/g, the electricity deduction is firstly discharged with 191.5mAh/g, and the first effect is 96.9%; the silver coin type is electrified for 50 weeks for circulation, and the capacity retention rate is 91.2%.
The electrical properties and compacted density of the large and medium mix two-shot pellets were compared to those of one of the two-shot pellets alone as shown in table 2 below: after the large and medium particles are mixed and twice burned, the cycle performance and the compaction density are higher than those of single particles; reasonable control of the weight ratio of the large and medium particles can improve the cycle performance and the compaction density under high pressure.
| Numbering | Head placing device | CE％ | Capacity retention at 50 weeks | Density of compaction |
| Big and middle | 191.5mAh/g | 96.9％ | 91.2％ | 4.05g/cm3 |
| Big (a) | 187.1mAh/g | 95.1％ | 83.3％ | 3.92g/cm3 |
| In | 188.2mAh/g | 95.7％ | 76.4％ | 3.74g/cm3 |
Example 3
A method for preparing a multimodal powder based on lithium transition metal oxide comprising the steps of:
(1) according to the Li/Co ratio of 1.05, mixing four materials of magnesium oxide (containing Mg2000ppm), aluminum oxide (containing Al 2000ppm), lithium carbonate and cobaltosic oxide in a ball mill for 6 hours, putting the mixture into a sagger, putting the sagger into a furnace for sintering, raising the temperature at a rate of 3 ℃/min, and preserving the temperature at 1040 ℃ for 12 hours to obtain the lithium cobaltate. Crushing the lithium cobaltate to obtain a large-particle lithium cobaltate-defective product D50 which is 17 micrometers, wherein only one peak is at 18 micrometers in a particle size test; adding alumina (containing Al1000ppm) and titanium dioxide (containing Ti 500ppm) into the monocalcined lithium cobaltate, ball-milling and mixing uniformly, firing at 800 ℃ for 6h, and finally synthesizing the biscalcined lithium cobaltate, namely the powder A second defective product, wherein only one particle size peak is 21 microns, and the BET is 0.14 square meters per gram
(2) In the continuous type Co3O4(D50 is 3 mu m), when the mixed material L/C is 1.015, mixing the magnesium oxide (containing Mg2000ppm), the aluminum oxide (containing Al 3000ppm), the lithium carbonate and the cobaltosic oxide in a ball mill for 6h, putting the mixture into a sagger, putting the sagger into a furnace for sintering, raising the temperature at the rate of 5 ℃/min, and keeping the temperature at 940 ℃ for 12h to obtain the lithium cobaltate. Crushing the lithium cobaltate to obtain a medium-particle lithium cobaltate defective product D50 which is 4.5 micrometers, namely a powder B defective product, wherein only one peak is in a 4.5 micrometer position in a particle size test;
(3) in the continuous type Co3O4(D50 ═ 1 μm), and when the blend L/C was 1.00, the magnesium oxide (containing Mg2000ppm), aluminum oxide (containing Al 500ppm), lithium carbonate and cobaltosic oxide were mixed in a ball mill for 6 hours, and the mixture was put into a sagger and sintered in a furnace at a temperature rise rate of 5 ℃/min and at 900 ℃ for 6 hours, to obtain lithium cobaltate. Crushing the lithium cobaltate to obtain a small-particle lithium cobaltate first defective product D50 which is 2.0 micrometers, namely a powder C first defective product, wherein only one peak is at a position of 1.8 micrometers in a particle size test;
(4) mixing the large secondary-burning particles, the medium primary-burning particles and the small primary-burning particles according to a weight ratio of 14:5:2, adding alumina (containing 800ppm of Al), titanium dioxide (containing 600ppm of Ti) and yttrium oxide (containing 800ppm of Y), mixing the three particles in a high-speed mixer for 60 minutes, and burning at 900 ℃ for 8 hours to finally synthesize a finished product of the high-pressure stable lithium cobaltate cathode material. The lithium cobaltate powder has three number distribution peaks as shown in fig. 5, and the SEM is shown in fig. 6.
