CN116741983A - Positive electrode material and preparation method and application thereof - Google Patents
Positive electrode material and preparation method and application thereof Download PDFInfo
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- CN116741983A CN116741983A CN202310717221.XA CN202310717221A CN116741983A CN 116741983 A CN116741983 A CN 116741983A CN 202310717221 A CN202310717221 A CN 202310717221A CN 116741983 A CN116741983 A CN 116741983A
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 132
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 30
- 238000009826 distribution Methods 0.000 claims abstract description 20
- 238000012360 testing method Methods 0.000 claims abstract description 16
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- 238000002156 mixing Methods 0.000 claims description 58
- 239000000203 mixture Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 32
- 239000011572 manganese Substances 0.000 claims description 31
- 239000002243 precursor Substances 0.000 claims description 30
- 239000010405 anode material Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229910013716 LiNi Inorganic materials 0.000 claims description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- 239000011163 secondary particle Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000011164 primary particle Substances 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- IWTZGPIJFJBSBX-UHFFFAOYSA-G aluminum;cobalt(2+);nickel(2+);heptahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Co+2].[Ni+2] IWTZGPIJFJBSBX-UHFFFAOYSA-G 0.000 claims description 4
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 54
- 239000001301 oxygen Substances 0.000 description 54
- 229910052760 oxygen Inorganic materials 0.000 description 54
- 239000000463 material Substances 0.000 description 30
- 239000012298 atmosphere Substances 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 26
- 238000001035 drying Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 238000001816 cooling Methods 0.000 description 15
- 238000001878 scanning electron micrograph Methods 0.000 description 15
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 14
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 14
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 14
- 238000000498 ball milling Methods 0.000 description 13
- 238000000975 co-precipitation Methods 0.000 description 13
- 238000006138 lithiation reaction Methods 0.000 description 13
- 238000004321 preservation Methods 0.000 description 13
- 238000000576 coating method Methods 0.000 description 8
- 238000005056 compaction Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/66—Nickelates containing alkaline earth metals, e.g. SrNiO3, SrNiO2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/70—Nickelates containing rare earth, e.g. LaNiO3
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a positive electrode material, a preparation method and application thereof, wherein the particle size distribution width SPAN of the positive electrode material is 1.30-1.90, the positive electrode material comprises M element, and the ionic radius of the M element is more than 0.075nm; the positive electrode material is of a layered structure, D104 of the positive electrode material is 60-75 nm, and D104 is the size of crystal grains in the direction vertical to the crystal face of the diffraction peak of the positive electrode material obtained by XRD (X-ray diffraction) testing. The positive electrode material is applied to the battery, and is beneficial to improving the energy density, the cycle performance and the safety of the battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a positive electrode material, a preparation method and application thereof.
Background
In recent years, in order to meet the increasing demand for high energy density of lithium ion batteries, positive electrode materials are being developed toward higher nickel and higher voltage. Wherein, higher Ni content can bring higher capacity; the voltage can be increased to increase the capacity of the material, and the voltage platform of the material can be increased. However, with the increase of the charging voltage, the interface stability between the positive electrode material and the electrolyte is reduced, which causes an increase of side reactions and seriously affects the cycle performance of the lithium ion battery. Therefore, how to improve both the energy density and the cycle performance of the battery is an important point of study in the art.
In order to achieve both the energy density and the cycle performance of the battery, the method of surface coating, single crystallization treatment or electrolyte additive addition of the positive electrode material is mainly used for improvement. For example, patent document CN114335547a discloses a high-rate ternary cathode material, a preparation method and application thereof, wherein a precursor is first subjected to element doping, and then subjected to element doping in two sintering steps, so that contact between the surface of the material and an electrolyte is reduced, and the cycle performance of the material is improved. However, the method has complicated steps, high preparation cost and difficult realization of large-scale production. Patent document CN111952585a discloses a high-compaction-density rubidium-doped lithium battery positive electrode material and a preparation method thereof, and the compaction density of the material is increased by solid-phase high-temperature calcination and grinding, rubidium/cesium ion doping and the like. However, the solid phase calcination method is difficult to realize uniform mixing of materials, is unfavorable for performance exertion of doping elements, and can only singly improve the energy density or the cycle performance of the battery, and has yet to be further improved for considering the energy density and the cycle performance of the battery.
Disclosure of Invention
The positive electrode material provided by the invention is applied to the battery, and is beneficial to improving the energy density, the cycle performance and the safety of the battery.
The invention also provides a preparation method of the positive electrode material, which can prepare the positive electrode material, and the positive electrode material is applied to a battery, thereby being beneficial to improving the energy density, the cycle performance and the safety of the battery.
The invention also provides a positive plate, which is beneficial to improving the energy density, the cycle performance and the safety of the battery by applying the positive plate to the battery due to the positive plate.
The invention also provides a battery which has high energy density, excellent cycle performance and safety due to the positive plate.
In a first aspect of the present invention, there is provided a positive electrode material, wherein the positive electrode material has a particle size distribution width SPAN of 1.30 to 1.90, and comprises an M element, and the M element has an ionic radius of greater than 0.075nm;
the positive electrode material is of a layered structure, D104 of the positive electrode material is 60-75 nm, and D104 is the size of crystal grains in the direction vertical to the crystal face of the diffraction peak of the positive electrode material obtained by XRD (X-ray diffraction) testing.
The positive electrode material as described above, wherein the M element includes at least one element of Na, ce, sr, K, ti, rb, ba, Y.
The positive electrode material as described above, wherein the positive electrode material is composed of primary particles and secondary particles; and/or the number of the groups of groups,
the first discharge capacity of the positive electrode material under the conditions of 2.5-4.25V and 0.1C is not less than 200mAh/g; and/or the number of the groups of groups,
the first effect of the positive electrode material is more than 90%.
