CN112919551A - Cathode material, preparation method thereof, cathode and lithium ion battery - Google Patents
Cathode material, preparation method thereof, cathode and lithium ion battery Download PDFInfo
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- 239000010406 cathode material Substances 0.000 title claims abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000007774 positive electrode material Substances 0.000 claims abstract description 60
- 239000013078 crystal Substances 0.000 claims abstract description 39
- 239000002245 particle Substances 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 229910019122 CoaMnb(OH)2 Inorganic materials 0.000 claims abstract description 8
- 229940126062 Compound A Drugs 0.000 claims abstract description 8
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 66
- 238000005245 sintering Methods 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 31
- 229910052759 nickel Inorganic materials 0.000 claims description 31
- 230000007704 transition Effects 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 6
- 238000003701 mechanical milling Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 150000002222 fluorine compounds Chemical class 0.000 claims description 3
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- 235000021317 phosphate Nutrition 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000010902 jet-milling Methods 0.000 claims description 2
- 239000010405 anode material Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 7
- 229910013716 LiNi Inorganic materials 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 2
- 229910011624 LiNi0.7Co0.1Mn0.2O2 Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910012623 LiNi0.5Co0.2 Inorganic materials 0.000 description 1
- 229910015973 LiNi0.8Mn0.2O2 Inorganic materials 0.000 description 1
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 description 1
- 229910021311 NaFeO2 Inorganic materials 0.000 description 1
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 description 1
- 229910017288 Ni0.8Mn0.2(OH)2 Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a positive electrode material and a preparation method thereof, a positive electrode and a lithium ion battery, wherein the positive electrode material is a single crystal positive electrode material and mainly comprises an inner core and a shell coating the inner core; wherein the inner core contains LiNi1‑x‑yCoxMny(OH)2The particle size of the compound A is 0.01-1 mu m, x and y both represent mole fractions, x is more than or equal to 0 and less than or equal to 0.5, and y is more than or equal to 0 and less than or equal to 0.5; the shell comprises LiNi1‑a‑bCoaMnb(OH)2The compound B of (a) and (B) both represent mole fractions, a is more than or equal to 0 and less than or equal to 0.5, B is more than or equal to 0 and less than or equal to 0.5, and x + y<a + b. The positive electrode material is applied to a battery, and can improve the capacity and the cycle stability of the batterySex, high temperature stability and energy density. In addition, the compound A is used as the inner core of the cathode material, so that the production cost of the cathode material can be reduced.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a positive electrode material, a preparation method of the positive electrode material, a positive electrode and a lithium ion battery.
Background
The anode material in the power battery is a key component of the power battery, and accounts for about 40% of the total cost of the battery. At present, the anode materials commonly used in the power battery are ternary materials and lithium iron phosphate materials, and are widely applied to the field of electric automobiles, and with the continuous improvement of the endurance mileage requirement of people on electric automobiles, the ternary anode materials with higher energy density gradually become the mainstream anode materials in the power battery. For example, the conventional ternary material LiNixCoyMnzO2(x + y + z ═ 1) and single crystal ternary materials.
The ternary material in the prior art can cause a serious hardening phenomenon after being sintered for one time, so that mutually adhered particles need to be separated by crushing equipment, and normal particles (the particle size is larger than 1 mu m) and micro powder (the particle size is not larger than 1 mu m) formed in the crushing process can be taken into a dust remover together. The micro powder has too small particle size and large specific surface area, so that the cycle performance and the high-temperature performance of the battery cell are reduced if the micro powder is coated on the positive electrode. Therefore, the fine powder cannot be used as a positive electrode material and is generally recovered as a waste material, which indirectly increases the production cost of the positive electrode material.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a positive electrode material, a method for preparing the same, a positive electrode, and a lithium ion battery, so as to solve the problem in the prior art that the production cost of the positive electrode material is increased because the fine powder cannot be directly used as the positive electrode material.
