CN117174817A - Positive electrode active material, preparation method, battery and device - Google Patents
Positive electrode active material, preparation method, battery and device Download PDFInfo
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- CN117174817A CN117174817A CN202311154108.1A CN202311154108A CN117174817A CN 117174817 A CN117174817 A CN 117174817A CN 202311154108 A CN202311154108 A CN 202311154108A CN 117174817 A CN117174817 A CN 117174817A
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 85
- 239000002245 particle Substances 0.000 claims abstract description 69
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 62
- 239000002243 precursor Substances 0.000 claims abstract description 43
- 239000002002 slurry Substances 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 238000005507 spraying Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000007921 spray Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 35
- 239000004576 sand Substances 0.000 claims description 28
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 20
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000000227 grinding Methods 0.000 claims description 14
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 10
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 7
- 239000005751 Copper oxide Substances 0.000 claims description 7
- 229910000431 copper oxide Inorganic materials 0.000 claims description 7
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 6
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 6
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 6
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 239000004280 Sodium formate Substances 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a positive electrode active material, a preparation method, a battery and a device. The preparation method comprises the following steps: mixing a first transition metal oxide, sodium salt and a solvent, and performing first sanding treatment to obtain a mixture; adding a second transition metal oxide with the bulk density smaller than that of the first transition metal oxide into the mixture, and performing second sanding treatment to obtain precursor slurry; and spraying and sintering the precursor slurry to obtain the positive electrode active material. The invention can prepare the positive electrode active material with more concentrated particle size distribution range and higher sanding efficiency, so that the consistency of the subsequent spray particles is higher, and the electrochemical performance of the layered oxide obtained by sintering is further improved.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to an anode active material, a preparation method, a battery and a device.
Background
The preparation of the sodium-electricity layered oxide anode material can be realized by grinding metal oxide, spray drying and granulating to form a precursor, and then sintering the precursor. But the problem of uneven grain size distribution of sand particles easily occurs in the sand grinding process, part of materials are not sufficiently ground, the particles are too large, and part of materials are excessively ground to cause coarsening, so that the sand grinding efficiency is reduced, the grain size distribution is too wide, the sphericity, loose density and element distribution uniformity of spray granulation are influenced, and the electrochemical performance of the layered oxide anode material obtained by sintering is influenced.
Disclosure of Invention
The invention mainly aims to provide a positive electrode active material, a preparation method, a battery and a device, and aims to solve the problems of uneven particle size distribution of sand grinding particles and poor electrochemical performance of the positive electrode material in the prior art.
To achieve the above object, a first aspect of the present invention provides a method for preparing a positive electrode active material, comprising the steps of:
mixing a first transition metal oxide, sodium salt and a solvent, and performing first sanding treatment to obtain a mixture;
adding a second transition metal oxide with the bulk density smaller than that of the first transition metal oxide into the mixture, and performing second sanding treatment to obtain precursor slurry;
and spraying and sintering the precursor slurry to obtain the positive electrode active material.
The apparent density is related to various factors such as the density of the particles, the particle diameter of the particles, the specific surface area, the degree of surface regularity of the particles, and the like, and the larger the particle diameter, the larger the density, the closer the appearance of the particles to a regular sphere, and the like, the larger the apparent density of the particles of the same composition. And the larger the particle diameter of the particles, the higher the density, and the longer the time required for sanding the particles with the appearance closer to the regular spherical shape, the greater the sanding difficulty.
Thus, in the present invention, a first transition metal oxide having a relatively higher bulk density is first subjected to a first sanding treatment, and then a second transition metal oxide having a relatively lower bulk density is added to perform a second sanding treatment. The metal oxide raw materials which are difficult to sand to the nano particles in a batch sanding mode are subjected to first sanding treatment, then the metal oxide raw materials which are easier to sand to the nano particles in a relative mode are added to carry out second sanding treatment, more concentrated particle size distribution range and higher sanding efficiency can be obtained, the consistency of subsequent spray particles is higher, and the electrochemical performance of the layered oxide obtained by sintering is further improved.
