CN110844947B - Preparation method of high-nickel single-crystal positive electrode material, positive electrode material and lithium ion battery - Google Patents
Preparation method of high-nickel single-crystal positive electrode material, positive electrode material and lithium ion battery Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 80
- 239000013078 crystal Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 110
- 239000000463 material Substances 0.000 claims abstract description 67
- 239000007787 solid Substances 0.000 claims abstract description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000005245 sintering Methods 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000007800 oxidant agent Substances 0.000 claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 14
- 239000010406 cathode material Substances 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims description 26
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 10
- 238000003837 high-temperature calcination Methods 0.000 claims description 8
- 239000011344 liquid material Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000009827 uniform distribution Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000203 mixture Substances 0.000 description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 19
- 229910052760 oxygen Inorganic materials 0.000 description 19
- 239000001301 oxygen Substances 0.000 description 19
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 15
- 239000010405 anode material Substances 0.000 description 12
- 239000011572 manganese Substances 0.000 description 9
- 235000010344 sodium nitrate Nutrition 0.000 description 8
- 239000004317 sodium nitrate Substances 0.000 description 8
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000008187 granular material Substances 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
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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
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a preparation method of a high-nickel single crystal cathode material, the cathode material and a lithium ion battery, and the preparation method comprises the steps ofThe preparation method comprises the following steps: s1, crushing the high-nickel secondary ball precursor; s2, coating the surface of the solid oxidant; s3, pre-oxidizing the precursor; s4, sintering the precursor mixed lithium; s5, crushing; s6, washing and sintering. According to the method, the high-nickel precursor with smaller particles and more uniform distribution can be obtained by crushing the high-nickel secondary ball precursor and then coating and fusing the high-nickel secondary ball precursor by the solid oxidant, the crushed high-nickel precursor can be pre-oxidized more thoroughly and can react with lithium more uniformly and more thoroughly in the subsequent lithium mixing and sintering process, so that the high-nickel single crystal material with uniform particle size distribution and better sintering uniformity is obtained, and better electrochemical performance is expressed. The invention also provides a high-nickel single crystal positive electrode material LiNi prepared by the preparation method x CoyM 1‑x‑y O 2 Wherein: x is more than or equal to 0.7, and M is one or two or more of Mn, Al, Mg and Ti.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a preparation method of a high-nickel single crystal positive electrode material.
Technical Field
With the strong support of the country on new energy automobiles, lithium ion batteries are rapidly developed. However, with the change of relevant national support policies and the continuous development of relevant technologies, the endurance mileage of new energy automobiles to lithium ion batteries is higher and higher. The endurance mileage is reflected on the anode material, and the anode material with higher capacity should be developed.
It is known that the capacity of the ternary cathode material is increased by 30% or more, which is mainly determined by the proportion of nickel content in the material, and the capacity of the ternary cathode material is increased by more than 30% when the NCM111 material is upgraded to the NCM811 material, and the cost of raw materials is further reduced because the NCM811 material has lower cobalt content, so the ternary material is increased in nickel content.
In the application process of the high nickel material, more lithium is extracted under high voltage due to higher nickel content, so that irreversible phase change is caused, and the structure is collapsed, and the cycle is deteriorated. Researches find that compared with a high-nickel secondary ball material, the high-nickel single crystal has a more stable structure, can ensure better cycle performance at higher voltage, and has relatively no obvious capacity loss.
However: the prior high-nickel single crystal anode material and the preparation thereof have the following defects:
1. the existing high-nickel single crystal material is mainly prepared by sintering a secondary spherical high-nickel precursor with the particle size of about 3-5 mu m at high temperature into a single crystal shape and then crushing, wherein the sintering mode easily causes uneven internal and external sintering: 1) on the one hand, this inhomogeneity is manifested in the material structure: different degrees of crystallinity and degrees of cation exclusion may result due to different degrees of internal and external oxygen contact; 2) on the other hand, it is also reflected in the particle size: because inside and outside degree of being heated is inconsistent, the condition that once granule is big outside and small in can appearing after the high temperature sintering, and the condition that lithium degree is different can appear taking off in the circulation to this kind of granule size inequality, and little granule takes off lithium degree higher, excessively takes off lithium and can arouse the structure collapse, and the granule pulverization to lead to the circulation to worsen.
2. Like the high nickel material of the secondary ball, the high nickel single crystal material has high nickel content, and if the nickel is not completely oxidized in the sintering process, more divalent nickel is easy to exist, so that the mixed arrangement of lithium and nickel is caused, and the exertion of capacity and circulation is influenced.