In order to achieve the purpose, the invention provides the following technical scheme:
in a first aspect, the invention provides a positive electrode material, which is a single-crystal positive electrode material and mainly comprises an inner core and a shell coating the inner core;
wherein the inner core comprises LiNi1-x-yCoxMny(OH)2The particle diameter of the compound A is 0.01-1 mu m, and x and y both represent mole fractionsX is more than or equal to 0 and less than or equal to 0.5, and y is more than or equal to 0 and less than or equal to 0.5;
the shell comprises LiNi1-a-bCoaMnb(OH)2The compound B of (A) and (B) both represent mole fractions, wherein a is more than or equal to 0 and less than or equal to 0.5, B is more than or equal to 0 and less than or equal to 0.5, and x + y<a+b。
In some alternative embodiments, the compound a is a fine powder formed from a high nickel positive electrode material during a jet milling or mechanical milling process.
In some optional embodiments, the cathode material further comprises a transition layer, the transition layer is positioned between the inner core and the outer shell, and the content c of nickel in the transition layer is 1-a-b < c < 1-x-y.
In some alternative embodiments, the nickel content in compound A is 0.7 ≦ 1-x-y ≦ 1, and the nickel content in compound B is 0.3 ≦ 1-a-B ≦ 0.8.
In a second aspect, the present invention also provides a method for preparing the cathode material according to any one of the above embodiments, the method comprising the steps of:
1) the chemical formula is LiNi1-x-yCoxMny(OH)2Compound A of (A) having the chemical formula Ni1-a-bCoaMnb(OH)2Mixing the precursor, the lithium source and the additive to obtain a mixed material; wherein a and b both represent mole fraction, and a is more than or equal to 0 and less than or equal to 0.5, b is more than or equal to 0 and less than or equal to 0.5, and x + y<a+b；
2) And sintering the mixed material at the temperature of 650-980 ℃ in an oxidizing atmosphere to obtain the cathode material.
In some embodiments, D of the precursor50The size is 2-6 μm.
In some alternative embodiments, the sintering comprises a first-stage sintering and a second-stage sintering which are sequentially carried out, wherein the temperature of the first-stage sintering is 650-800 ℃, and the time of the first-stage sintering is 2-6 h; the temperature of the second-stage sintering is 800-980 ℃, and the time of the second-stage sintering is 6-15 h.
In some alternative embodiments, the mass ratio of the compound a and the precursor is (0.1-0.6): 1;
preferably, the molar ratio of the lithium element in the lithium source to the precursor is (0.99-1.1): 1;
preferably, the additive is selected from at least one of oxides, fluorides, hydroxides, carbonates, bicarbonates and phosphates of group IIA, group IIIA and transition elements, and the mass of group IIA, group IIIA and transition elements in the additive is 0.0001-1% of the mass of the positive electrode material.
In a third aspect, the present invention also provides a positive electrode comprising the positive electrode material described in any of the above embodiments.
In a fourth aspect, the present invention further provides a lithium ion battery, which includes a positive electrode, a negative electrode, an electrolyte and a separator; wherein the positive electrode is the positive electrode described in the above embodiment.
The embodiment provided by the invention has at least the following beneficial effects:
1) the positive electrode material provided by the invention takes micro powder with the particle size of 0.01-1 mu m as an inner core, and the outer core is coated with the outer shell to form the single crystal positive electrode material, wherein the content of nickel in the inner core is greater than that of nickel in the outer shell to form a content gradient. In addition, the production cost of the cathode material can be reduced by adopting the micro powder as the core of the cathode material.
2) According to the preparation method of the cathode material, the micro powder with the particle size of 0.01-1 mu m is used as the seed crystal and the seed crystal is used as the crystal nucleus, so that the growth of the single crystal of the shell part with low nickel content can be promoted, the sintering temperature for forming the single crystal can be reduced, and the single crystallization degree is improved, so that the prepared single crystal cathode material has high capacity, good cycle stability, high-temperature stability and high energy density; in addition, the micro powder is used as the core of the anode material, so that the manufacturing cost of the battery can be greatly reduced.