The positive electrode material, wherein the molecular formula of the positive electrode material is LiNi x Co y A Z M g N h O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0.6 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.4, z is more than or equal to 0 and less than or equal to 0.4, g is more than or equal to 0 and less than or equal to 0.05, h is more than or equal to 0 and less than or equal to 0.05, and A comprises at least one of Mn and Al; m is Na, ce, sr, Y, K, ti, rb, ba; n is at least one of Ta, nb, ge, W, zr, B, ca, mo.
The positive electrode material is prepared from a precursor, a lithium source and a compound for providing M element through sintering treatment and vibration treatment in sequence.
The positive electrode material as described above, wherein the vibration frequency of the vibration treatment is not less than 180 times/min; and/or the number of the groups of groups,
the temperature of the vibration treatment is 100-350 ℃; and/or the number of the groups of groups,
the sintering treatment temperature is 720-850 ℃.
In a second aspect of the present invention, there is provided a method for preparing the positive electrode material according to the first aspect, comprising the steps of: and mixing the precursor, the lithium source and the compound for providing the M element, and then sequentially carrying out sintering treatment and vibration treatment to obtain the anode material.
The preparation method comprises the steps of mixing a precursor, a lithium source and an additive to obtain a first mixture; performing first sintering treatment on the first mixture to obtain an intermediate;
and sequentially carrying out crushing treatment, water washing treatment and vibration treatment on the intermediate to obtain the anode material.
The preparation method as described above, wherein the precursor comprises at least one of nickel cobalt manganese hydroxide and nickel cobalt aluminum hydroxide.
The preparation method comprises the step of performing second sintering treatment on the vibration treatment product and the compound for providing the N element after the vibration treatment, so as to obtain the positive electrode material.
In a third aspect of the present invention, there is provided a positive electrode sheet comprising the positive electrode material according to the first aspect or the positive electrode material produced by the production method according to the second aspect.
In a fourth aspect of the present invention, there is provided a lithium ion battery including the positive electrode sheet according to the third aspect.
The implementation of the invention has at least the following beneficial effects:
according to the positive electrode material provided by the invention, as the M element ion radius is larger, the M element is mainly doped on the crystal surface, so that the crystal surface becomes smooth, the fluidity is better, the dispersibility of particles is improved, at the same time, at least part of secondary particles are split into primary particles through vibration treatment, the particle size distribution of the positive electrode material is improved, the particle size distribution width SPAN of the positive electrode material is limited to be 1.30-1.90, and the particle size distribution of the positive electrode material is further ensured. When the positive electrode material is coated on the positive electrode current collector, primary particles can be distributed at gaps of secondary particles, so that the compaction density of powder can be improved, the volume energy density of a battery can be effectively improved, the stress borne by the particles is ensured to be more uniform, the crushing probability is reduced, the gas yield is reduced, and the cycle performance and the safety of the battery are improved.
Drawings
FIG. 1 is an SEM image (magnification of 10K) of a positive electrode material according to example 1 of the present invention;
FIG. 2 is an SEM image (magnification of 10K) of a positive electrode material according to example 2 of the present invention;
FIG. 3 is an SEM image (magnification of 10K) of a positive electrode material according to example 3 of the present invention;
FIG. 4 is an SEM image (magnification of 10K) of a positive electrode material according to example 4 of the present invention;
FIG. 5 is an SEM image (magnification of 10K) of a positive electrode material according to example 5 of the present invention;
FIG. 6 is an SEM image (magnification of 10K) of a positive electrode material of comparative example 1 of the present invention;
FIG. 7 is an SEM image (magnification of 10K) of a positive electrode material of comparative example 2 of the present invention;
FIG. 8 is an SEM image (magnification of 10K) of a positive electrode material of comparative example 3 of the present invention;
fig. 9 is an SEM image (magnification 10K) of the positive electrode material of comparative example 4 of the present invention;
FIG. 10 is an SEM image (magnification of 10K) of a positive electrode material of comparative example 5 of the present invention;
FIG. 11 is an SEM image (magnification of 10K) of a positive electrode material according to example 6 of the present invention;
FIG. 12 is an SEM image (magnification of 10K) of a positive electrode material according to example 7 of the present invention;
FIG. 13 is an SEM image (magnification of 10K) of a positive electrode material according to example 8 of the present invention;
fig. 14 is an SEM image (magnification 10K) of the positive electrode material of example 9 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. 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.
In a first aspect of the present invention, there is provided a positive electrode material, wherein the positive electrode material has a particle size distribution width SPAN of 1.30 to 1.90, and comprises an element M, and the ion radius of the element M is greater than 0.075nm; the positive electrode material is of a layered structure, D104 of the positive electrode material is 60-75 nm, and D104 is the size of crystal grains in the direction vertical to the crystal face of the diffraction peak of the positive electrode material obtained by XRD (X-ray diffraction) testing.
Because the ionic radius of the M element is larger than 0.075nm, the M element does not enter the primary particles, and the M element is mainly concentrated on the outer surface and in the pores of the secondary particles, so that the crystallinity of the surfaces of the secondary particles is improved, and meanwhile, the M element with large ionic radius is introduced, so that the surface anisotropy of the particles is increased, and the particles are easier to disperse in the subsequent vibration treatment.
The positive electrode material provided by the invention consists of a plurality of lamellar sheets, and van der Waals force exists between the lamellar sheets, so that intercalation and deintercalation of lithium ions can be accommodated. The positive electrode material with the layered structure has higher ion transmission efficiency and electrochemical performance.