In any embodiment, the first transition metal oxide has a bulk density of greater than 1g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The bulk density of the second transition metal oxide is less than or equal to 1g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Optionally, the first transition metal oxide has a bulk density of 1.08 to 2.5g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The bulk density of the second transition metal oxide is 0.86-0.98 g/cm 3 。
In any embodiment, the first transition metal oxide has a particle size of 1 to 30 μm; and/or the particle size of the second transition metal oxide is 1-5 μm.
In any embodiment, the solid particles in the mixture have a median particle diameter Dv50 of 700 to 2000nm; and/or the number of the groups of groups,
the median diameter Dv50 of the solid particles in the precursor slurry is 200-500 nm.
In any embodiment, in the step of mixing the first transition metal oxide, the sodium salt, and the solvent and then performing the first sanding treatment to obtain the mixture,
the sanding time of the first sanding treatment is 60-150 min, and the sanding speed is 2800-3000 rpm.
In any embodiment, in the step of adding a second transition metal oxide having a bulk density less than that of the first transition metal oxide to the mixture, and performing a second sanding treatment to obtain a precursor slurry,
the second sand grinding treatment has the sand grinding time of 60-90 min and the sand grinding speed of 2800-3000 rpm.
In any embodiment, the first transition metal oxide comprises at least one of nickel oxide, manganese oxide, cobalt oxide, iron oxide, copper oxide, tungsten oxide.
In any embodiment, the second transition metal oxide comprises at least one of nickel oxide, manganese oxide, cobalt oxide, iron oxide, copper oxide, tungsten oxide.
In any embodiment, the first transition metal oxide and the second transition metal oxide have a total mass of M1, sodium salt has a mass of M2, and solvent has a mass of M3, M1: m2: m3=1 (0.63-0.69): 1-10.
In any embodiment, the sodium salt comprises at least one of anhydrous sodium carbonate, sodium hydroxide, sodium formate, sodium acetate, and/or the solvent comprises deionized water.
In any embodiment, in the step of spraying and sintering the precursor slurry to obtain the positive electrode active material,
the spray meets at least one condition that the air inlet temperature is 230-250 ℃, the feeding speed is 80-100 ml/min, and the air outlet temperature is 100-115 ℃.
In any embodiment, in the step of spraying and sintering the precursor slurry to obtain the positive electrode active material,
the sintering process includes: the first sintering, the second sintering and the third sintering with gradually increased sintering temperatures are sequentially performed.
In any embodiment, the sintering temperature of the first sintering is 450-600 ℃, and the heat preservation time is 2-6 h; and/or the number of the groups of groups,
the sintering temperature of the secondary sintering is 750-850 ℃, and the heat preservation time is 2-6 h; and/or the number of the groups of groups,
the sintering temperature of the third sintering is 900-1000 ℃ and the heat preservation time is 10-16 h.
In any embodiment, the temperature rising rate of the first sintering, the second sintering and the third sintering is 1-5 ℃/min; and/or the sintering atmosphere of the first sintering, the second sintering and the third sintering is air or oxygen.
Based on the above preparation method, the second aspect of the present invention provides a positive electrode active material prepared by the preparation method according to the first aspect, wherein the positive electrode active material is single crystal particles, and/or the median particle diameter Dv50 of the positive electrode active material is 1-10 μm.
The third aspect of the invention provides a battery comprising a positive electrode plate, a negative electrode plate and a separation film, wherein the positive electrode plate comprises the positive electrode active material provided by the second aspect of the invention.