3) The positive electrode provided by the invention is coated with the positive electrode material, so that the positive electrode is applied to a battery, and the battery has high capacity, good cycle stability, high-temperature stability and high energy density.
4) The lithium ion battery provided by the invention comprises the anode, so that the lithium ion battery has high capacity, better cycle stability and high-temperature stability and high energy density, and has lower manufacturing cost.
In addition to the technical problems solved by the present invention, the technical features constituting the technical solutions, and the advantageous effects brought by the technical features of the technical solutions described above, other technical problems that can be solved by the positive electrode material and the preparation method thereof, the positive electrode and the lithium ion battery provided by the present invention, other technical features included in the technical solutions, and advantageous effects brought by the technical features will be further described in detail in the detailed description.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is an X-ray diffraction (XRD) pattern of the fine powder of the present invention and the positive electrode materials prepared in example 1 and comparative example 1;
FIG. 2 is a graph showing cycle characteristics of the positive electrode materials prepared in example 1 of the present invention and comparative example 1;
FIG. 3 is a Scanning Electron Microscope (SEM) image of the positive electrode material prepared in example 1 of the present invention;
FIG. 4 is a Scanning Electron Microscope (SEM) image of a positive electrode material prepared in comparative example 1 of the present invention;
fig. 5 is a linear scanning distribution diagram of the nickel content in the cathode material prepared in example 1 of the present invention.
Detailed Description
The embodiments or implementation modes in the present specification are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments may be referred to each other.
In the description of the present specification, reference to the description of the terms "one embodiment", "some embodiments", "an illustrative embodiment", "an example", "a specific example", or "some examples", etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The term "micropowder", as used herein, refers to particles having a particle size of 1 μm or less.
Firstly, the invention provides a positive electrode material which is a single crystal positive electrode material and mainly comprises an inner core and a shell coating the inner core. Wherein the inner core contains LiNi1-x-yCoxMny(OH)2The particle size of the compound is in the range of 0.01-1 mu m, x and y both represent mole fractions, x is more than or equal to 0 and less than or equal to 0.5, and y is more than or equal to 0 and less than or equal to 0.5; the shell comprises LiNi1-a-bCoaMnb(OH)2A and b represent mole fraction, a is more than or equal to 0 and less than or equal to 0.5, b is more than or equal to 0 and less than or equal to 0.5, and x + y<a+b。
As described above, a single crystal positive electrode material is formed by using a fine powder having a particle size of 0.01 to 1 μm as a core and coating the core with a shell. And the inner core contains LiNi1-x-yCoxMny(OH)2The compound and the shell contain LiNi1-a-bCoaMnb(OH)2And x + y<a + b, it can be seen that the nickel content in the core is greater than the nickel content in the shell to form a content gradient. And the cathode material is singleThe crystal material can make the surface of the anode material more stable. Therefore, when applied to a battery, the capacity, cycle stability, high temperature stability, and energy density of the battery can be improved. In addition, the production cost of the cathode material can be reduced by adopting the micro powder as the core of the cathode material.
In embodiments provided herein, the inner core comprises LiNi1-x-yCoxMny(OH)2The compound of (1), namely micropowder, is in the preparation process of the high-nickel ternary material, each raw material is hardened after one-time sintering to enable particles to be adhered to each other, the adhered particles are separated and crushed by crushing equipment, wherein the crushing mode is usually airflow milling or mechanical milling, the normal particles obtained after the airflow milling or mechanical milling can be directly used as the anode material, and the micropowder has too small particle size and large specific surface area and can not be directly used as the anode material. Therefore, the micro powder is used as the inner core, and the outer shell is coated outside the inner core, so that the micro powder has relatively smaller specific surface area when being used as the positive electrode material, thereby improving the high-temperature stability and the cycling stability of the positive electrode material.
