CN116544406A - Positive electrode material, preparation method thereof, positive electrode and lithium ion battery - Google Patents
Positive electrode material, preparation method thereof, positive electrode and lithium ion battery Download PDFInfo
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- CN116544406A CN116544406A CN202310826896.8A CN202310826896A CN116544406A CN 116544406 A CN116544406 A CN 116544406A CN 202310826896 A CN202310826896 A CN 202310826896A CN 116544406 A CN116544406 A CN 116544406A
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 128
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 69
- 239000003607 modifier Substances 0.000 claims abstract description 40
- 238000001354 calcination Methods 0.000 claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 6
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 5
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 5
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000012546 transfer Methods 0.000 abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052744 lithium Inorganic materials 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000047 product Substances 0.000 description 11
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 239000002033 PVDF binder Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 230000037303 wrinkles Effects 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910015386 Ni0.9Co0.1(OH)2 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
-
- 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
Abstract
The invention relates to the technical field of lithium battery materials, and discloses a positive electrode material, a preparation method thereof, a positive electrode and a lithium ion battery. The disclosed positive electrode material has a corrugated structure on the particle surface; the preparation method of the positive electrode material comprises the following steps: uniformly mixing a positive electrode material substrate and a surface modifier, and calcining at 630-750 ℃ for 6-12 hours; the surface modifier is at least one selected from tungsten trioxide, titanium dioxide, magnesium oxide, cobalt oxide, aluminum hydroxide and cobalt hydroxide, and the average particle size of the surface modifier is 50-300 nm. The positive electrode is prepared from the positive electrode material disclosed by the application; a lithium ion battery comprising the positive electrode disclosed herein. The positive electrode material disclosed by the application has a corrugated structure on the particle surface, so that the prepared battery has low charge transfer impedance.
Description
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to a positive electrode material and a preparation method thereof, a positive electrode and a lithium ion battery.
Background
The lithium ion battery is widely applied to the fields of new energy automobiles, 3C numbers, electric tools, energy storage and the like, and provides great convenience for daily life of people. The positive electrode material is used as an important component of the lithium ion battery, and the performance quality of the positive electrode material directly determines the performance quality of the lithium ion battery, such as the processing performance, capacity-rate performance, cycle performance, safety performance and the like of the positive electrode material.
Regarding modification of the cathode material, most of the modifications are focused on doping or surface coating, and the current research has been very extensive and intensive, and good effects are obtained. But relatively lack of research on the surface micro-morphology of the cathode material.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a positive electrode material with folds on the surface, a preparation method thereof, a positive electrode and a lithium ion battery, wherein the surface of the positive electrode material has a fold-shaped structure, and the battery prepared from the positive electrode material has small charge transfer impedance.
The invention is realized in the following way:
in a first aspect, the present invention provides a positive electrode material, the particle surface of which has a corrugated structure.
In a second aspect, the present invention provides a method for preparing a positive electrode material, comprising:
uniformly mixing a positive electrode material substrate and a surface modifier, and calcining at 630-750 ℃ for 6-12 hours;
the surface modifier is at least one selected from tungsten trioxide, titanium dioxide, magnesium oxide, cobalt oxide, aluminum hydroxide and cobalt hydroxide, and the average particle size of the surface modifier is 50-300 nm.
In an alternative embodiment, the calcination temperature is 650-720 ℃ and the calcination time is 8-10 h.
In an alternative embodiment, the particle size of the positive electrode material substrate is 3 to 5 μm.
In an alternative embodiment, the mass ratio of the positive electrode material substrate to the surface modifier is 1:0.001-0.01.
In a third aspect, the present invention provides a positive electrode comprising a positive electrode material as in the previous embodiments or a positive electrode material prepared by a method as in any of the previous embodiments.
In a fourth aspect, the present invention provides a lithium ion battery comprising the positive electrode of the previous embodiment.
