CN117747839A - High-nickel ternary positive electrode active material, preparation method thereof and lithium ion battery - Google Patents
High-nickel ternary positive electrode active material, preparation method thereof and lithium ion battery Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 70
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 68
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 43
- 238000005245 sintering Methods 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- 239000011572 manganese Substances 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004917 carbon fiber Substances 0.000 claims description 6
- 239000002019 doping agent Substances 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000006258 conductive agent Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 239000002048 multi walled nanotube Substances 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000002109 single walled nanotube Substances 0.000 claims description 3
- ZYKTVIDNXTWTNS-UHFFFAOYSA-L [Co].[Mn].[Ni](O)O Chemical group [Co].[Mn].[Ni](O)O ZYKTVIDNXTWTNS-UHFFFAOYSA-L 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 5
- 230000001976 improved effect Effects 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 238000005336 cracking Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 17
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 10
- 239000006182 cathode active material Substances 0.000 description 7
- 238000005056 compaction Methods 0.000 description 5
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 5
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 5
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 239000006183 anode active material Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Abstract
The invention relates to a high-nickel ternary positive electrode active material, a preparation method thereof and a lithium ion battery. The chemical composition of the high nickel ternary positive electrode active material is Li x Ni y Co z Mn u A v O 2 Wherein x is more than or equal to 0.9 and less than or equal to 1.1,0.6, y is more than or equal to 1, z is more than or equal to 0 and less than or equal to 0.4, u is more than or equal to 0 and less than or equal to 0.1, v is more than or equal to 0 and less than or equal to 0.1, A is ion valence greater than or equal toAt a valence of 4. A is one or more of Nb, zr, cr, mo, ti, W and V. The ion radius of the doping element A is smaller, and the doping element A easily enters the crystal structure of primary grains, so that the particle strength of the high-nickel ternary positive electrode active material is improved, and the cracking risk of the high-nickel ternary positive electrode active material particles is reduced; the doping process is improved, the doping can be carried out at the temperature lower than 800 ℃ to obtain the primary-grain-smaller high-nickel ternary positive electrode active material, the high grain strength is maintained, the structural stability is good, and further the high-nickel ternary positive electrode active material has high cycling stability.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a high-nickel ternary positive electrode active material, a preparation method thereof and a lithium ion battery.
Background
The long endurance mileage is a primary technical index of the new energy passenger car, and on the premise of ensuring safety, the continuous improvement of the energy density of the battery is a necessary development trend. The positive electrode active material is an important component of the battery, and its performance affects the performance of the battery. As the nickel content in the positive electrode active material increases, the energy density of the battery increases, and therefore, increasing the nickel content in the positive electrode active material is one of means for increasing the energy density of the battery.
Because of high nickel content, lithium-deficient phase or rock salt phase nickel oxide compound and the like are easy to generate at a correspondingly lower sintering temperature, so that the difficulty of synthesizing a pure phase material is greatly increased; in addition, due to the segregation of nickel and the difference of migration rate in the sintering process, the uniformity difference of micro-areas of the material is reduced, so that the uniformity of the form of the sintered particles is poor, and the anisotropically accumulated stress is not released, so that the particles are easy to crack or are easier to crack in subsequent application.
When the problem that the high-nickel material is easy to crack in use is solved, the doping and cladding modification of the anode material are mainly considered from the aspect of material modification. The elements doped with lithium sites or transition metal sites are adopted to achieve the effects of improving conductivity, improving the stability of the lithium intercalation and deintercalation skeleton and the like; in the aspect of coating, a low-temperature coating mode is mostly adopted on the basis of water washing, so that the purposes of improving capacity exertion and stability are achieved.
However, the existing doping sintering process adopts higher sintering temperature, so that the production cost is high, primary grains of the material are increased, the strength of the material particles is reduced, the structural stability is poor, and the electrochemical attenuation is serious.
Accordingly, improvements are needed in the art.
Disclosure of Invention
In the prior art, the high-nickel material, particularly the ultrahigh-nickel positive electrode material, has poor structural stability, poor cycling stability and low strength of doped material particles, and cannot bear high pressure, and is easy to crack and break in the rolling process of preparing electrode plates and in the charge-discharge cycle of batteries, so that the invention provides the high-nickel ternary positive electrode active material, the preparation method thereof and the lithium ion battery.