In the embodiment provided by the invention, the single crystal cathode material with the concentration gradient further comprises a transition layer, the transition layer is positioned between the inner core and the outer shell, and the content c of nickel in the transition layer is 1-a-b < c < 1-x-y. In the process of charging and discharging, because the nickel contents of the inner core and the outer shell of the concentration gradient material are different, under the same charging and discharging voltage, the lithium removal degrees of the inner core and the outer shell are different, which can cause the volume changes of the inner core and the outer shell caused by phase change to be different, so that separation cracking between the inner layer and the outer layer can occur, and the problem can be relieved by the existence of the transition layer. As shown in fig. 5, which is a linear scanning distribution diagram of nickel content in a particle section of the cathode material, it can be seen from the graph that the middle part of the curve represents the inner core, the curve with more gentle ends represents the outer shell, and the transition layer between the inner core and the outer shell has a thickness of about 600nm, and in this interval, the nickel content gradually decreases, so that the problem of uneven volume change during phase transition caused by sudden change of nickel content can be alleviated.
In some alternative embodiments, the nickel content in compound A is 0.7. ltoreq. 1-x-y. ltoreq.1 and the nickel content in compound B is 0.3. ltoreq. 1-a-B. ltoreq.0.8.
Illustratively, the core in the positive electrode material comprises LiNi0.7Co0.1Mn0.2O2And the housing comprises LiNi0.5Co0.2M0.3(OH)2。
In order to further increase the capacity of the battery, the content of nickel in the core of the positive electrode material can be appropriately increased and the compounds contained in the core and the shell can be appropriately selected. Thus, in some preferred embodiments, the core comprises LiNi0.9Co0.05Mn0.05O2Said housing comprising LiNi0.7Co0.1M0.2(OH)2。
Further, the core comprises LiNi0.95Mn0.05O2The housing contains LiNi0.8Mn0.2(OH)2。
Secondly, the invention also provides a preparation method of the cathode material in any one of the above embodiments, which comprises the following steps:
1) the chemical formula is LiNi1-x-yCoxMny(OH)2Compound A of (A) having the chemical formula Ni1-a-bCoaMnb(OH)2Mixing the precursor, the lithium source and the additive to obtain a mixed material; wherein a and b both represent mole fraction, and a is more than or equal to 0 and less than or equal to 0.5, b is more than or equal to 0 and less than or equal to 0.5, and x + y<a+b
2) And sintering the mixed material at 650-980 ℃ in an oxidizing atmosphere to obtain the cathode material.
In the embodiment provided by the invention, the raw materials for preparing the cathode material are reasonably configured, so that the electrical property of the cathode material can be improved. In some alternative embodiments, the mass ratio of compound a to precursor is (0.1-0.6): 1, preferably (0.3-0.6): 1.
further, in some alternative embodiments, D of the precursor50The size is controlled within the range of 2-6 μm,thus, the specific surface area of the cathode material can be reduced, and the electrical property of the cathode material can be further improved.
In some alternative embodiments, the molar ratio of lithium element to precursor in the lithium source is (0.99-1.1): 1. the lithium source may be lithium carbonate or lithium hydroxide.
In some alternative embodiments, the additive is selected from at least one of group IIA, group IIIA and transition element oxides, fluorides, hydroxides, carbonates, bicarbonates and phosphates, and the mass of the group IIA, group IIIA and transition element in the additive is 0.0001-1% of the mass of the positive electrode material.
Wherein, the IIA group can be selected from Mg, Ca and Sr, and the additive can be selected from MgO. Group IIIA B and Al can be selected, and the additive can be alumina (Al)2O3). The transition group can be selected from Mn, Ti, V, Zr, Y, Nb, Ta, La, W, Mo, Re and Sc, and the additive can be selected from titanium dioxide (TiO)2) Or zirconium dioxide (ZrO)2)。
In some alternative embodiments, the oxidizing atmosphere may be an oxygen atmosphere or an air atmosphere.