In summary, the preparation process of the high-nickel single-crystal cathode material needs to be further optimized.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a high-nickel single crystal anode material, which can obtain a high-nickel precursor with smaller particles and more uniform distribution by crushing a high-nickel secondary sphere precursor and then coating and fusing a solid oxidant, wherein the crushed high-nickel precursor can be pre-oxidized more thoroughly and can react with lithium more uniformly and more thoroughly in the subsequent lithium mixing and sintering process, so that the high-nickel single crystal material with uniform particle size distribution and better sintering uniformity is obtained, and better electrochemical performance is expressed.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the high-nickel single crystal cathode material comprises the following steps:
s1, crushing the high-nickel secondary ball precursor: crushing the small-particle high-nickel secondary ball precursor to obtain a first precursor; the high nickel secondary ball precursor is Ni x CoyM 1-x-y (OH) 2 Wherein: x is more than or equal to 0.7, M is one or two or more of Mn, Al, Mg and Ti;
s2, coating the surface of the solid oxidant: carrying out surface coating treatment on the first precursor obtained in the step S1 by using a solid oxidant to obtain a second precursor;
s3, pre-oxidizing a precursor: performing primary high-temperature calcination treatment on the second precursor obtained in the step S2 to obtain a third precursor; the primary high-temperature calcination temperature is 200-600 ℃, and the calcination time is 2-8 h;
s4, sintering of mixed lithium precursor: mixing the third precursor obtained in the step S3 with a lithium source according to a certain molar ratio, and then carrying out secondary high-temperature calcination treatment; the secondary high-temperature calcination temperature is 700-900 ℃, and the calcination time is 8-16 h;
s5, crushing treatment: crushing the material subjected to high-temperature treatment in S4;
s6, washing and sintering: washing the material crushed in the step S5 to remove impurities introduced in the oxidation process, and then carrying out high-temperature treatment again to remove impurities such as water and the like to obtain the final high-nickel single crystal material; the calcination temperature of the second high-temperature sintering is 100-600 ℃, and the calcination time is 1-6 h; the high-nickel single crystal positive electrode material is LiNi x CoyM 1-x-y O 2 Wherein: x is more than or equal to 0.7, and M is one or two or more of Mn, Al, Mg and Ti.
Preferably, in step S4, the molar ratio of the lithium element in the lithium source to the sum of the molar numbers of the three elements of nickel, cobalt and M in the third precursor is (1.0 to 1.2): 1. in the actual synthesis process, the lithium source is generally lost to some extent, and the lithium source needs to be added in a slight excess.
Further, the air conditioner is provided with a fan,
in step S1, the particle size D50 of the high-nickel secondary ball precursor is less than 5 μm.
Further, the air conditioner is provided with a fan,
in the step S1, the crushing method specifically includes processing for 10-120 min by using a crushing device. Preferably, the crushing equipment is one or a combination of two or more of a ball mill, a mechanical mill and a jet mill.
The specific crushing treatment time is determined according to different crushing equipment and different working frequencies corresponding to different working steps of the equipment.
In step S2, the solid oxidizer is one or two or more of other oxidisable nitrates such as potassium chlorate, sodium chlorate, potassium permanganate, manganese nitrate, potassium nitrate, etc., and the particle size of the solid oxidizer is less than 100 nm.
Further, in step S2, the amount of the solid oxidizing agent added is 1% to 20% by mass of the first precursor.
Further, in step S2, the surface coating treatment method is dry coating, and the specific treatment condition is low-speed treatment at 5 to 20Hz for 10 to 120 min.
Further, in step S2, one or a combination of two or more of a ball mill, a high speed mixer, and a VC machine is used for dry coating.
Further, in step S4, the lithium salt is one or a combination of two or more of lithium hydroxide, lithium fluoride and lithium nitrate.
Further, in step S5, the crushing treatment is performed by using one or a combination of two or more of a ball mill, a mechanical mill, and a jet mill.
Further, in step S6, the washing treatment specifically adopts water washing, alcohol washing or water-alcohol mixed liquor washing, wherein: the liquid-material ratio is (1-5): 1.
The invention has the beneficial effects that:
1. according to the invention, the high-nickel precursor with smaller particles and more uniform distribution can be obtained by crushing the high-nickel secondary ball precursor and then coating and fusing the solid oxidant, and compared with the existing preparation process of the high-nickel single crystal cathode material, the high-nickel precursor after crushing can react with lithium more uniformly and more thoroughly in the lithium mixing and sintering process to obtain the high-nickel single crystal material with uniform particle size distribution and better sintering uniformity, so that better electrochemical performance can be expressed.