The crystal grain size of the positive electrode material is 60-75 nm in the direction vertical to the crystal face of the 104 diffraction peak, which is obtained by XRD ray diffraction test.
The positive electrode material provided by the invention consists of primary particles and secondary particles. In some embodiments, the positive electrode material has a particle size distribution width SPAN of 1.30 to 1.90. The width of the particle size distribution of the positive electrode material means substantially the width of the particle size distribution of all the primary particles and the secondary particles in the positive electrode material. The particle size distribution width of the positive electrode material is calculated according to a formula (D90-D10)/D50, wherein D10 is the particle size corresponding to the volume cumulative distribution percentage of the sample reaching 10%; d50 is the corresponding particle size when the cumulative volume distribution percentage of the sample reaches 50%; d90 is the particle size corresponding to the cumulative percentage distribution of the sample volume reaching 90%.
The present invention is not limited to the method for testing D90, D50, and D10 of the positive electrode material, and may be, for example, measured by a laser particle size analyzer.
The specific values of D90, D50, and D10 of the positive electrode material are not limited in the present invention, as long as the width of the particle size distribution of the positive electrode material is ensured within the above-described range. In some embodiments, the D90 of the positive electrode material is 17.0 to 21.0 μm; the D10 of the positive electrode material is 2.5-5.5 mu m; the D50 of the positive electrode material is 9.0-12.0 mu m. When the D90, D50 and D10 of the positive electrode material are limited in the above range, the particle size distribution width of the positive electrode material can be realized, the compaction density of the prepared positive electrode plate is improved, the stress of particles is ensured to be more uniform, the particles are prevented from cracking, and the energy density, the cycle performance and the safety of the battery are further improved.
According to the research of the invention, the application of the positive electrode material in the battery is beneficial to improving the energy density and the cycle performance of the battery. This is because, on the one hand, since the positive electrode material contains an M element having a large ion radius, the M element is doped on the crystal surface during the sintering treatment, so that the crystal surface becomes smooth, the fluidity is better, and the dispersibility and the particle strength of the particles are favorably improved, and on the other hand, by defining the particle size distribution of the positive electrode material, the compaction density of the positive electrode material is favorably improved. When the positive electrode material is coated on the positive electrode current collector, primary particles can be distributed at gaps of secondary particles, so that the compaction density of powder can be improved, the volume energy density of a battery can be effectively improved, the stress borne by the particles is ensured to be more uniform, the crushing probability is reduced, the gas yield is reduced, and the cycle performance and the safety of the battery are improved.
The invention is not limited to the specific type of M element, so long as the ionic radius of the M element is ensured to be more than 0.075 nm. For example, in some embodiments, the M element includes at least one element of Na, ce, sr, K, ti, rb, ba, Y. The positive electrode material consists of primary particles and secondary particles; and/or the number of the groups of groups,
in the invention, the first discharge capacity of the positive electrode material under the conditions of 2.5-4.25V and 0.1C is not less than 200mAh/g; and/or, the first effect of the positive electrode material is greater than 90%; and/or, I003/I004=2.0-2.5 of the positive electrode material, and the ratio of the relative intensities of the X-ray diffraction peak (003) and the X-ray diffraction peak (004) of the positive electrode material is marked as I003/I004.
The positive electrode material with the layered structure is mainly lithium cobaltate and ternary material. In some embodiments, the positive electrode material of the present invention has a molecular formula of LiNi x Co y A Z M g N h O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0.6 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.4, z is more than or equal to 0 and less than or equal to 0.4, g is more than or equal to 0 and less than or equal to 0.05, h is more than or equal to 0 and less than or equal to 0.05, and A comprises at least one of Mn and Al; m is Na, ce, sr, Y, K, ti, rb, ba; n is at least one of Ta, nb, ge, W, zr, B, ca, mo.
In the invention, the positive electrode material is prepared by sequentially sintering and vibrating a precursor, a lithium source and a compound for providing M element. Sintering refers to the conversion of a powdery material into secondary particles. And mixing the precursor, lithium hydroxide and the compound for providing M element, and then sintering to obtain a sintered product. The sintered product is mainly secondary particles composed of a plurality of primary particles agglomerated. The secondary particles have a spherical or approximately spherical shape, for example an ellipsoidal shape. In the present invention, the vibration treatment means drying while vibrating. When the sintering product is subjected to vibration treatment, on one hand, primary particles in at least part of secondary particles are dispersed in the vibration process, so that the particle size distribution of the positive electrode material is improved, and the compaction density of the positive electrode material powder is improved; on the other hand, the drying treatment is carried out while vibrating, which is beneficial to improving the production efficiency.
Wherein the precursor is nickel cobalt manganese hydroxide (NCM) or nickel cobalt aluminum hydroxide (NCA).
The particle size distribution width of the positive electrode material is favorably controlled by regulating and controlling the parameters of vibration treatment. In some embodiments, the vibration frequency of the vibration treatment is not less than 180 times/min.
The present invention is not limited to the temperature of the vibration treatment, and may be realized by drying. In some embodiments, the temperature of the vibration treatment is 100 to 350 ℃. When the temperature of vibration treatment is 100-200 ℃, the dried material can be subjected to secondary sintering treatment to obtain the anode material. When the temperature of the vibration treatment is 200-350 ℃, secondary sintering treatment can be realized in the vibration treatment process, and the dried material can be directly used as a positive electrode material.
The temperature of the sintering treatment is not limited in the present invention, as long as sintering of the precursor, the lithium source, and the compound that provides the M element can be achieved. In some embodiments, the sintering process is in the range of 720-850 ℃, e.g., 720 ℃, 750 ℃, 780 ℃, 800 ℃, 820 ℃, 850 ℃, or any two of these. By limiting the sintering temperature to the above range, it is advantageous to achieve a D104 of 60 to 75nm for the positive electrode material.