The sintering comprises a first-stage sintering and a second-stage sintering which are sequentially carried out, and the temperature of the first-stage sintering is not more than that of the second-stage sintering. Wherein, the first-stage sintering is low-temperature sintering, which is to form a transition layer on the surface of the core, namely a transition region with high-to-low nickel content; the second-stage sintering is high-temperature sintering, so that the transition layer and the shell can form single crystals, and the high-temperature stability and the high-temperature cycle performance of the anode material are improved.
In some alternative embodiments, the temperature of the first stage sintering is 650-; the temperature of the second-stage sintering is 800-980 ℃, and the time of the second-stage sintering is 6-15 h.
According to the preparation method of the cathode material, the micro powder with the particle size of 0.01-1 mu m is used as the seed crystal and the seed crystal is used as the crystal nucleus, so that the growth of the single crystal of the shell part with low nickel content can be promoted, the sintering temperature for forming the single crystal can be reduced, and the single crystallization degree is improved, so that the prepared single crystal cathode material can enable the battery to have high capacity, good cycle stability, high-temperature stability and high energy density; in addition, the micro powder is used as the core of the anode material, so that the manufacturing cost of the battery can be greatly reduced.
The invention further provides a positive electrode, which comprises a current collector and a positive electrode material coated on the current collector, wherein the positive electrode material is the positive electrode material in any one of the embodiments.
The positive electrode provided by the invention contains the positive electrode material, so that the positive electrode is applied to a battery, and the battery has high capacity, good cycle stability, high-temperature stability and high energy density.
Finally, the invention also provides a lithium ion battery, which comprises a positive electrode, a negative electrode, electrolyte and a diaphragm; wherein the positive electrode is the positive electrode described in the above embodiment.
In the embodiments provided herein, the electrolyte, the negative electrode, and the separator are not particularly limited, and may be a conventional electrolyte, a negative electrode, and a separator known to those skilled in the art.
The lithium ion battery provided by the invention comprises the anode, so that the lithium ion battery has high capacity, better cycle stability and high-temperature stability and high energy density, and has lower manufacturing cost.
Hereinafter, the positive electrode material of the present invention will be described in detail with reference to specific examples.
Unless otherwise specified, the chemical materials and instruments used in the following examples and comparative examples are all conventional chemical materials and conventional instruments, and are commercially available.
Example 1
The embodiment provides a preparation method of a cathode material, which comprises the following steps:
1) 30g of LiNi were weighed out separately0.7Co0.1Mn0.2O2Jet mill micropowder, 100g of Ni0.5Co0.2Mn0.3(OH)2Precursor (D)50＝3.2 μm), 41.56g of Li2CO3And 0.25g TiO2Adding the materials into a high-speed mixer for fully mixing, and uniformly mixing to obtain a mixed material;
2) under the air atmosphere, the mixed material is firstly subjected to first-stage sintering at 760 ℃ for 4 hours, and then subjected to second-stage sintering at 910 ℃ for 12 hours; cooling, dissociating and sieving to obtain single crystal anode material with LiNi as core0.7Co0.1Mn0.2O2The average particle diameter is 0.7 μm, and the shell is LiNi0.5Co0.2Mn0.3O2D of single-crystal positive electrode material50And was 4.0 μm.
Comparative example 1
The comparative example provides a method for preparing a positive electrode material, comprising the steps of:
1) 100g of Ni were weighed out separately0.5Co0.2Mn0.3(OH)2Precursor (D)503.2 μm), 41.56g of Li2CO3And 0.25g TiO2Adding the materials into a high-speed mixer for fully mixing, and uniformly mixing to obtain a mixed material;
2) under the air atmosphere, the mixed material is firstly subjected to first-stage sintering at 760 ℃ for 4h, and then subjected to second-stage sintering at 910 ℃ for 12 h; cooling, dissociating and sieving to obtain LiNi0.5Co0.2Mn0.3O2A single crystal positive electrode material.