The invention has the following beneficial effects:
according to the positive electrode material provided by the invention, as the surfaces of the particles are provided with the fold-shaped structures, the particles with the fold-shaped structures have larger specific surface area compared with smooth particles, and the contact area of the particles is larger when the positive electrode material is used for preparing a positive electrode, so that the adhesion of PVDF and a conductive agent is facilitated, the slurry uniformity dispersibility and uniformity of the positive electrode material can be effectively reduced, and the charge transfer impedance of a lithium ion battery is reduced.
According to the preparation method of the positive electrode material, provided by the invention, the surface modifier with a proper particle size range is used for coating the positive electrode material substrate particles, and proper calcination temperature and time are controlled, so that the coating agent partially permeates into the positive electrode material substrate particles, partially is positioned on the surfaces of the substrate particles, and forms a wrinkled coating layer on the surfaces of the particles. On one hand, the prepared positive electrode material is coated with metal oxide, so that the positive electrode material and electrolyte can be isolated, the side reaction on the surface of the positive electrode material is reduced, and the cycle performance and the safety performance of the positive electrode material are improved; on the other hand, as the surface of the positive electrode material has a fold-shaped structure, the adhesion of PVDF and a conductive agent is facilitated, the slurry uniformity, dispersion and uniformity of the positive electrode material can be effectively reduced, and the charge transfer impedance of the lithium ion battery can be reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of the positive electrode material prepared in example 1;
FIG. 2 is an SEM image of the positive electrode material prepared in example 2;
FIG. 3 is an SEM image of the positive electrode material prepared in example 3;
FIG. 4 is an SEM image of the positive electrode material prepared in example 4;
FIG. 5 is an SEM image of the positive electrode material prepared in example 5;
fig. 6 is an SEM image of the positive electrode material prepared in comparative example 1;
fig. 7 is an SEM image of the positive electrode material prepared in comparative example 2;
fig. 8 is an SEM image of the positive electrode material prepared in comparative example 3;
fig. 9 is an SEM image of the positive electrode material prepared in comparative example 4;
fig. 10 is an SEM image of the positive electrode material prepared in comparative example 5.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The following describes the positive electrode material and the preparation method thereof.
The positive electrode material provided by the embodiment of the application has a corrugated structure on the particle surface.
At present, the particle surfaces of common uncoated positive electrode materials and coated positive electrode materials are mostly in a smooth morphology state. The positive electrode material provided by the embodiment of the application has the advantages that the particle surface of the positive electrode material is provided with the fold-shaped structure, the particles with the fold-shaped structure have larger specific surface area compared with smooth particles, the contact area of the particles is larger when the positive electrode material is used for preparing a positive electrode, the adhesion of PVDF and a conductive agent is facilitated, the slurry uniformity dispersibility and uniformity of the positive electrode material can be effectively reduced, and the charge transfer impedance of a lithium ion battery is reduced.
The preparation method of the positive electrode material provided by the embodiment of the application comprises the following steps:
uniformly mixing a positive electrode material substrate and a surface modifier, and calcining at 630-750 ℃ for 6-12 hours;
the surface modifier is at least one selected from tungsten trioxide, titanium dioxide, magnesium oxide, cobalt oxide, aluminum hydroxide and cobalt hydroxide, and the particle size of the surface modifier is 50-300 nm.
According to the preparation method of the positive electrode material, provided by the embodiment of the application, the surface modifier with the proper particle size range is used for coating the positive electrode material substrate particles, and proper calcination temperature and time are controlled, so that the coating agent partially permeates into the positive electrode material substrate particles, is partially positioned on the surfaces of the substrate particles, and forms the wrinkled coating layer on the surfaces of the particles. On one hand, the prepared positive electrode material is coated with metal oxide, so that the positive electrode material and electrolyte can be isolated, the side reaction on the surface of the positive electrode material is reduced, and the cycle performance and the safety performance of the positive electrode material are improved; on the other hand, as the surface of the positive electrode material has a fold-shaped structure, the adhesion of PVDF and a conductive agent is facilitated, the slurry uniformity, dispersion and uniformity of the positive electrode material can be effectively reduced, and the charge transfer impedance of the lithium ion battery can be reduced.