A fourth aspect of the invention provides an electrical device comprising a battery as provided in the third aspect of the invention.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of a precursor slurry provided in example 1 of the present invention;
fig. 2 is a scanning electron microscope image of the precursor slurry provided in comparative example 1 of the present invention.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. In addition, the meaning of "and/or" as it appears throughout includes three parallel schemes, for example "A and/or B", including the A scheme, or the B scheme, or the scheme where A and B are satisfied simultaneously. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be regarded as not exist and not within the protection scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The preparation of the sodium-electricity layered oxide anode material can be realized by grinding metal oxide, spray drying and granulating to form a precursor, and then sintering the precursor. Generally, 2 or more kinds of metal elements are used as the structural frame, and for example, a transition metal element such as Fe, mn, ni, cu, co, W may be used. Among them, the higher the proportion of Ni, the higher the capacity is generally. Fe can also provide capacity in a certain electrochemical window, and the material cost is low, and the higher the proportion is, the more the raw material cost can be reduced. The valence state of Mn does not change in the structure, the increasing proportion can generally improve the stability and the cycle performance of the material structure, and the price of raw materials is relatively low. Cu can provide capacity in sodium electricity and also improve structural stability and cycle performance. It can be seen that the sodium-electricity layered oxide positive electrode material has various uses and contains a large number of metal elements. Thus, the sanding process requires consideration of the morphology of the various metal oxides, particle size, ease of sanding to the nanoparticles, and the like. The problem of uneven sand grain size distribution of sand particles easily occurs in the sand grinding process, part of materials are not sufficiently ground, the particles are too large, and part of materials are excessively ground to cause coarsening, so that the sand grinding efficiency is reduced, the particle size distribution is too wide, the sphericity, loose packing density and element distribution uniformity of spray granulation are influenced, and the electrochemical performance of the layered oxide anode material obtained through sintering is influenced.
In view of this, the present invention proposes a method for preparing a positive electrode active material, comprising the steps of:
mixing a first transition metal oxide, sodium salt and a solvent, and performing first sanding treatment to obtain a mixture;
adding a second transition metal oxide with the bulk density smaller than that of the first transition metal oxide into the mixture, and performing second sanding treatment to obtain precursor slurry;
and spraying and sintering the precursor slurry to obtain the positive electrode active material.
Herein, "bulk density" refers to the ratio of the mass m of a powder to its filled volume V (including the voids between the powders) without vibration of the powder. It should be understood that bulk density is related to various factors such as the density of the particles, the particle size of the particles, the specific surface area, the degree of surface regularity of the particles, etc. For particles of the same composition, the larger the particle diameter, the greater the density, the closer the particle appearance to a regular sphere, etc., the greater the bulk density. And the larger the particle diameter of the particles, the higher the density, and the longer the time required for sanding the particles with the appearance closer to the regular spherical shape, the greater the sanding difficulty.
Thus, in the present invention, a first transition metal oxide having a relatively higher bulk density is first subjected to a first sanding treatment, and then a second transition metal oxide having a relatively lower bulk density is added to perform a second sanding treatment. The metal oxide raw materials which are difficult to sand to the nano particles in a batch sanding mode are subjected to first sanding treatment, then the metal oxide raw materials which are easier to sand to the nano particles in a relative mode are added to carry out second sanding treatment, more concentrated particle size distribution range and higher sanding efficiency can be obtained, the consistency of subsequent spray particles is higher, and the electrochemical performance of the layered oxide obtained by sintering is further improved.
In any embodiment, the first transition metal oxideThe bulk density of the material is greater than 1g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The bulk density of the second transition metal oxide is less than or equal to 1g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Optionally, the first transition metal oxide has a bulk density of 1.08 to 2.5/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The bulk density of the second transition metal oxide is 0.86-0.98 g/cm 3 . Unexpectedly, the bulk density is greater than 1g/cm 3 The transition metal oxide is relatively more difficult to sand to particles with a desired particle size, and the grinding efficiency can be improved by reasonably dividing the transition metal oxide.
In any embodiment, the first transition metal oxide has a particle size of 1 to 30 μm; the particle size of the second transition metal oxide is 1-5 mu m.
In any embodiment, the solid particles in the mixture have a median particle diameter Dv50 of 700 to 2000nm; the median diameter Dv50 of the solid particles in the precursor slurry is 200-500 nm. Therefore, the first transition metal oxide is firstly sanded to the particle size of 700-1000 nm, and then the second sanding treatment is carried out, so that the more concentrated particle size distribution range and the higher sanding efficiency are facilitated.
In any embodiment, in the step of mixing the first transition metal oxide, the sodium salt and the solvent and then performing the first sanding treatment to obtain the mixture, the sanding time of the first sanding treatment is 60-120 min, and the sanding speed is 2800-3000 rpm. At this suitable sanding time and speed, it is advantageous to obtain a mixture of suitable particle sizes.