In a second aspect of the present invention, there is provided a method for preparing the positive electrode material of the first aspect, comprising the steps of: and mixing the precursor, the lithium source and the compound for providing the M element, and then sequentially carrying out sintering treatment and vibration treatment to obtain the anode material.
The method for mixing the precursor, the lithium source and the additive is not limited, for example, in some embodiments, the precursor, the lithium source and the additive are mixed to obtain a first mixture; performing first sintering treatment on the first mixture to obtain an intermediate; and (3) sequentially carrying out crushing treatment, water washing treatment and vibration treatment on the intermediate to obtain the positive electrode material.
Wherein the first sintering treatment is to convert the powdery material into a compact (polycrystalline material); crushing the sintered product to prevent adhesion; the water washing treatment is to remove residual powder on the surface of the sintered product.
The present invention is not limited to specific parameters of the first sintering treatment and the vibration treatment, and for example, the temperature of the first sintering treatment is 720 to 850 ℃ and the temperature of the vibration treatment is 100 to 350 ℃. The temperature of the vibration treatment is limited to be 100-350 ℃, which is favorable for removing residual moisture in the water washing process. When the temperature of the vibration treatment is 100-200 ℃, the material after the vibration treatment can be subjected to secondary sintering treatment to obtain the anode material. When the temperature of the vibration treatment is 200-350 ℃, the secondary sintering treatment can be realized by directly adding the coating material under the temperature condition after the vibration treatment is finished, secondary sintering ingredients are not needed, and the dried material can be directly used as a positive electrode material.
Wherein the vibration treatment may be performed in a vibration drying apparatus, such as a vibration oven.
In some embodiments, after the vibration treatment, a second sintering treatment is performed on the vibration treatment product and the compound providing the N element, so as to obtain the positive electrode material.
In the above embodiment, the compound that provides the N element is coated on the surface of the vibration-treated product by the second sintering treatment. According to the invention, the M element is introduced and the vibration treatment is carried out, so that the obtained vibration treatment product has excellent dispersibility, the coating of the N element in the second sintering treatment is facilitated, and the coating uniformity and the interface protection are improved.
In a third aspect of the present invention, there is provided a positive electrode sheet comprising the positive electrode material of the first aspect or the positive electrode material produced by the production method of the second aspect.
The positive plate can also be prepared by adopting the conventional technical means in the field, specifically, the positive electrode material, the conductive agent and the binder can be uniformly dispersed in a solvent to obtain positive electrode active layer slurry, then the positive electrode active layer slurry is coated on at least one functional surface of a positive electrode current collector, and the positive electrode plate can be obtained after drying.
The specific types of the conductive agent and the adhesive are not particularly limited, and the conductive agent, the adhesive and the like can be conventional materials in the field, for example, the conductive agent can be one or more selected from conductive carbon black, carbon nano tubes, conductive graphite and graphene, and the adhesive can be one or more selected from polyvinylidene fluoride (PVDF), acrylic modified PVDF, polyacrylate polymers, polyimide, styrene-butadiene rubber and styrene-acrylic rubber.
The coating method is not particularly limited, and the coating of the positive electrode active layer slurry can be realized by adopting any coating method such as gravure coating, extrusion coating, spray coating, screen printing and the like.
In a fourth aspect of the present invention, there is provided a lithium ion battery including the positive electrode sheet provided in the third aspect. The lithium ion battery provided by the invention comprises a diaphragm, a negative plate and electrolyte besides the positive plate. The composition of the negative electrode sheet can refer to a conventional negative electrode sheet in the field, and the separator can also adopt a separator conventionally used in the field, such as a PP film, a PE film and the like.
The lithium ion battery can be prepared by adopting a conventional method in the art, specifically, the positive plate, the diaphragm and the negative plate are sequentially stacked and placed, the battery core is obtained through lamination or winding process, and then the lithium ion battery is obtained through the procedures of baking, liquid injection, formation, encapsulation and the like.
The present invention will be further illustrated by the following specific examples and comparative examples.