FIG. 1 is an XRD pattern of the fine powder of this example and the positive electrode materials prepared in example 1 and comparative example 1, and it can be seen from the XRD patterns that all three materials are α -NaFeO2The layered structure belongs to an R-3m space point group. However, the diffraction intensity of example 1 is significantly higher than that of comparative example 1, which shows that the positive electrode material has higher crystallinity and better crystal growth by using the fine powder as the seed crystal.
FIG. 2 is a graph showing cycle characteristics of the positive electrode materials prepared in example 1 of the present invention and comparative example 1; the batteries containing the positive electrode materials of example 1 and comparative example 1 were subjected to cycle performance test using a model LAND tester CT2001A, with a charging voltage range of 3.0-4.4V and a test temperature of 25 ℃. As can be seen from fig. 1, in example 1, the material used as a seed crystal was more monocrystalline, and therefore had better cycle stability.
FIG. 3 is a Scanning Electron Microscope (SEM) image of the positive electrode material prepared in example 1 of the present invention; fig. 4 is a Scanning Electron Microscope (SEM) image of the cathode material prepared in comparative example 1 of the present invention. As can be seen from FIG. 3, the fine powder is used as the seed crystal in example 1, so that a better single crystal morphology is obtained. While comparative example 1 only obtained a single crystal-like morphology at the same sintering temperature, indicating that the growth of single crystals can be promoted by using the micro powder as seed crystals.
Fig. 5 is a linear scanning distribution diagram of the nickel content in the cathode material prepared in example 1 of the present invention. It can be seen from fig. 5 that the nickel content of the core is high, the nickel content of the shell is low, a transition region with a thickness of about 600nm is formed between the core and the shell, and the nickel content is gradually reduced in the transition region, so that the problem of uneven volume change caused by sudden change of the nickel content can be effectively solved.
Example 2
The embodiment provides a preparation method of a cathode material, which comprises the following steps:
1) 60g of LiNi are respectively weighed0.9Co0.05Mn0.05O2Mechanically ground micropowder, 100g Ni0.7Co0.1Mn0.2(OH)2Precursor (D)504.0 μm), 46.12g of LiOH · H2O and 0.34g Al2O3Adding the materials into a high-speed mixer for fully mixing, and uniformly mixing to obtain a mixed material;
2) under the oxygen atmosphere, the mixed material is firstly subjected to first-stage sintering at 720 ℃ for 6 hours, and then subjected to second-stage sintering at 870 ℃ for 8 hours; cooling, dissociating and sieving to obtain single crystal anode material with LiNi as core0.9Co0.05Mn0.05O2Having an average particle diameter of 0.5 μm and a shell of LiNi0.7Co0.1Mn0.2O2D of single-crystal positive electrode material50It was 4.6 μm.
Example 3
The embodiment provides a preparation method of a cathode material, which comprises the following steps:
1) 40g of LiNi were weighed out separately0.95Mn0.05O2Jet mill micropowder, 100g of Ni0.8Mn0.2(OH)2Precursor (D)505.0 μm) and 46.93g of LiOH · H)2O and 0.15g ZrO2Adding 0.12g LiF into a high-speed mixer, fully mixing, and uniformly mixing to obtain a mixed material;
2) in the oxygen atmosphere, the mixed material is firstly subjected to first-stage sintering at 740 ℃ for 6 hours, and then subjected to second-stage sintering at 870 ℃ for 8 hours; cooling, dissociating and sieving to obtain single crystal anode material with LiNi as core0.95Mn0.05O2The average particle diameter is 0.6 μm, and the shell is LiNi0.8Mn0.2O2D of single-crystal positive electrode material50And 5.8 μm.
The positive electrode materials prepared in examples 1 to 3 and comparative example 1 were subjected to a tap density test, a pole piece compaction density test, a cycle performance test, a morphology characterization and a specific surface area test, respectively, and the results are shown in table 1.
The tap density test is carried out according to national standard GB/T5162-.