In any embodiment, in the step of adding a second transition metal oxide having a bulk density smaller than that of the first transition metal oxide to the mixture and performing a second sanding treatment to obtain a precursor slurry, the sanding time of the second sanding treatment is 60-90 min, and the sanding speed is 2800-3000 rpm. At this suitable sanding time and speed, it is advantageous to obtain a precursor of suitable particle size.
In any embodiment, the first transition metal oxide comprises at least one of nickel oxide, manganese oxide, cobalt oxide, iron oxide, copper oxide, tungsten oxide. The second transition metal oxide includes at least one of nickel oxide, manganese oxide, cobalt oxide, iron oxide, copper oxide, and tungsten oxide.
In any embodiment, the first transition metal oxide and the second transition metal oxide have a total mass of M1, sodium salt has a mass of M2, and solvent has a mass of M3, M1: m2: m3=1 (0.63-0.69): 1-10. Under the proper proportion, the sanding efficiency is improved, and the electrical property of the anode material is improved.
In any embodiment, the sodium salt comprises at least one of anhydrous sodium carbonate, sodium hydroxide, sodium formate, sodium acetate, and the solvent comprises deionized water.
In any embodiment, in the step of spraying and sintering the precursor slurry to obtain the positive electrode active material, the spraying satisfies at least one condition of an air inlet temperature of 230-250 ℃, a feeding speed of 80-100 ml/min and an air outlet temperature of 100-115 ℃. Under the proper spraying condition, the median particle diameter Dv50 of the precursor powder obtained by spraying the precursor slurry is 10-30 mu m; the mass ratio of water in the precursor powder is less than 3%; the bulk density of the precursor powder is greater than 0.6g/cm 3 . Therefore, under the proper spraying condition, the precursor powder obtained by spraying the precursor slurry has proper particle size, small moisture, high loose density, good sphericity and good consistency.
In any embodiment, in the step of spraying and sintering the precursor slurry to obtain the positive electrode active material, the sintering process includes: the first sintering, the second sintering and the third sintering with gradually increased sintering temperatures are sequentially performed.
In any embodiment, the sintering temperature of the first sintering is 450-600 ℃, and the heat preservation time is 2-6 h; the sintering temperature of the secondary sintering is 750-850 ℃, and the heat preservation time is 2-6 h; the sintering temperature of the third sintering is 900-1000 ℃ and the heat preservation time is 10-16 h. Therefore, the water bound in the structure is removed in the first sintering construction, the sodium carbonate is fully melted and broken to be combined with the transition metal in a reaction manner through the second sintering, and the crystal is fully nucleated and grown through the third sintering.
In any embodiment, the temperature rising rate of the first sintering, the second sintering and the third sintering is 1-5 ℃/min; and/or the sintering atmosphere of the first sintering, the second sintering and the third sintering is air or oxygen.
The invention also provides the positive electrode active material prepared by the preparation method, wherein the positive electrode active material is single crystal particles, and the median particle diameter Dv50 of the positive electrode active material is 1-10 mu m.
The invention also provides a battery, which comprises a positive electrode plate, a negative electrode plate and a separation film, wherein the positive electrode plate comprises the positive electrode active material.
The invention also provides an electric device comprising the battery.
The following technical solutions of the present invention will be described in further detail with reference to specific examples and drawings, and it should be understood that the following examples are only for explaining the present invention and are not intended to limit the present invention.
Example 1
The mass ratio is 1.04:0.33:0.33:0.33 anhydrous sodium carbonate, 1 micron iron oxide, 10 micron nickel oxide and 10 micron manganese oxide were weighed separately, 2kg total, and 8kg deionized water was weighed. Adding anhydrous sodium carbonate, nickel oxide, manganese oxide and deionized water into a sand mill for primary sand milling to obtain a mixture, wherein the sand milling speed is 2800rpm, the median particle diameter Dv50 of solid particles in the mixture is 700nm, adding ferric oxide into the sand mill for secondary sand milling to obtain precursor slurry, the sand milling speed is 3000rpm, and the sand milling time is 60min, wherein the median particle diameter Dv50 of the solid particles in the precursor slurry is 500nm.