Example 1
1kg of precursor Ni obtained by the coprecipitation method is added into a 2L ball milling tank 0.85 Co 0.06 Mn 0.09 (OH) 2 Adding 4635 g of lithium hydroxide monohydrate and 1.23g of CeO according to the molar ratio of the lithiation coefficient of 1:1.03 2 Adding into a 5L high-speed mixer, mixing at 350rpm for 15min, placing the mixture into a sagger, introducing oxygen atmosphere (oxygen concentration is not less than 80%), heating to 760 ℃ at 2 ℃/min for sintering for 12h, cooling to room temperature, and then using 1:1, washing with water for 10 min, centrifuging at 1000rpm for 15min, drying at 200deg.C in a vibration oven at 200 times/min for 5 hr, mixing the dried material with 2.5g WO 3 Adding into a 2L high-speed mixer, mixing at 250rpm for 15min, placing the mixture into a sagger after uniform mixing, introducing oxygen atmosphere (oxygen concentration is more than or equal to 80%), heating to 320 ℃ at 2 ℃/min, and sintering for 10h under heat preservation to obtain the anode material LiNi 0.847 Co 0.06 Mn 0.09 Ce 0.001 W 0.002 O 2 。
Example 2
1kg of precursor Ni obtained by the coprecipitation method is added into a 2L ball milling tank 0.85 Co 0.06 Mn 0.09 (OH) 2 Adding lithium hydroxide monohydrate 4635 g and NaCl in the molar ratio of 1 to 1.03, adding into a 5L high-speed mixer, mixing at 350rpm for 15min, placing the mixture into a sagger, introducing oxygen atmosphere (oxygen concentration is more than or equal to 80%), heating to 760 ℃ at 2 ℃/min for sintering for 12h, cooling to room temperature, and then using 1:1, washing with water for 10 min, centrifuging at 1000rpm for 15min, drying at 200deg.C under vibration oven at vibration frequency of 200 times/min for 5 hr, mixing the dried material with 2.5g WO 3 Adding into a 2L high-speed mixer, mixing at 250rpm for 15min, placing the mixture into a sagger after uniform mixing, introducing oxygen atmosphere (oxygen concentration is more than or equal to 80%), heating to 320 ℃ at 2 ℃/min, and sintering for 10h under heat preservation to obtain the anode material LiNi 0.847 Co 0.06 Mn 0.09 Na 0.001 W 0.002 O 2 。
Example 3
1kg of precursor Ni obtained by the coprecipitation method is added into a 2L ball milling tank 0.85 Co 0.06 Mn 0.09 (OH) 2 Adding lithium hydroxide monohydrate 460 g and KCl 1.91g according to a lithiation coefficient molar ratio of 1:1.03, adding into a 5L high-speed mixer, mixing for 15min at a speed of 350rpm, placing the mixture into a sagger, introducing oxygen atmosphere (the oxygen concentration is more than or equal to 80%), heating to 760 ℃ at 2 ℃/min for sintering for 12h, cooling to room temperature, and then using 1:1, washing with water for 10 min, centrifuging at 1000rpm for 15min, drying at 200deg.C under vibration oven at vibration frequency of 200 times/min for 5 hr, mixing the dried material with 2.5g WO 3 Adding into a 2L high-speed mixer, mixing at 250rpm for 15min, placing the mixture into a sagger after uniform mixing, introducing oxygen atmosphere (oxygen concentration is more than or equal to 80%), heating to 320 ℃ at 2 ℃/min, and sintering for 10h under heat preservation to obtain the anode material LiNi 0.847 Co 0.06 Mn 0.09 K 0.001 W 0.002 O 2 。
Example 4
1kg of the mixture was fed into a 2L ball millPrecursor Ni obtained by precipitation method 0.85 Co 0.06 Mn 0.09 (OH) 2 Adding 4635 g of lithium hydroxide monohydrate and 1.54g of CeF according to the molar ratio of lithiation coefficient of 1:1.03 4 Adding into a 5L high-speed mixer, mixing at 350rpm for 15min, and placing the mixture into a sagger. Placing the mixture into a sagger, introducing oxygen atmosphere (the oxygen concentration is more than or equal to 80%), heating to 760 ℃ at 2 ℃/min for sintering for 12h, cooling to room temperature, and then using 1:1, washing with water for 10 min, centrifuging at 1000rpm for 15min, drying at 200deg.C under vibration oven at vibration frequency of 200 times/min for 5 hr, mixing the dried material with 2.5g WO 3 Adding into a 2L high-speed mixer, mixing at 250rpm for 15min, placing the mixture into a sagger after uniform mixing, introducing oxygen atmosphere (oxygen concentration is more than or equal to 80%), heating to 320 ℃ at 2 ℃/min, and sintering for 10h under heat preservation to obtain the anode material LiNi 0.847 Co 0.06 Mn 0.09 Ce 0.001 W 0.002 O 2 。
Example 5
1kg of precursor Ni obtained by the coprecipitation method is added into a 2L ball milling tank 0.85 Co 0.06 Mn 0.09 (OH) 2 Adding 4635 g of lithium hydroxide monohydrate and 1.23g of CeO according to the molar ratio of the lithiation coefficient of 1:1.03 2 Adding into a 5L high-speed mixer, mixing at 350rpm for 15min, placing the mixture into a sagger, introducing oxygen atmosphere (oxygen concentration is not less than 80%), heating to 760 ℃ at 2 ℃/min for sintering for 12h, cooling to room temperature, and then using 1:1, washing with water for 10 min, centrifuging at 1000rpm for 15min, drying at 200deg.C under vibration oven at vibration frequency of 200 times/min for 3 hr, and adding 2.5g WO 3 Continuously vibrating and drying for 3 hours to obtain a positive electrode material LiNi 0.847 Co 0.06 Mn 0.09 Ce 0.001 W 0.002 O 2 。
Example 6