2. According to the method, the high-nickel secondary ball precursor is crushed and then calcined by the oxidant for preoxidation, so that the precursor can be preoxidized more thoroughly, cation mixed discharge in the high-nickel material can be reduced more favorably, and the electrochemical performance of the material is improved.
3. In the process of sintering the lithium mixture, chlorate such as potassium chlorate, sodium chlorate and the like is used as a solid oxidant, and chloride formed after reduction can play a role of a fluxing agent, so that the single crystallization degree is favorably improved; meanwhile, metal ions contained in the solid oxidant can play a role in doping and stabilizing crystal lattices, for example, potassium permanganate and manganese nitrate are used as the solid oxides, and the metal manganese ions can be doped and stabilized crystal lattices, so that the electrochemical performance of the single crystal material can be improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an SEM image of a Ni0.8Co0.1Mn0.1(OH)2 precursor having a particle size of about 3 μm provided in example 1 and comparative example 1;
FIG. 2 is a high nickel single crystal LiNi obtained in example 1 0.8 Co 0.1 Mn 0.1 O 2 SEM comparison of positive electrode material a 17;
FIG. 3 is a high nickel single crystal LiNi obtained in comparative example 1 0.8 Co 0.1 Mn 0.1 O 2 SEM of cathode Material B17Comparing the images;
FIG. 4 is a graph comparing the chargeback cycle performance curves (room temperature, 3.0-4.4V, 1C cycle 200 weeks) for sample A17 from example 1 and sample B17 from comparative example 1.
Detailed Description
In order to better illustrate the content of the invention, the invention is further verified by the following specific examples. It should be noted that the examples are given for the purpose of describing the invention more directly and are only a part of the present invention, which should not be construed as limiting the invention in any way.
Example 1, comparative example 1
Provides a high nickel single crystal anode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 The preparation method comprises the following specific steps:
1) 3kg of Ni with a particle size D50 of 3 microns 0.8 Co 0.1 Mn 0.1 And (OH)2 secondary ball precursor A11 is placed in a universal pulverizer, and is treated for 30min at a high speed of 80Hz to obtain a crushed first precursor A12.
2) 0.3kg of potassium chlorate solid with the granularity of 50nm is added into the first precursor A12 which is processed at high speed, and the coated second precursor A13 is obtained after processing for 15min at the frequency of 15Hz at low speed.
As comparative example 1, synchronously, 3kg of the precursor in the same batch in the step 1) is taken, 0.3kg of potassium chlorate solid with the particle size of 50nm is mixed, and the mixture is treated for 15min at the low speed of 15Hz to obtain a coated second precursor B13.
3) And (3) putting the treated second precursors A13 and B13 into a muffle furnace continuously filled with oxygen, calcining for 4 hours at 400 ℃ to obtain pre-oxidized third precursors A14 and B14, and cooling for later use.
4) Taking the treated third precursors A14 and B14, and mixing with lithium hydroxide according to the molar ratio of 1: 1.05, placing the mixture in a muffle furnace with oxygen, calcining the mixture for 15 hours at 800 ℃ to respectively obtain LiNi 0.8 Co 0.1 Mn 0.1 O 2 Materials a15 and B15.
5) Crushing the materials A15 and B15 by using an air flow mill to respectively obtain the single crystal LiNi 0.8 Co 0.1 Mn 0.1 O 2 Materials a16, B16.
6) Respectively taking the A16 and B16 materials, and mixing with deionized water according to the weight ratio of 1: 1, washing, drying, removing impurities introduced in the oxidation process, then placing in a muffle furnace with oxygen at 400 ℃ for calcining for 2 hours, removing impurities such as moisture and the like, and obtaining the final finished product, wherein the liquid-material ratio is A17 and B17.
Example 2, comparative example 2
Provides a high nickel single crystal anode material LiNi 0.88 Co 0.10 Al 0.02 O 2 The preparation method of the material comprises the following specific steps:
1) 3kg of Ni with a particle size D50 of 3.5 microns 0.88 Co 0.10 Mn 0.02 And (OH)2 secondary ball precursor A21 is placed in a VC high-speed mixer, and is treated for 40min at the frequency of 70Hz at a high speed to obtain a crushed first precursor A22.