And pumping the precursor slurry into a feed inlet of a spray dryer by using a peristaltic pump, setting the feed temperature to be 250 ℃, setting the rotating speed of an atomizer to be 30000rpm, setting the feed speed to be 80ml/min, introducing air to 2400rpm, and enabling the discharge temperature of the material to be about 100 ℃ to obtain precursor powder of the positive electrode material.
Sintering the precursor powder by using a box furnace, wherein the sintering is carried out: the temperature is kept for 2h at 450 ℃ for the first sintering, 4h at 850 ℃ for the second sintering, 12h at 950 ℃ for the third sintering, and the temperature rising rate is 3 ℃/min for the third sintering, and the sintering is carried out in air atmosphere. Cooling to room temperature, discharging, and crushing to obtain the positive electrode active material which is a layered oxide single crystal material, wherein the median particle diameter Dv50 of the positive electrode active material is 5.5 mu m.
Examples 2 to 15
Examples 2-15 positive electrode active materials were prepared in a similar manner to example 1. Wherein, the mass ratio of the example 5 is 1.04:0.4:0.3:0.2:0.1 anhydrous sodium carbonate, 1 micron iron oxide, 10 micron manganese oxide, 10 micron nickel oxide and 30 micron copper oxide were weighed separately, except for the differences noted in tables 1 and 2.
Comparative example 1
This comparative example 1 is different from example 1 in that this comparative example adopts a form of primary sanding, and anhydrous sodium carbonate, nickel oxide, manganese oxide, deionized water, iron oxide are added to a sand mill and sand-milled to obtain a precursor slurry.
Table 1 table of preparation parameters of examples 1-9
Performance testing
The products obtained in examples 1 to 17 and comparative example 1 were mixed with polyvinylidene fluoride and conductive carbon black in a ratio of 8:1:1, and N-methylpyrrolidone solvent was added, and the obtained mixture was sufficiently and uniformly stirred using a mechanical centrifugal stirrer. Uniformly coating on aluminum foil by a coating machine, and placing in a 100 ℃ oven for vacuum drying for 12 hours. Subsequently, a circular pole piece having a diameter of 12mm was cut by a cutter, and weighed, whereby the mass of the active material was calculated to be 10mg.
Scanning electron microscope tests were performed on the precursor slurries of example 1 and comparative example 1 after sanding.
Referring to fig. 1 and 2, comparing the sem images of the precursor slurries of example 1 and comparative example 1, the present invention can obtain more uniform and consistent particles by performing the batch-wise twice sanding process.
Electrochemical performance test: all cell assemblies were completed in a glove box (water oxygen values all below 0.01 ppm). The constant current charge and discharge test and the long-cycle test of the button cell are realized by a New Wei CT4008 charge and discharge tester, and the test voltage window is 2-4.0V. The test results are shown in Table 3.
TABLE 3 Performance test results
As can be seen from Table 3, comparing inventive examples 1-17 with comparative example 1, a mixture was obtained by mixing a first transition metal oxide, a sodium salt, and a solvent and then performing a first sanding treatment; adding a second transition metal oxide with the bulk density smaller than that of the first transition metal oxide into the mixture, and performing second sanding treatment to obtain precursor slurry; the positive electrode active material obtained by the method of spraying and sintering the precursor slurry can obtain higher first charge capacity, first discharge capacity, higher first effect and higher cycle retention rate.
As can be seen from examples 1 to 11, the positive electrode active material prepared by using the different first transition metal oxide and second transition metal oxide and performing the sanding treatment twice can each obtain a high first charge capacity, a high first discharge capacity, a high first effect and a high cycle retention rate.
It can be seen from examples 12 to 17 that the positive electrode active materials prepared by using different sanding treatment times and speeds, different spraying processes and different sintering treatment processes can all obtain high first charge capacity, first discharge capacity, high first efficiency and high cycle retention rate.