1kg of precursor Ni obtained by the coprecipitation method is added into a 2L ball milling tank 0.85 Co 0.06 Mn 0.09 (OH) 2 Adding lithium hydroxide monohydrate 460 g and SrO 1.18g according to the molar ratio of the lithiation coefficient of 1:1.03, addingMixing in 5L high mixer at 350rpm for 15min, placing the mixture into a sagger, introducing oxygen atmosphere (oxygen concentration is not less than 80%), heating to 760 ℃ at 2 ℃/min for sintering for 12h, cooling to room temperature, and then using 1:1, washing with water for 10 min, centrifuging at 1000rpm for 15min, drying at 200deg.C in a vibration oven at 200 times/min for 5 hr, mixing the dried material with 2.5g WO 3 Adding into a 2L high-speed mixer, mixing at 250rpm for 15min, placing the mixture into a sagger after uniform mixing, introducing oxygen atmosphere (oxygen concentration is more than or equal to 80%), heating to 320 ℃ at 2 ℃/min, and sintering for 10h under heat preservation to obtain the anode material LiNi 0.847 Co 0.06 Mn 0.09 Sr 0.001 W 0.002 O 2 。
Example 7
1kg of precursor Ni obtained by the coprecipitation method is added into a 2L ball milling tank 0.85 Co 0.06 Mn 0.09 (OH) 2 Adding lithium hydroxide monohydrate 460 g and Rb 1.09g according to the molar ratio of the lithiation coefficient of 1:1.03 2 O, adding the mixture into a 5L high-speed mixer, mixing for 15min at a speed of 350rpm, putting the mixture into a sagger, introducing oxygen atmosphere (the oxygen concentration is more than or equal to 80%), heating to 760 ℃ at 2 ℃/min, sintering for 12h, cooling to room temperature, and then using 1:1, washing with water for 10 min, centrifuging at 1000rpm for 15min, drying at 200deg.C in a vibration oven at 200 times/min for 5 hr, mixing the dried material with 2.5g WO 3 Adding into a 2L high-speed mixer, mixing at 250rpm for 15min, placing the mixture into a sagger after uniform mixing, introducing oxygen atmosphere (oxygen concentration is more than or equal to 80%), heating to 320 ℃ at 2 ℃/min, and sintering for 10h under heat preservation to obtain the anode material LiNi 0.847 Co 0.06 Mn 0.09 Rb 0.001 W 0.002 O 2 。
Example 8
1kg of precursor Ni obtained by the coprecipitation method is added into a 2L ball milling tank 0.85 Co 0.06 Mn 0.09 (OH) 2 Adding lithium hydroxide monohydrate 460 g and BaO 0.90g into a 5L high-speed mixer according to the molar ratio of the lithiation coefficient of 1:1.03, mixing for 15min at the speed of 350rpm, mixingPlacing the materials into a sagger, introducing oxygen atmosphere (the oxygen concentration is more than or equal to 80%), heating to 760 ℃ at 2 ℃/min for sintering for 12h, cooling to room temperature, and then using 1:1, washing with water for 10 min, centrifuging at 1000rpm for 15min, drying at 200deg.C in a vibration oven at 200 times/min for 5 hr, mixing the dried material with 2.5g WO 3 Adding into a 2L high-speed mixer, mixing at 250rpm for 15min, placing the mixture into a sagger after uniform mixing, introducing oxygen atmosphere (oxygen concentration is more than or equal to 80%), heating to 320 ℃ at 2 ℃/min, and sintering for 10h under heat preservation to obtain the anode material LiNi 0.847 Co 0.06 Mn 0.09 Ba 0.001 W 0.002 O 2 。
Example 9
1kg of precursor Ni obtained by the coprecipitation method is added into a 2L ball milling tank 0.85 Co 0.06 Mn 0.09 (OH) 2 Adding 4635 g of lithium hydroxide monohydrate and 1.28g of Y according to the molar ratio of lithiation coefficient of 1:1.03 2 O 3 Adding into a 5L high-speed mixer, mixing at 350rpm for 15min, placing the mixture into a sagger, introducing oxygen atmosphere (oxygen concentration is not less than 80%), heating to 760 ℃ at 2 ℃/min for sintering for 12h, cooling to room temperature, and then using 1:1, washing with water for 10 min, centrifuging at 1000rpm for 15min, drying at 200deg.C in a vibration oven at 200 times/min for 5 hr, mixing the dried material with 2.5g WO 3 Adding into a 2L high-speed mixer, mixing at 250rpm for 15min, placing the mixture into a sagger after uniform mixing, introducing oxygen atmosphere (oxygen concentration is more than or equal to 80%), heating to 320 ℃ at 2 ℃/min, and sintering for 10h under heat preservation to obtain the anode material LiNi 0.847 Co 0.06 Mn 0.09 Y 0.001 W 0.002 O 2 。
Comparative example 1
1kg of precursor Ni obtained by the coprecipitation method is added into a 2L ball milling tank 0.85 Co 0.06 Mn 0.09 (OH) 2 465g of lithium hydroxide monohydrate is added according to the molar ratio of the lithiation coefficient of 1:1.03, the mixture is added into a 5L high-speed mixer and mixed for 15min at the speed of 350rpm, the mixture is put into a sagger, and oxygen atmosphere (the oxygen concentration is more than or equal to 80 percent) is introduced, and the mixture is added into a kettle at the speed of 2 percentHeating to 760 ℃ in a period of time for sintering for 12 hours, cooling to room temperature, and then using 1:1, washing with water for 10 min, centrifuging at 1000rpm for 15min, drying at 200deg.C under vibration oven at vibration frequency of 200 times/min for 5 hr, mixing the dried material with 2.5g WO 3 Adding into a 2L high-speed mixer, mixing at 250rpm for 15min, placing the mixture into a sagger after uniform mixing, introducing oxygen atmosphere (oxygen concentration is more than or equal to 80%), heating to 320 ℃ at 2 ℃/min, and sintering for 10h under heat preservation to obtain the anode material LiNi 0.848 Co 0.06 Mn 0.09 W 0.002 O 2 。
Comparative example 2
1kg of precursor Ni obtained by the coprecipitation method is added into a 2L ball milling tank 0.85 Co 0.06 Mn 0.09 (OH) 2 Adding lithium hydroxide monohydrate 460 g and MgO 1.66g according to the molar ratio of the lithiation coefficient of 1:1.03, adding into a 5L high-speed mixer, mixing for 15min at the speed of 350rpm, putting the mixture into a sagger, introducing oxygen atmosphere (the oxygen concentration is more than or equal to 80%), heating to 760 ℃ at the speed of 2 ℃/min for sintering for 12h, cooling to room temperature, and then using 1:1, washing with water for 10 min, centrifuging at 1000rpm for 15min, drying at 200deg.C under vibration oven at vibration frequency of 200 times/min for 5 hr, mixing the dried material with 2.5g WO 3 Adding into a 2L high-speed mixer, mixing at 250rpm for 15min, placing the mixture into a sagger after uniform mixing, introducing oxygen atmosphere (oxygen concentration is more than or equal to 80%), heating to 320 ℃ at 2 ℃/min, and sintering for 10h under heat preservation to obtain the anode material LiNi 0.847 Co 0.06 Mn 0.09 Mg 0.001 W 0.002 O 2 。