Specifically, the preparation method comprises the following steps:
s1, preparation of positive electrode material base material
Uniformly mixing the precursor and a lithium source according to the molar ratio of the metal element in the precursor and the lithium element in the lithium source of 1:1.01-1.08 (for example, 1:1.01, 1:1.03, 1:1.05 or 1:1.08), and calcining at 650 ℃ -900 ℃ (for example, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃ or 900 ℃), thereby obtaining a primary product of the positive electrode material.
The chemical formula of the precursor is as follows:x is more than or equal to 0.6 and less than or equal to 1.0, y is more than or equal to 0 and less than or equal to 0.4, and M is one or more than two of Mn, al, ti, mg, W, mo, nb, sr, zr, V, ba, B.
The chemical composition and the morphological characteristics of the precursor have a direct effect on the overall performance of the positive electrode material, but have no difference in the effect of the surface wrinkles of the crystal grains involved in the present invention. The above-described precursor is selected only because it is currently the most common precursor.
S2, crushing
And crushing the primary product of the positive electrode material, and sieving to obtain a positive electrode material substrate with the D50 of 3-5 μm (for example, 3 μm, 4 μm or 5 μm).
S3, coating modification
Uniformly mixing a positive electrode material substrate and a surface modifier, and then calcining;
the surface modifier is at least one selected from tungsten trioxide, titanium dioxide, magnesium oxide, cobalt oxide, aluminum hydroxide and cobalt hydroxide, and has an average particle diameter of 50nm to 300nm (for example, 50nm, 100nm, 150 nm, 200 nm or 300 nm).
To ensure that a portion of the surface modifier penetrates into the substrate particles, a portion remains outside the substrate particles and forms a crimped coating on the surface of the particles. The calcination conditions included:
the calcination temperature is 630-750 ℃ (e.g. 630 ℃, 650 ℃, 680 ℃, 700 ℃, 720 ℃ or 750 ℃), the calcination time is 6-12 hours (e.g. 6 hours, 8 hours, 10 hours or 12 hours), and the sintering atmosphere is pure oxygen.
Preferably, the calcination temperature to achieve a better surface wrinkle morphology is 650 ℃ -720 ℃ (e.g. 650 ℃, 680 ℃, 700 ℃ or 720 ℃), and the calcination time is 8 h-10 h (e.g. 8h, 10h or 12 h).
Preferably, in order to obtain a positive electrode material with a better surface wrinkle morphology after calcination, the mass ratio of the positive electrode material substrate to the surface modifier is 1:0.001-0.01 (e.g. 1:0.001, 1:0.002, 1:0.005, 1:0.008 or 1:0.01).
The positive electrode provided by the embodiment of the application comprises the positive electrode material provided by the embodiment of the application or the positive electrode material prepared by the preparation method provided by the embodiment of the application.
The positive electrode comprises the positive electrode material provided by the embodiment of the application, so that the positive electrode has the characteristic of low charge transfer impedance.
The lithium ion battery provided by the embodiment of the application comprises the positive electrode provided by the embodiment of the application.
The lithium ion battery comprises the positive electrode provided by the embodiment of the application, so that the charge transfer impedance of the lithium ion battery is low.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
Precursor Ni 0.9 Co 0.1 (OH) 2 Mixing with lithium hydroxide uniformly according to the molar ratio of metal element to lithium of 1:1.05, and calcining at 800 ℃ to obtain the primary product of the anode material.
And crushing and sieving the primary product of the positive electrode material to obtain a positive electrode material substrate with the D50 of 4.0 mu m.
Uniformly mixing a positive electrode material substrate and a surface modifier according to a mass ratio of 1:0.005, wherein the surface modifier is alumina, and the average particle size of the surface modifier is 100nm.
The calcination temperature is 720 ℃, the calcination time is 8 hours, and the calcination process is carried out under an oxygen atmosphere.
The prepared positive electrode material particles are shown in fig. 1, and the surface of the particles is obviously wrinkled as seen in fig. 1.