In a first aspect, the present invention provides a high nickel ternary positive electrode active material having a chemical composition of Li x Ni y Co z Mn u A v O 2 Wherein x is more than or equal to 0.9 and less than or equal to 1.1,0.6, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 0.4, u is more than or equal to 0 and less than or equal to 0.1, v is more than or equal to 0 and less than or equal to 0.1, and A is an element with an ionic valence of more than or equal to 4.
In one implementation, a is one or more of Nb, zr, cr, mo, ti, W and V.
In one implementation, x is a range consisting of 0.95, 0.96, 0.97, 0.98, 0.99, 1.00, 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, or any two thereof; y is 0.70, 0.75, 0.80, 0.83, 0.85, 0.88, 0.90, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.99 or any two of these; z is in the range of 0.01, 0.05, 0.06, 0.1, 0.12, 0.15, 0.18, 0.20, 0.25, 0.30 or any two thereof.
In a second aspect, the present invention provides a method for preparing a high-nickel ternary positive electrode active material, which is used for preparing the high-nickel ternary positive electrode active material, and comprises the following specific steps:
s1, mixing a nickel-cobalt-manganese precursor and a lithium source to obtain a mixed material, and performing primary sintering treatment on the mixed material to obtain first particles;
s2, uniformly mixing the first particles and the doping agent to obtain a mixed material, and performing secondary sintering treatment on the mixed material to obtain second particles;
and S3, reducing the temperature of the second particles to room temperature, and collecting a product to obtain the high-nickel ternary positive electrode active material.
In one implementation, in S1, the nickel cobalt manganese precursor is cobalt nickel cobalt manganese hydroxide, the lithium source is lithium hydroxide, and the dopant is an oxide or hydroxide comprising element a.
In one implementation, in S1 and S2, the mixing process is performed in a high speed mixer, the rotational speed of the high speed mixer is controlled to be 500-1500 rpm/min, and the mixing time is 10-30 min.
In one implementation manner, in the step S1, the primary sintering treatment is performed under an oxygen atmosphere, the oxygen concentration is more than or equal to 80%, the heating rate is 1-5 ℃/min, the sintering temperature is 450-600 ℃, and the time is 5-15 h.
In one implementation, in S2, the secondary sintering treatment is performed under an oxygen atmosphere, the oxygen concentration is greater than or equal to 99%, the temperature rising rate is 1-5 ℃/min, the sintering temperature is 700-900 ℃, and the time is 5-15 h.
In a third aspect, the invention provides a lithium ion battery, which comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate comprises a positive current collector and a positive active layer arranged on the surface of the positive current collector, and the positive active layer comprises the high-nickel ternary positive active material.
In one implementation, the positive electrode active layer further includes a conductive agent including any one or more of conductive carbon black, acetylene black, ketjen black, conductive graphite, conductive carbon fiber, carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, and carbon fiber, and a binder including any one or more of polyvinylidene fluoride, polytetrafluoroethylene, and lithium polyacrylate.
The beneficial effects are that: the high-nickel ternary positive electrode active material provided by the invention is beneficial to inducing Ni by doping the element A with the ion valence of more than or equal to 4 3+ To Ni 2+ The transition is realized, and the ion radius of the doped element A is smaller, so that the doped element A easily enters the crystal structure of primary grains, thereby being beneficial to improving the particle strength of the high-nickel ternary positive electrode active material and reducing the activity of the high-nickel ternary positive electrodeRisk of cracking of the particles of sexual material; the doping process is improved, the doping can be carried out at the temperature lower than 800 ℃ to obtain the primary-grain-smaller high-nickel ternary positive electrode active material, the high grain strength is maintained, the structural stability is good, and further the high-nickel ternary positive electrode active material has high cycling stability.
Drawings
Fig. 1 is an SEM image of a high nickel ternary positive electrode active material provided in example 1 of the present invention;
FIG. 2 is an SEM image of the high nickel ternary positive electrode active material provided in example 1 after being pressurized to 300 MPa;
fig. 3 is an SEM image of the high nickel ternary positive electrode active material provided in comparative example 1 of the present invention;
FIG. 4 is an SEM image of the high nickel ternary positive electrode active material provided in comparative example 1 after being pressurized to 300 MPa;
FIG. 5 is a cross-sectional SEM image of a high nickel ternary positive electrode active material provided in example 1 of the present invention;
FIG. 6 is a cross-sectional SEM image of a high nickel ternary positive electrode active material provided by comparative example 1;
fig. 7 is a graph showing the comparison of the compacted density of the positive electrode active materials provided in example 1, example 2, example 3, example 4 and comparative example 1 according to the present invention, in the process of pressurizing from 0 to 300 MPa.