Comparative example 3
1kg of precursor Ni obtained by the coprecipitation method is added into a 2L ball milling tank 0.85 Co 0.06 Mn 0.09 (OH) 2 Adding 4635 g of lithium hydroxide monohydrate and 1.23g of CeO according to the molar ratio of the lithiation coefficient of 1:1.03 2 Adding into 5L high-speed mixer, mixing at 350rpm for 15min, placing the mixture into sagger, introducing oxygen atmosphere (oxygen concentration is not less than 80%), heating to 760 deg.C at 2 deg.C/min, sintering for 12 hr, cooling to room temperature, and cooling to obtain the final product1:1, washing with water for 10 min, centrifuging at 1000rpm for 15min, drying at 200deg.C under vibration oven at vibration frequency of 200 times/min for 5 hr, mixing the dried material with 2.5g WO 3 Adding into a 2L high-speed mixer, mixing at 250rpm for 15min, placing the mixture into a sagger after uniform mixing, introducing oxygen atmosphere (oxygen concentration is more than or equal to 80%), heating to 320 ℃ at 2 ℃/min, and sintering for 10h under heat preservation to obtain the anode material LiNi 0.847 Co 0.06 Mn 0.09 Ce 0.001 W 0.002 O 2 。
Comparative example 4
1kg of precursor Ni obtained by the coprecipitation method is added into a 2L ball milling tank 0.85 Co 0.06 Mn 0.09 (OH) 2 Adding 4635 g of lithium hydroxide monohydrate and 1.23g of CeO according to the molar ratio of the lithiation coefficient of 1:1.03 2 Adding into a 5L high-speed mixer, mixing at 350rpm for 15min, placing the mixture into a sagger, introducing oxygen atmosphere (the oxygen concentration is more than or equal to 80%), heating to 650 ℃ at 2 ℃/min for sintering for 12h, cooling to room temperature, and then using 1:1, washing with water for 10 min, centrifuging at 1000rpm for 15min, drying at 200deg.C under vibration oven at vibration frequency of 200 times/min for 5 hr, mixing the dried material with 2.5g WO 3 Adding into a 2L high-speed mixer, mixing at 250rpm for 15min, placing the mixture into a sagger after uniform mixing, introducing oxygen atmosphere (oxygen concentration is more than or equal to 80%), heating to 320 ℃ at 2 ℃/min, and sintering for 10h under heat preservation to obtain the anode material LiNi 0.847 Co 0.06 Mn 0.09 Ce 0.001 W 0.002 O 2 。
Comparative example 5
1kg of precursor Ni obtained by the coprecipitation method is added into a 2L ball milling tank 0.85 Co 0.06 Mn 0.09 (OH) 2 Adding 4635 g of lithium hydroxide monohydrate and 1.23g of CeO according to the molar ratio of the lithiation coefficient of 1:1.03 2 Adding into a 5L high-speed mixer, mixing at 350rpm for 15min, placing the mixture into a sagger, introducing oxygen atmosphere (the oxygen concentration is more than or equal to 80%), heating to 880 ℃ at 2 ℃/min for sintering for 12h, cooling to room temperature, and then using 1:1, washing with water for 10 minutes, thenCentrifuging at 1000rpm for 15min, drying at 200deg.C in a vibration oven at vibration frequency of 200 times/min for 5 hr, mixing the dried material with 2.5g WO 3 Adding into a 2L high-speed mixer, mixing at 250rpm for 15min, placing the mixture into a sagger after uniform mixing, introducing oxygen atmosphere (oxygen concentration is more than or equal to 80%), heating to 320 ℃ at 2 ℃/min, and sintering for 10h under heat preservation to obtain the anode material LiNi 0.847 Co 0.06 Mn 0.09 Ce 0.001 W 0.002 O 2 。
Test examples
1. Capacity testing
The positive electrode materials in the embodiment are assembled into a button cell, and the specific method is as follows: the positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) are weighed according to the mass ratio of 94:3:3, evenly mixed, added with NMP and stirred for 2 hours, become sticky slurry, evenly coated on aluminum foil, baked in vacuum at 80 ℃, tabletted and cut into positive electrode plates with the diameter of 14 mm. Pure lithium sheets with the diameter of 16mm are used as a negative electrode sheet, a mixed solution of 1mol/L LiPF6+ DEC/EC (volume ratio of 1:1) is used as an electrolyte, a poly Celgard propylene microporous membrane is used as a diaphragm, a button cell is assembled in a glove box filled with argon, and the button cell is subjected to capacity test.
2. Cycle performance and gas production test
The gas production and cycle retention rate was measured using a full cell:
the positive electrode materials prepared in the above examples and comparative examples were respectively prepared into positive electrode sheets: the positive electrode material, the conductive carbon black SP, the conductive graphite KS-6 and the binder PVDF are mixed according to the mass ratio of 94.5 percent: 2%:1%:2.5% NMP (N-methyl pyrrolidone) is mixed to prepare positive electrode slurry, and the positive electrode slurry is prepared into a positive electrode plate through a coating and rolling process;
the positive plate, the negative electrode (graphite), the diaphragm (poly Celgard propylene microporous membrane) and the electrolyte (1 mol/L LiPF 6 +DEC/EC (volume ratio 1:1) to form a 503048 full cell, the cell capacity was about 800mAh, and the test was performed.