Example 2
Precursor Ni 0.92 Co 0.04 Mn 0.04 (OH) 2 Mixing with lithium hydroxide uniformly according to the molar ratio of metal element to lithium of 1:1.05, and calcining at 820 ℃ to obtain the primary product of the anode material.
And crushing and sieving the primary product of the positive electrode material to obtain a positive electrode material substrate with the D50 of 3.5 mu m.
Uniformly mixing a positive electrode material substrate and a surface modifier according to a mass ratio of 1:0.002, wherein the surface modifier is titanium dioxide, and the average particle size of the surface modifier is 50nm.
The calcination temperature was 650 ℃ and the calcination time was 10 hours, and the calcination process was performed under an oxygen atmosphere.
The prepared positive electrode material particles are shown in fig. 2, and the surface of the particles is obviously wrinkled as can be seen from fig. 2.
Example 3
Precursor Ni 0.92 Co 0.03 Mn 0.03 Al 0.02 (OH) 2 Mixing with lithium hydroxide uniformly according to the molar ratio of metal element to lithium of 1:1.03, and calcining at 830 ℃ to obtain the primary product of the anode material.
And crushing and sieving the primary product of the positive electrode material to obtain a positive electrode material substrate with the D50 of 3.5 mu m.
Uniformly mixing a positive electrode material substrate and a surface modifier according to a mass ratio of 1:0.005, wherein the surface modifier is cobalt hydroxide, and the average particle size of the surface modifier is 300nm.
The calcination temperature is 680 ℃, the calcination time is 9h, and the calcination process is carried out under an oxygen atmosphere.
The prepared positive electrode material particles are shown in fig. 3, and the surface of the particles is obviously wrinkled as seen in fig. 3.
Example 4
This example is essentially the same as example 2 except that the positive electrode material substrate was mixed with the surface modifier and then calcined at 630 ℃.
The positive electrode material particles are shown in fig. 4, and as can be seen from fig. 4, the surfaces of the particles are in a remarkable fold shape.
Example 5
This example is substantially the same as example 1 except that the calcination temperature after mixing the positive electrode material substrate with the surface modifier is 750 ℃.
The positive electrode material particles are shown in fig. 5, and as can be seen from fig. 5, the particle surfaces are in the shape of obvious folds.
Example 6
This embodiment is substantially the same as embodiment 1, except that: the mass ratio of the positive electrode material substrate to the surface modifier is 1:0.01.
Example 7
This embodiment is substantially the same as embodiment 1, except that: the mass ratio of the positive electrode material substrate to the surface modifier is 1:0.001.
Example 8
This embodiment is substantially the same as embodiment 1, except that: the mass ratio of the positive electrode material substrate to the surface modifier is 1:0.02.
Example 9
This embodiment is substantially the same as embodiment 1, except that: the mass ratio of the positive electrode material substrate to the surface modifier is 1:0.0002.
Comparative example 1
This embodiment is substantially the same as embodiment 4, except that: the calcination temperature was 600 ℃.
The prepared positive electrode material particles are shown in fig. 6, and as can be seen from fig. 6, the surfaces of the particles are smooth.
Comparative example 2
This embodiment is substantially the same as embodiment 5, except that: the calcination temperature was 790 ℃.
The prepared positive electrode material particles are shown in fig. 7, and as can be seen from fig. 7, the surfaces of the particles are smooth.
Comparative example 3
This comparative example is substantially the same as example 3, except that: the average particle diameter of the particles of the surface modifier was 500nm.
The prepared positive electrode material particles are shown in fig. 8, and as can be seen from fig. 8, the surfaces of the particles are smooth.
Comparative example 4
This comparative example is substantially the same as example 2, except that: the average particle diameter of the particles of the surface modifier was 20nm.
The prepared positive electrode material particles are shown in fig. 9, and as can be seen from fig. 9, the surfaces of the particles are smooth.
Comparative example 5
This comparative example is substantially the same as example 1, except that: the primary product of the positive electrode material is not subjected to subsequent cladding sintering compared with the embodiment 1, namely the primary product of the positive electrode material is the existing common ternary positive electrode material.