The surface area of the positive electrode material based on the lithium cobaltate is 0.18 square meters per gram, and the compaction density is 4.12g/cm3. Charging silver coin type, wherein the charging is carried out at 3.0-4.5V and the multiplying power is 0.1C, the activation cycle N is 1, the charging is firstly carried out at 198.1mAh/g, the discharging is firstly carried out at 191.7mAh/g, and the first effect is 96.76%; the silver coin type is electrified for 50 weeks for circulation, and the capacity retention rate is 91.3%.
The electrical properties and the compaction density of the large, medium and small mixed three-shot pellets were compared to those of one of the two-shot pellets alone as shown in table 3 below: after the large, medium and small particles are mixed and twice burned, the 50-week cycle performance and the compaction density are superior to those of single particles; the reasonable control of the weight ratio of the large, medium and small particles can improve the cycle performance and the compaction density under high pressure.
| Numbering | Head placing device | CE％ | Capacity retention at 50 weeks | Density of compaction |
| Big + medium + small | 191.7mAh/g | 96.76％ | 91.3％ | 4.13g/cm3 |
| Big (a) | 188.3mAh/g | 95.0％ | 84.4％ | 4.05g/cm3 |
| In | 189.7mAh/g | 95.7％ | 80.7％ | 3.91g/cm3 |
| Small | 190.4mAh/g | 96.13％ | 62.9％ | 3.72g/cm3 |
Example 4
A method for preparing a multimodal powder based on lithium transition metal oxide comprising the steps of:
(1) mixing magnesium oxide (containing 2500ppm of Mg), aluminum oxide (containing 1500ppm of Al), lithium carbonate and cobaltosic oxide for 5 hours in a ball mill according to the Li/Co ratio of 1.055, putting the mixture into a sagger, putting the sagger into a furnace for sintering, raising the temperature at a rate of 5 ℃/min, preserving the heat for 1.5 hours at 720 ℃, continuously raising the temperature to 1000 ℃, preserving the heat for 12 hours, and obtaining the lithium cobaltate. Crushing the lithium cobaltate to obtain large-particle lithium cobaltate D50 of 19.5 microns, namely a defective powder A, wherein a quantity peak is 19.5 microns in a particle size test, and the BET is 0.12 square meters per gram;
(2) in the continuous type Co3O4(D50 ═ 5 μm), and when the blend L/C was 1.015, the five materials of magnesium oxide (containing Mg1500ppm), aluminum oxide (containing Al 2500ppm), titanium dioxide (containing Ti 1000ppm), lithium carbonate and cobaltosic oxide were mixed in a ball mill for 6 hours, and the mixture was charged into a sagger and sintered in a furnace at a temperature rise rate of 3 ℃/min and held at 950 ℃ for 10 hours to obtain lithium cobaltate. Crushing the lithium cobaltate to obtain a medium-particle lithium cobaltate defective product D50 which is 5.5 micrometers, namely a powder B defective product, wherein a peak is in a position of 5.5 micrometers in a particle size test;
(3) in the continuous type Co3O4(D50 ═ 2 μm), and when the blend L/C was 1.00, the magnesium oxide (containing Mg1500ppm), aluminum oxide (containing Al 500ppm), lithium carbonate and cobaltosic oxide were mixed in a ball mill for 4 hours, and the mixture was put into a sagger and sintered in a furnace at a temperature rise rate of 2 ℃/min and at 880 ℃, for 8 hours, to obtain lithium cobaltate. Crushing the lithium cobaltate to obtain a small-particle lithium cobaltate first defective product D50 which is 2.8 micrometers, namely a powder C first defective product, wherein only one peak is in a 2.8 micrometer position in a particle size test;
(4) mixing the large, medium and small particles according to the weight ratio of 11: 3:1, adding alumina (containing 800ppm of Al), titanium dioxide (containing 800ppm of Ti), zirconium oxide (containing 800ppm of Zr) and lanthanum oxide (containing 500ppm of La), mixing the three particles in a high-speed mixer for 30 minutes, firing at 870 ℃ for 8 hours and finally synthesizing the finished product of the high-pressure stable lithium cobaltate cathode material. The lithium cobaltate powder has four number distribution peaks as shown in fig. 7, and the SEM is shown in fig. 8.