TABLE 1
As can be seen from table 1, the positive electrode material prepared in example 1 has better electrical properties than the positive electrode material prepared in comparative example 1. Among them, the single crystal positive electrode material of example 1 has a higher nickel content core and thus a higher capacity; and the cathode material in example 1 has a higher single crystal degree at the same sintering temperature, so that the cycling stability is better. Because the embodiment 1 has higher single crystal degree, the anode material also has smaller specific surface area, higher tap density and compaction density, and the smaller specific surface area can reduce the contact area with the electrolyte, thereby reducing gas generation and leading the anode material to have better high-temperature stability and cycle stability; the higher tap density and compaction density can enable the positive pole piece to bear more active substances, so that the energy density of the battery core is improved.
In addition, both example 2 and example 3 also had better electrical properties.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The positive electrode material is characterized by being a single-crystal positive electrode material and mainly comprising an inner core and a shell coating the inner core;
wherein the inner core comprises LiNi1-x-yCoxMny(OH)2The particle size of the compound A is 0.01-1 mu m, x and y both represent mole fractions, x is more than or equal to 0 and less than or equal to 0.5, and y is more than or equal to 0 and less than or equal to 0.5;
the shell comprises LiNi1-a-bCoaMnb(OH)2The compound B of (A) and (B) both represent mole fractions, wherein a is more than or equal to 0 and less than or equal to 0.5, B is more than or equal to 0 and less than or equal to 0.5, and x + y<a+b。
2. The positive electrode material according to claim 1, wherein the compound a is a fine powder formed from the high nickel positive electrode material during a process of air-jet milling or mechanical milling.
3. The positive electrode material according to claim 1, further comprising a transition layer, wherein the transition layer is located between the inner core and the outer shell, and the content c of nickel in the transition layer is 1-a-b < c < 1-x-y.
4. The positive electrode material as claimed in claim 1, wherein the content of nickel in the compound A is 0.7. ltoreq. 1-x-y. ltoreq.1, and the content of nickel in the compound B is 0.3. ltoreq. 1-a-B. ltoreq.0.8.
5. A method for preparing a positive electrode material according to any one of claims 1 to 4, comprising the steps of:
1) the chemical formula is LiNi1-x-yCoxMny(OH)2Compound A of (A) having the chemical formula Ni1-a-bCoaMnb(OH)2Mixing the precursor, the lithium source and the additive to obtain a mixed material; wherein a and b both represent mole fraction, and a is more than or equal to 0 and less than or equal to 0.5, b is more than or equal to 0 and less than or equal to 0.5, and x + y<a+b；
2) And sintering the mixed material at the temperature of 650-980 ℃ in an oxidizing atmosphere to obtain the cathode material.
6. The method according to claim 5, wherein D of the precursor is50The size is 2-6 μm.
7. The preparation method according to claim 5, wherein the sintering comprises a first stage sintering and a second stage sintering which are sequentially carried out, the temperature of the first stage sintering is 650-800 ℃, and the time of the first stage sintering is 2-6 h; the temperature of the second-stage sintering is 800-980 ℃, and the time of the second-stage sintering is 6-15 h.
8. The production method according to any one of claims 5 to 7, wherein the mass ratio of the compound A to the precursor is (0.1 to 0.6): 1;
preferably, the molar ratio of the lithium element in the lithium source to the precursor is (0.99-1.1): 1;
preferably, the additive is selected from at least one of oxides, fluorides, hydroxides, carbonates, bicarbonates and phosphates of group IIA, group IIIA and transition elements, and the mass of group IIA, group IIIA and transition elements in the additive is 0.0001-1% of the mass of the positive electrode material.
9. A positive electrode comprising the positive electrode material according to any one of claims 1 to 4.
10. A lithium ion battery is characterized by comprising a positive electrode, a negative electrode, an electrolyte and a diaphragm; wherein the positive electrode is the positive electrode according to claim 9.
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