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
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. Furthermore, the descriptions of the terms "one embodiment," "some embodiments," "examples," "particular examples," or "some examples," etc., described below mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily for the same embodiment or example. The technical features of the respective embodiments of the present invention may be combined with each other as long as they do not collide with each other.
The invention provides a high nickel ternary positive electrode active material, which comprises the chemical composition Li x Ni y Co z Mn u A v O 2 Wherein x is more than or equal to 0.9 and less than or equal to 1.1,0.6, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 0.4, u is more than or equal to 0 and less than or equal to 0.1, v is more than or equal to 0 and less than or equal to 0.1, and A is an element with an ionic valence of more than or equal to 4. Wherein A is one or more of Nb, zr, cr, mo, ti, W and V. Further, x is 0.95, 0.96, 0.97, 0.98, 0.99, 1.00, 1.01, 1.02, 1.03, 1.04, 1.05, 1.06 or a range of any two of them; y is 0.70, 0.75, 0.80, 0.83, 0.85, 0.88, 0.90, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.99 or any two of these; z is in the range of 0.01, 0.05, 0.06, 0.1, 0.12, 0.15, 0.18, 0.20, 0.25, 0.30 or any two thereof.
The invention provides a preparation method of a high-nickel ternary positive electrode active material, which is used for preparing the high-nickel ternary positive electrode active material and comprises the following specific steps of:
s1, mixing a nickel-cobalt-manganese precursor and a lithium source to obtain a mixed material, and performing primary sintering treatment on the mixed material to obtain first particles;
s2, uniformly mixing the first particles and the doping agent to obtain a mixed material, and performing secondary sintering treatment on the mixed material to obtain second particles;
and S3, reducing the temperature of the second particles to room temperature, and collecting a product to obtain the high-nickel ternary positive electrode active material.
Specifically, in S1, the nickel cobalt manganese precursor is cobalt nickel hydroxide manganese, the lithium source is lithium hydroxide, and the dopant is an oxide or hydroxide including element a. In S1 and S2, the mixing process is carried out in a high-speed mixer, the rotating speed of the high-speed mixer is controlled to be 500-1500 rpm/min, and the mixing time is controlled to be 10-30 min.
Specifically, in S1, the primary sintering treatment is performed in an oxygen atmosphere, the oxygen concentration is more than or equal to 80%, the heating rate is 1-5 ℃/min, the sintering temperature is 450-600 ℃, and the time is 5-15 h. In S2, the secondary sintering treatment is performed in an oxygen atmosphere, the oxygen concentration is greater than or equal to 99%, the heating rate is 1-5 ℃/min, the sintering temperature is 700-900 ℃, and the time is 5-15 h. The preparation method of the high-nickel ternary positive electrode active material provided by the invention can be used for carrying out element doping at a low temperature to obtain the high-nickel ternary positive electrode active material with smaller primary crystal grains, and the preparation process is simple. During sintering, the mixed material is placed in a sagger, and is placed in any one of high-temperature heating equipment such as a tube furnace, a muffle furnace, a box furnace, a roller kiln, a pusher kiln or a rotary kiln for sintering.
In addition, in S3, crushing the second particles prepared in S2 to make the D50 of the particles 7-15 μm, and characterizing the dispersibility of the first particles by the D50, wherein when the D50 is too small, the crushing degree is too high, the particles are easy to crush, and when the D50 is too high, the particles are agglomerated, and further crushing is needed.
In addition, after the secondary sintering is finished, metal impurities introduced in the process need to be removed, iron is generally mainly used, and iron is usually removed by using a magnetic separation mode, so that the process can be performed according to conventional operation by a person skilled in the art.
The invention provides a lithium ion battery, which comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate comprises a positive current collector and a positive active layer arranged on the surface of the positive current collector, and the positive active layer comprises the high-nickel ternary positive active material.