The specific surface area of the positive electrode material based on the lithium cobaltate is 0.16 square meter/g, and the compaction density is 4.15g/cm3. The silver coin type electricity deduction is carried out at 3.0-4.5V and the multiplying power of 0.1C, the activation cycle N is 1, the electricity deduction is firstly charged to 198.2mAh/g, the electricity deduction is firstly discharged to 191.9mAh/g, and the first effect is 96.8%; the silver coin type is electrified for 50 weeks for circulation, and the capacity retention rate is 93.3%.
The electrical properties and compacted density of the large and medium mix two-shot pellets were compared to those of one of the two-shot pellets alone as shown in table 4 below: after the large and medium particles are mixed and twice burned, the cycle performance and the compaction density are higher than those of single particles; reasonable control of the weight ratio of the large and medium particles can improve the cycle performance and the compaction density under high pressure.
| Numbering | Head placing device | CE％ | Capacity retention at 50 weeks | Density of compaction |
| Big + medium + small | 191.9mAh/g | 96.82％ | 93.3％ | 4.21g/cm3 |
| Big (a) | 188.7mAh/g | 95.6％ | 88.4％ | 4.08g/cm3 |
| In | 187.7mAh/g | 96.2％ | 87.7％ | 3.80g/cm3 |
| Small | 192.4mAh/g | 96.36％ | 52.6％ | 3.68g/cm3 |
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other multiple sintering cases such as two sintering of large, medium and small particles respectively, three sintering with mixing, etc. any other changes, modifications, substitutions, combinations, simplifications, which do not depart from the spirit and principle of the present invention, should be regarded as equivalent replacements, and all are included in the protection scope of the present invention.
Claims (6)
1. A method for preparing a multimodal powder based on lithium transition metal oxide, characterized in that it comprises the following steps:
(1) mixing a lithium source, a cobalt source and transition metal oxide or hydroxide powder, wherein the molar ratio of Li to Co in the mixture is 0.98-1.08, and sintering in air or oxygen atmosphere to obtain a powder A defective product; the grain diameter of the obtained powder A-defective product is 15-30 mu m;
in the step (1), the transition metal in the transition metal oxide or hydroxide is more than one of Ni, Mn, Al, Ti, V, Mg, Y, Ce, Zr, Sb or La, and the total content of the transition metal in the mixture in the step (1) is 1000-10000 ppm;
(2) mixing a lithium source, a cobalt source and transition metal oxide or hydroxide powder, wherein the molar ratio of Li to Co in the mixture is more than 1, and sintering the mixture in air or oxygen-containing atmosphere at the temperature of at least 850 ℃ to obtain a primary powder B; the grain diameter of the primary powder B is 4-12 μm;
in the step (2), the transition metal in the transition metal oxide or hydroxide is Mg, Al and Ti, and the total content of the transition metal in the mixture in the step (2) is 1000-10000 ppm;
(3) mixing a lithium source, a cobalt source and transition metal oxide or hydroxide powder, wherein the molar ratio of L/Co in the mixture is 1.00-1.08, and sintering the mixture at a temperature of at least 800 ℃ in an oxygen-containing atmosphere, wherein the oxygen concentration in the atmosphere is not less than 15% by volume fraction to obtain a primary powder C; the grain diameter of the primary powder C is 0.5-4.0 μm;
in the step (3), the transition metal in the transition metal oxide or hydroxide is more than one of Ni, Mn, Mg, Al, Y, Yb, Nb, Sn, Cr or Zr, and the total content of the transition metal in the mixture in the step (3) is 1000-3000 ppm;
(4) mixing the powder A-defective product with the powder B-defective product and/or the powder C primary product, adding a transition metal oxide or hydroxide for mixing, and sintering at a temperature of at least 800 ℃ in an oxygen-containing atmosphere to obtain multimodal powder based on a lithium transition metal oxide;