The prepared positive electrode material particles are shown in fig. 10, and as can be seen from fig. 10, the surfaces of the particles are smooth.
Experimental example
The positive electrode materials prepared in examples 1 to 9 and comparative examples 1 to 5 were assembled into 2025 button cells, and their electrochemical properties were tested under 3.0v to 4.3v conditions. This is recorded in table 1 below.
Table 1 results of electrochemical performance test of each of examples and comparative examples table
As can be seen from table 1, the positive electrode materials provided in the examples of the present application have better electrochemical properties, and the charge transfer resistance is significantly lower than that of comparative example 5 (common ternary positive electrode material).
Comparing example 4 with example 2, comparing example 5 with example 1; the calcination temperatures of examples 1 and 2 were in the preferred calcination temperature range of 650 ℃ to 720 ℃, while examples 4 and 5 were not in the above range, and examples 1 and 2 were found to have higher initial efficiency and lower charge transfer resistance values, indicating lower charge transfer resistance when the positive electrode materials prepared in the preferred calcination temperature range of 650 ℃ to 720 ℃ were made into batteries.
Comparing example 8 and example 9 with example 6 and example 7, respectively, it can be seen that the charge transfer impedance of example 8 and example 9 is significantly higher, which indicates that the charge transfer impedance of the prepared positive electrode material made into a battery is lower when the addition amount of the surface modifier is within the range of 1:0.001-0.01 required by the invention.
Comparative examples 3 and 4 were compared with examples 3 and 2, respectively, and the average particle diameter of the surface modifier of the comparative example was not in the range required by the present invention, and the positive electrode material was produced without having a wrinkle structure and had significantly higher charge transfer resistance.
In summary, the surface of the positive electrode material provided by the embodiment of the application is provided with the fold-shaped structure, so that the particles with the fold-shaped structure have larger specific surface area compared with smooth particles, and the contact area of the particles is larger when the positive electrode material is used for preparing a positive electrode, thereby being beneficial to the adhesion of PVDF and a conductive agent, effectively reducing the slurry uniformity dispersibility and uniformity of the positive electrode material and reducing the charge transfer impedance of a lithium ion battery.
According to the preparation method of the positive electrode material, provided by the embodiment of the application, the surface modifier with the proper particle size range is used for coating the positive electrode material substrate particles, and proper calcination temperature and time are controlled, so that the coating agent partially permeates into the positive electrode material substrate particles, is partially positioned on the surfaces of the substrate particles, and forms the wrinkled coating layer on the surfaces of the particles. On one hand, the prepared positive electrode material is coated with metal oxide, so that the positive electrode material and electrolyte can be isolated, the side reaction on the surface of the positive electrode material is reduced, and the cycle performance and the safety performance of the positive electrode material are improved; on the other hand, as the surface of the positive electrode material has a fold-shaped structure, the adhesion of PVDF and a conductive agent is facilitated, the slurry uniformity, dispersion and uniformity of the positive electrode material can be effectively reduced, and the charge transfer impedance of the lithium ion battery can be reduced.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The positive electrode material is characterized in that the particle surfaces of the positive electrode material have a fold-shaped structure.
2. A method for preparing a positive electrode material, comprising:
uniformly mixing a positive electrode material substrate and a surface modifier, and calcining at 630-750 ℃ for 6-12 hours;
the surface modifier is at least one selected from tungsten trioxide, titanium dioxide, magnesium oxide, cobalt oxide, aluminum hydroxide and cobalt hydroxide, and the average particle size of the surface modifier is 50 nm-300 nm.
3. The preparation method according to claim 2, wherein the calcination temperature is 650-720 ℃ and the calcination time is 8-10 h.
4. The method according to claim 2, wherein the D50 of the positive electrode material base material is 3 μm to 5 μm.
5. The method according to claim 2, wherein the mass ratio of the positive electrode material base material to the surface modifier is 1:0.001-0.01.
6. A positive electrode comprising the positive electrode material according to claim 1 or the positive electrode material produced by the production method according to any one of claims 2 to 5.
7. A lithium ion battery comprising the positive electrode of claim 6.
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