The positive electrode active layer further comprises a conductive agent and a binder, wherein the conductive agent comprises any one or more of conductive carbon black, acetylene black, ketjen black, conductive graphite, conductive carbon fibers, carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes and carbon fibers, and the binder comprises any one or more of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) and lithium Polyacrylate (PAALi). In the preparation process, firstly, mixing an anode active material, a conductive agent and a binder according to a certain proportion, dispersing the mixture in a solvent, typically NMP, and uniformly stirring to obtain anode active material layer slurry; secondly, uniformly coating the slurry of the positive electrode active material layer on the surface of a positive electrode current collector, typically an aluminum foil, and drying to form the positive electrode active material layer; finally tabletting and cutting to obtain the positive plate. The choice of the negative plate, the diaphragm and the electrolyte is not particularly required, and is conventional in the art.
The technical scheme provided by the invention is explained in detail below with reference to specific embodiments. Unless otherwise indicated, reagents, materials and equipment used in the examples below are conventional in the art, conventional materials and conventional equipment, and are commercially available, and reagents involved can be synthesized by methods conventional in the art.
The ternary precursors used in the following examples and comparative examples were all selected from the same ternary precursor.
Example 1:
ni is added with 0.92 Co 0.06 Mn 0.02 (OH) 2 The precursor and the lithium hydroxide monohydrate are uniformly mixed in a high-speed mixer according to the mole ratio of Li/(Ni+Co+Mn) of 1.02, and sintered for 10 hours at 500 ℃ in pure oxygen atmosphere to obtain the primary sintered material. Pre-sintering material and WO 3 And (0.5 mol%) uniformly mixing in a high-speed mixer, and sintering at 800 ℃ for 7.5 hours in pure oxygen atmosphere to obtain the two-fired material, namely the high-nickel ternary positive electrode active material.
Example 2:
ni is added with 0.92 Co 0.06 Mn 0.02 (OH) 2 The precursor and the lithium hydroxide monohydrate are uniformly mixed in a high-speed mixer according to the mole ratio of Li/(Ni+Co+Mn) of 1.02, and sintered for 10 hours at 500 ℃ in pure oxygen atmosphere to obtain the primary sintered material. Pre-sintering material and MoO 3 And (0.5 mol%) uniformly mixing in a high-speed mixer, and sintering at 760 ℃ for 7.5 hours in pure oxygen atmosphere to obtain the two-fired material, namely the high-nickel ternary positive electrode active material.
Example 3:
ni is added with 0.92 Co 0.06 Mn 0.02 (OH) 2 The precursor and the lithium hydroxide monohydrate are uniformly mixed in a high-speed mixer according to the mole ratio of Li/(Ni+Co+Mn) of 1.02And then sintering for 10 hours at 500 ℃ in pure oxygen atmosphere to obtain the primary sintered material. The presintered material is mixed with Ta 2 O 5 And (0.5 mol%) uniformly mixing in a high-speed mixer, and sintering at 770 ℃ for 7.5h in pure oxygen atmosphere to obtain the secondary sintered material, namely the high-nickel ternary positive electrode active material.
Example 4:
ni is added with 0.92 Co 0.06 Mn 0.02 (OH) 2 The precursor and the lithium hydroxide monohydrate are uniformly mixed in a high-speed mixer according to the mole ratio of Li/(Ni+Co+Mn) of 1.02, and sintered for 10 hours at 500 ℃ in pure oxygen atmosphere to obtain the primary sintered material. The presintering material is mixed with Nb 2 O 5 And (0.5 mol%) uniformly mixing in a high-speed mixer, and sintering at 760 ℃ for 7.5 hours in pure oxygen atmosphere to obtain the two-fired material, namely the high-nickel ternary positive electrode active material.
Comparative example 1:
ni is added with 0.92 Co 0.06 Mn 0.02 (OH) 2 The precursor and the lithium hydroxide monohydrate are uniformly mixed in a high-speed mixer according to the mole ratio of Li/(Ni+Co+Mn) of 1.02, and sintered for 10 hours at 500 ℃ in pure oxygen atmosphere to obtain the primary sintered material. And (3) uniformly mixing the presintered materials in a high-speed mixer, and sintering at 740 ℃ for 7.5 hours in pure oxygen atmosphere to obtain the two-fired material, namely the high-nickel ternary anode active material.