or, respectively preserving the primary powder A at the temperature of 800-; after sintering, obtaining a finished product of multimodal powder based on lithium transition metal oxide;
the transition metal in the transition metal oxide or hydroxide in the step (4) is one of the following combinations:
al, Ti and Zr;
② Al, Ti and Y;
③ Al, Ti, Zr and La;
the total content of the transition metal in the mixture in the step (4) is 1000-10000 ppm;
mixing the defective powder A with the defective powder B and/or the primary powder C in a weight ratio of (12-15) to (0-5) to (0-2);
mixing the defective powder A and the defective powder B and/or the primary powder C in a weight ratio of (12-15) to (0-5) to (0-2);
the ratio of the D50 value of the primary or secondary powder A to the D50 value of the first defective powder B is greater than 2:1, and the ratio of the D50 value of the first defective powder B to the D50 value of the first defective powder C is greater than 4: 3; meanwhile, the specific surface area of the powder A primary or secondary defective product is less than 0.2m2The specific surface area of the powder B-defective product is 0.25-0.9m2(g), the specific surface area of the powder C-defective product is more than 0.8m2(ii)/g; the specific surface area is measured by a BET device;
the powder A primary defective product or secondary product consists of an inner core and an outer layer, or consists of an inner core, an inclusion layer and an outer layer, and at least has one particle size peak, and the D50 particle size is at least 18 mu m;
the inner core is composed of lithium cobalt oxide doped with transition metal ions, has a layered structure, and has a molecular formula of Li1+a(Co1-xMx)1-aO2Wherein M is more than one of Ni, Mn, Al, Ti, V, Mg, Y, Ce, Zr, Sb or La, a is more than or equal to-0.02 and less than or equal to 0.035, x is more than 0 and less than 0.2;
the outer layer is composed of lithium transition metal oxide with molecular formula of Li (Co)1-zM‘‘z)O2Wherein M' is more than one of Ni, Mn, Al, Ti, V, Mg, Y, Ce, Zr, Sb or La, and z is more than or equal to 0.005;
the inclusion layer is positioned between the inner core and the outer layer, and the molecular formula of the inclusion layer is Li1+b(Co1-yM‘y)1-bO2Wherein M' is more than one of Ni, Mn, Al, Ti, V, Mg, Y, Ce, Zr, Sb or La, b is more than or equal to-0.01 and less than or equal to 0.025, and Y is more than 0 and less than 0.06;
the multi-modal lithium transition metal oxide based powder has at least three number particle size peaks;
the multimodal powder based on lithium transition metal oxide has a charged cut-off voltage of 4.5V.
2. The method of claim 1, wherein: the lithium source is more than one of lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate or lithium oxide.
3. The method of claim 1, wherein: the cobalt source is more than one of cobaltosic oxide, cobaltous hydroxide, cobalt chloride, cobalt nitrate or cobalt oxalate.
4. Multimodal powder based on lithium transition metal oxide, characterized in that: is prepared by the method of any one of claims 1 to 3.
5. Multimodal powder according to claim 4, characterized in that:
the powder B-defective product is a layered crystal structure consisting of Li and a material N, and has at least one particle size peak, wherein the particle size of D50 is 4-12 mu m;
the molecular formula of the material N is Co1-mM‘‘‘mWherein 0 < m.ltoreq.0.07, wherein M ' ' ' is Mg, Al and Ti;
in the defective powder B, the Li/N molar ratio is 0.99-1.02;
the defective powder C contains lithium cobalt transition metal oxide and has not less than one particle size peak, and the particle size of D50 is not more than 3 mu m.
6. Use of the multimodal powder as claimed in any of claims 4 to 5 as a positive electrode material for rechargeable batteries.
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