And (3) testing the cycle performance: a Xinwei test cabinet (CT 3008-5V3A-A 1) is adopted, the circulation voltage is 4.25-3V, the constant voltage cut-off current is 20mA, and the circulation is 300 circles under the condition of 45 ℃.
Gas production performance test: firstly, fully charging the battery, then testing the volume V1 of the battery, then storing the fully charged battery at 70 ℃ for 7 days, and then testing the volume V2 of the battery, wherein the gas yield is (V2-V1)/V1 multiplied by 100%; the volumetric measurement device is an electronic solid densitometer TW-120E.
The test results are shown in Table 1.
SEM images of the cathode materials of examples and comparative examples are shown in fig. 1 to 14.
TABLE 1
In the table, the ratio of the relative intensities of the X-ray diffraction peak (003) and the X-ray diffraction peak (004) is labeled as I003/I004.
As can be seen from table 1, the positive electrode material of the present invention is prepared by sintering a precursor, a lithium source, and an additive in this order, and by vibration treatment, the ion radius of the doping element is greater than 0.075nm, and the D104 of the positive electrode material is 60 to 75nm, and the positive electrode material is applied to a battery, so that the battery has excellent energy density, cycle performance, and safety.
Comparative examples 1 to 9 and comparative examples 1 to 2 are advantageous in improving the cycle performance and safety of the battery by incorporating a doping element having an ionic radius of more than 0.075 nm.
As is clear from comparative examples 1 to 9 and comparative example 3, the particle size distribution width of the positive electrode material can be increased by the vibration treatment, and it is difficult to achieve the energy density, cycle performance and safety of the battery by the static drying method.
As can be seen from comparative examples 1 to 9 and comparative examples 4 to 5, the D104 value of the positive electrode material is advantageously adjusted to be between 60 and 75nm by adjusting the sintering temperature, and if the temperature is too high or too low, the D104 value of the positive electrode material is not within the range of 60 to 75nm, which is disadvantageous for improving the electrochemical performance.
Preferred embodiments of the present invention and experimental verification are described in detail above. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention without requiring creative effort by one of ordinary skill in the art. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (11)
1. The positive electrode material is characterized in that the particle size distribution width SPAN of the positive electrode material is 1.30-1.90; the positive electrode material comprises an M element, and the ionic radius of the M element is larger than 0.075nm;
the positive electrode material is of a layered structure, D104 of the positive electrode material is 60-75 nm, and D104 is the size of crystal grains in the direction vertical to the crystal face of the diffraction peak of the positive electrode material obtained by XRD (X-ray diffraction) testing.
2. The positive electrode material according to claim 1, wherein the M element includes at least one element of Na, ce, sr, K, ti, rb, ba, Y.
3. The positive electrode material according to claim 1, wherein the positive electrode material is composed of primary particles and secondary particles; and/or the number of the groups of groups,
the first discharge capacity of the positive electrode material under the conditions of 2.5-4.25V and 0.1C is not less than 200mAh/g; and/or the number of the groups of groups,
the first effect of the positive electrode material is more than 90%.
4. A positive electrode material according to any one of claims 1 to 3, wherein the positive electrode material has a molecular formula LiNi x Co y A Z M g N h O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0.6 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.4, z is more than or equal to 0 and less than or equal to 0.4, g is more than or equal to 0 and less than or equal to 0.05, h is more than or equal to 0 and less than or equal to 0.05, and A comprises at least one of Mn and Al; m is Na, ce, sr, Y, K, ti, rb, ba; n is Ta, nb, ge,W, zr, B, ca, mo.
5. The positive electrode material according to any one of claims 1 to 4, wherein the positive electrode material is obtained by subjecting a precursor, a lithium source, and a compound that provides an element M to sintering treatment and vibration treatment in this order.
6. The positive electrode material according to claim 5, wherein a vibration frequency of the vibration treatment is not less than 180 times/min; and/or the number of the groups of groups,
the temperature of the vibration treatment is 100-350 ℃; and/or the number of the groups of groups,
the sintering treatment temperature is 720-850 ℃.
7. A method for producing the positive electrode material according to any one of claims 1 to 6, comprising the steps of: and mixing the precursor, the lithium source and the compound for providing the M element, and then sequentially carrying out sintering treatment and vibration treatment to obtain the anode material.
8. The method of claim 7, wherein the precursor, the lithium source, and the additive are mixed to obtain a first mixture; performing first sintering treatment on the first mixture to obtain an intermediate;
and sequentially carrying out crushing treatment, water washing treatment and vibration treatment on the intermediate to obtain the anode material.
9. The method of preparing according to claim 8, wherein the precursor comprises at least one of nickel cobalt manganese hydroxide, nickel cobalt aluminum hydroxide; and/or the number of the groups of groups,
and after the vibration treatment, performing second sintering treatment on the vibration treatment product and the compound for providing the N element to obtain the positive electrode material.
10. A positive electrode sheet, characterized in that the positive electrode sheet comprises the positive electrode material according to any one of claims 1 to 6 or the positive electrode material produced by the production method according to any one of claims 7 to 9.
11. A lithium ion battery comprising the positive electrode sheet of claim 10.
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| CN117038962A (en) * | 2023-09-19 | 2023-11-10 | 巴斯夫杉杉电池材料有限公司 | High sphericity monocrystal positive electrode material and preparation method thereof |
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| CN117038962A (en) * | 2023-09-19 | 2023-11-10 | 巴斯夫杉杉电池材料有限公司 | High sphericity monocrystal positive electrode material and preparation method thereof |
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