The high nickel cathode materials obtained in the examples and comparative examples were assembled into a button cell by using the technical scheme for preparing the cathode materials into lithium ion batteries, which is well known to those skilled in the art, and the specific method is as follows: the prepared high-nickel anode material, acetylene black and polyvinylidene fluoride (PVDF) are weighed according to the mass ratio of 95:2:3, evenly mixed, added with NMP and stirred to form sticky slurry, evenly coated on an aluminum foil, and then baked in vacuum at 80 ℃, pressed into tablets, and the diameter of the anode tablet is 14 mm. Pure lithium sheets with the diameter of 16mm are used as a negative electrode sheet, a 1g/L LiPF6+DEC/EC (volume ratio of 1:1) mixed solution is used as an electrolyte, a polypropylene microporous membrane is used as a diaphragm, and the battery is assembled in a glove box filled with argon.
The following description is made for the capacity retention test: the new wire test cabinet (CT-4008-5V 10mA 80 CH) is adopted, the circulation voltage is 2.5-4.3V at 25 ℃, the constant voltage cut-off current is 0.062mA, the 1C theoretical capacity is 215mAh/g, and the charge and discharge circulation is 40 circles under the condition of 0.5C current density.
The powder compaction density testing method comprises the following steps: 2g of the high nickel cathode materials obtained in the examples and comparative examples were weighed respectively using PCD2000 test equipment, placed in a sample pan with a radius of 13mm, and the powder compaction density values were recorded under 300MPa pressure. The compression resistance of the positive electrode material is characterized by a compaction density value, and the excessive compaction density value indicates that the breaking degree of the positive electrode material is too high.
Test results for positive electrode active materials and batteries provided in table 1, examples 1-4, and comparative example 1:
。
referring to table 1 and fig. 1 to 7 in combination, fig. 1 is an SEM image of the high-nickel ternary cathode active material provided in example 1 of the present invention, fig. 2 is an SEM image of the high-nickel ternary cathode active material provided in example 1 of the present invention after being pressurized to 300MPa, fig. 3 is an SEM image of the high-nickel ternary cathode active material provided in comparative example 1 of the present invention, fig. 4 is an SEM image of the high-nickel ternary cathode active material provided in comparative example 1 after being pressurized to 300MPa, fig. 5 is a cross-sectional SEM image of the high-nickel ternary cathode active material provided in example 1 of the present invention, fig. 6 is a cross-sectional SEM image of the high-nickel ternary cathode active material provided in comparative example 1 of the present invention, and fig. 7 is a compaction density comparison curve during pressurization of the cathode active materials provided in examples 1, 2, 3, 4 and 1 of the present invention from 0 to 300 MPa.
Taking fig. 1 as an example, in fig. 1: SED 15.0kV means an operating voltage of 15.0kV; WD 13.0mm means a working distance of 13.0mm; std-PC represents a standard industrial and agricultural work computer; highVac (High Vacuum) it represents a high vacuum mode; x3,000 represents a magnification of 3,000; STD 7768 represents model 7768 of the secondary topology detector; nov.15 2023 represents work date 2023-11-15.
As can be seen from table 1, the positive electrode active materials provided in examples 1 to 4 have lower compacted densities at 300MPa pressure than comparative example 1; as can be seen from fig. 7, the positive electrode active materials provided in examples 1 to 4 have a slower tendency to increase in compacted density as the pressure increases, compared to comparative example 1; according to fig. 1 to 4, compared with comparative example 1, the positive electrode active material provided in example 1 was less cracked by chipping, and most of the particles were still able to maintain sphericity intact under a pressure of 300 MPa. According to fig. 5 to 6, the positive electrode active material provided in example 1 has a radial distribution in cross section and has higher pressure resistance, and remains in a block shape even after the material particles are cracked, whereas the positive electrode active material provided in comparative example 1 has a granular distribution in cross section and has poor pressure resistance, and the material particles are crushed after being cracked.