As can be seen from examples 1 and 17, the positive electrode active material prepared by the three-stage sintering method has a higher cycle retention rate than the positive electrode active material prepared by the two-stage sintering method.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the scope of the present invention, but various modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (17)
1. A method for preparing a positive electrode active material, comprising the steps of:
mixing a first transition metal oxide, sodium salt and a solvent, and performing first sanding treatment to obtain a mixture;
adding a second transition metal oxide with the bulk density smaller than that of the first transition metal oxide into the mixture, and performing second sanding treatment to obtain precursor slurry;
and spraying and sintering the precursor slurry to obtain the positive electrode active material.
2. The method of claim 1, wherein the first transition metal oxide has a bulk density of greater than 1g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The bulk density of the second transition metal oxide is less than or equal to 1g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Optionally, the first transition metal oxide has a bulk density of 1.08 to 2.5g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The bulk density of the second transition metal oxide is 0.86-0.98 g/cm 3 。
3. The production method according to claim 1 or 2, wherein the particle size of the first transition metal oxide is 1 to 30 μm; and/or the number of the groups of groups,
the particle size of the second transition metal oxide is 1-5 mu m.
4. The method of claim 1, wherein the solid particles in the mixture have a median particle diameter Dv50 of 700-2000 nm; and/or the number of the groups of groups,
the median diameter Dv50 of the solid particles in the precursor slurry is 200-500 nm.
5. The method according to claim 1, wherein in the step of mixing the first transition metal oxide, the sodium salt, and the solvent and then performing the first sanding treatment to obtain the mixture,
the sanding time of the first sanding treatment is 60-120 min, and the sanding speed is 2800-3000 rpm.
6. The method according to claim 1, wherein in the step of adding a second transition metal oxide having a bulk density smaller than that of the first transition metal oxide to the mixture and performing a second sand milling treatment to obtain a precursor slurry,
the second sand grinding treatment has the sand grinding time of 60-90 min and the sand grinding speed of 2800-3000 rpm.
7. The method according to claim 1, wherein the first transition metal oxide comprises at least one of nickel oxide, manganese oxide, cobalt oxide, iron oxide, copper oxide, and tungsten oxide.
8. The method according to claim 1, wherein the second transition metal oxide comprises at least one of nickel oxide, manganese oxide, cobalt oxide, iron oxide, copper oxide, and tungsten oxide.
9. The preparation method according to claim 1, wherein the first transition metal oxide and the second transition metal oxide have a molar mass of M1, a sodium salt of M2, a solvent of M3, and M1: m2: m3=1 (0.63-0.69): 1-10.
10. The method according to claim 1, wherein the sodium salt comprises at least one of anhydrous sodium carbonate, sodium hydroxide, sodium formate, sodium acetate, and/or,
the solvent comprises deionized water and absolute ethyl alcohol.
11. The method according to claim 1, wherein in the step of spraying and sintering the precursor slurry to obtain the positive electrode active material,
the spray meets at least one condition that the air inlet temperature is 230-250 ℃, the feeding speed is 80-100 ml/min, and the air outlet temperature is 100-115 ℃.
12. The method according to claim 1, wherein in the step of spraying and sintering the precursor slurry to obtain the positive electrode active material,
the sintering process includes: the first sintering, the second sintering and the third sintering with gradually increased sintering temperatures are sequentially performed.
13. The method according to claim 12, wherein the sintering temperature of the first sintering is 450-600 ℃ and the holding time is 2-6 h; and/or the number of the groups of groups,
the sintering temperature of the secondary sintering is 750-850 ℃, and the heat preservation time is 2-6 h; and/or the number of the groups of groups,
the sintering temperature of the third sintering is 900-1000 ℃ and the heat preservation time is 10-16 h.
14. The method according to claim 12, wherein the temperature rise rate of the first sintering, the second sintering and the third sintering is 1 to 5 ℃/min; and/or the number of the groups of groups,
the sintering atmosphere of the first sintering, the second sintering and the third sintering is air or oxygen.
15. A positive electrode active material prepared by the preparation method according to any one of claims 1 to 14, characterized in that the positive electrode active material is single crystal particles and/or the median particle diameter Dv50 of the positive electrode active material is 1 to 10 μm.
16. A battery comprising a positive electrode sheet, a negative electrode sheet, and a separator, the positive electrode sheet comprising the positive electrode active material according to claim 15.
17. An electrical device comprising the battery of claim 16.
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