Therefore, compared with comparative example 1, the positive electrode active material provided in example 1 has higher particle strength, can bear higher pressure, and is not easy to generate cracks in the process of pole piece roller pair and in the subsequent charge and discharge process; in addition, the sections are radially distributed, which is favorable for rapid intercalation and deintercalation of lithium ions, so that the positive electrode active material provided in the embodiment 1 has good cycle and rate performance. By introducing an element with a valence of 4 or more, a positive electrode material with high particle strength can be obtained, and further excellent capacity, rate and capacity retention rate can be obtained.
In conclusion, the high-nickel ternary positive electrode active material provided by the invention has good crystal stability and surface stability, and the crystal structure comprises the doping element A, so that the particle strength and the structural stability of the positive electrode active material are improved, the multiplying power, the circulation and other comprehensive performances of the high-nickel ternary positive electrode active material are effectively improved, and the preparation method is simple.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes using the descriptions and drawings of the present invention or directly or indirectly applied to other related technical fields are included in the scope of the invention.
Claims (10)
1. A high-nickel ternary positive electrode active material is characterized by comprising the chemical composition of Li x Ni y Co z Mn u A v O 2 Wherein x is more than or equal to 0.9 and less than or equal to 1.1,0.6, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 0.4, u is more than or equal to 0 and less than or equal to 0.1, v is more than or equal to 0 and less than or equal to 0.1, and A is an element with an ionic valence of more than or equal to 4.
2. The high nickel ternary positive electrode active material of claim 1, wherein a is one or more of Nb, zr, cr, mo, ti, W and V.
3. The high nickel ternary positive electrode active material of claim 1, wherein x is in the range of 0.95, 0.96, 0.97, 0.98, 0.99, 1.00, 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, or any two thereof; y is 0.70, 0.75, 0.80, 0.83, 0.85, 0.88, 0.90, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.99 or any two of these; z is in the range of 0.01, 0.05, 0.06, 0.1, 0.12, 0.15, 0.18, 0.20, 0.25, 0.30 or any two thereof.
4. A method for preparing a high-nickel ternary positive electrode active material, which is characterized by being used for preparing the high-nickel ternary positive electrode active material according to any one of claims 1-3, and comprising the following specific steps:
s1, mixing a nickel-cobalt-manganese precursor and a lithium source to obtain a mixed material, and performing primary sintering treatment on the mixed material to obtain first particles;
s2, uniformly mixing the first particles and the doping agent to obtain a mixed material, and performing secondary sintering treatment on the mixed material to obtain second particles;
and S3, reducing the temperature of the second particles to room temperature, and collecting a product to obtain the high-nickel ternary positive electrode active material.
5. The method for preparing a high nickel ternary positive electrode active material according to claim 4, wherein in S1, the nickel cobalt manganese precursor is cobalt nickel hydroxide manganese, the lithium source is lithium hydroxide, and the dopant is an oxide or hydroxide including element a.
6. The method for preparing a high nickel ternary positive electrode active material according to claim 4, wherein in S1 and S2, the mixing process is performed in a high-speed mixer, the rotation speed of the high-speed mixer is controlled to be 500-1500 rpm/min, and the mixing time is controlled to be 10-30 min.
7. The method for preparing a high nickel ternary positive electrode active material according to claim 4, wherein in S1, the primary sintering treatment is performed in an oxygen atmosphere, the oxygen concentration is 80% or more, the temperature rising rate is 1-5 ℃/min, the sintering temperature is 450-600 ℃, and the time is 5-15 h.
8. The method for preparing a high nickel ternary positive electrode active material according to claim 4, wherein in S2, the secondary sintering treatment is performed in an oxygen atmosphere, wherein the oxygen concentration is 99% or more, the temperature rising rate is 1-5 ℃/min, the sintering temperature is 700-900 ℃ and the time is 5-15 h.
9. The lithium ion battery is characterized by comprising a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate comprises a positive current collector and a positive active layer arranged on the surface of the positive current collector, and the positive active layer comprises the high-nickel ternary positive active material according to any one of claims 1-3 or the positive active material prepared by the preparation method of the high-nickel ternary positive active material according to any one of claims 4-8.
10. The lithium ion battery of claim 9, wherein the positive electrode active layer further comprises a conductive agent comprising any one or more of conductive carbon black, acetylene black, ketjen black, conductive graphite, conductive carbon fibers, carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, and carbon fibers, and a binder comprising any one or more of polyvinylidene fluoride, polytetrafluoroethylene, and lithium polyacrylate.
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