2) 0.2kg of manganese nitrate solid with the particle size of 60nm is taken and added into the first precursor A22 which is processed at high speed, and the coated second precursor A23 is obtained after processing for 30min at the frequency of 10Hz at low speed.
As comparative example 2, synchronously, 3kg of the precursor in the same batch in the step 1) is mixed with 0.2kg of manganese nitrate solid with the particle size of 60nm, and the mixture is treated for 30min at the low speed of 10Hz to obtain a coated second precursor B23.
3) And (3) putting the treated second precursors A23 and B23 into a muffle furnace continuously filled with oxygen, calcining for 6h at 500 ℃ to obtain pre-oxidized third precursors A24 and B24, and cooling for later use.
4) Taking the treated third precursors A24 and B24, and mixing with lithium nitrate according to the molar ratio of nickel-cobalt-manganese in the precursors to lithium in a lithium source of 1: 1.06, placing the mixture in a muffle furnace filled with oxygen, and calcining the mixture for 12 hours at 900 ℃ to obtain the single crystal LiNi 0.88 Co 0.10 Al 0.02 O 2 Materials a25, B25.
5) Crushing the A25 and B25 materials obtained in the step 4) by using a mechanical mill to obtain crushed single crystal LiNi 0.88 Co 0.10 Al 0.02 O 2 Materials a26, B26.
6) Mixing the single crystal materials A26 and B26 obtained in the step 5) with ethanol solution according to the liquid-material ratio of 2: 1, washing, drying, removing impurities introduced in the oxidation process, calcining for 2 hours in an oxygen furnace at 300 ℃, and removing impurities such as moisture to obtain final finished products A27 and B26.
Example 3, comparative example 3
Provides a high nickel single crystal anode material LiNi 0.90 Co 0.06 Mg 0.04 O 2 The preparation method of the material comprises the following specific steps:
1) taking 3kg Ni with the particle size D50 of 4 microns 0.90 Co 0.06 Mg 0.04 And (OH)2 secondary ball precursor A31 is placed in a high-speed mixer and treated for 50min at the frequency of 65Hz to obtain a crushed first precursor A32.
2) Taking 0.15kg of sodium nitrate solid with the granularity of 50nm, adding the sodium nitrate solid into the first precursor A32 treated at a high speed, and treating the mixture for 40min at the frequency of 10Hz at a low speed to obtain a second precursor A33 coated with sodium nitrate;
as comparative example 3, synchronously, 3kg of the same batch of precursor in the step 1) is taken, 0.15kg of 50nm sodium nitrate solid is mixed, and the mixture is treated for 40min at a low speed of 10Hz to obtain a coated second precursor B33.
3) And (3) putting the treated second precursors A33 and B33 into a muffle furnace continuously filled with oxygen, calcining for 5 hours at 450 ℃ to obtain pre-oxidized third precursors A34 and B34, and cooling for later use.
4) Taking the treated third precursors A34 and B34, and mixing with lithium fluoride according to the molar ratio of nickel-cobalt-manganese in the precursors to lithium in a lithium source of 1: 1.08, placing the mixture in a muffle furnace filled with oxygen, and calcining the mixture for 16 hours at 850 ℃ to obtain the single crystal LiNi 0.90 Co 0.06 Mg 0.04 O 2 Materials a35, B35.
5) Crushing the materials A35 and B35 obtained in the step 4) by using an air flow mill to obtain crushed single crystal LiNi 0.90 Co 0.06 Mg 0.04 O 2 Materials a36, B36.
6) Mixing the monocrystalline materials A36 and B36 obtained in the step 5) with deionized water according to the liquid-material ratio of 3 to 1, washing, drying, removing impurities introduced in the oxidation process, calcining for 1h at 250 ℃ in an oxygen furnace, and removing impurities such as moisture to obtain final finished products A37 and B37.
Example 4, comparative example 4
Provides a high nickel single crystal anode material LiNi 0.92 Co 0.06 Ti 0.02 O 2 The preparation method of the material comprises the following specific steps:
1) 3kg of Ni with a particle size D50 of 3 microns 0.92 Co 0.06 Ti 0.02 (OH) 2 And (3) placing the secondary ball precursor A41 in a high-speed mixer, and treating for 40min at a high speed of 70Hz to obtain a crushed first precursor A42.
2) Taking 0.18kg of sodium nitrate solid with the granularity of 80nm, adding the sodium nitrate solid into the first precursor A42 treated at a high speed, and treating the mixture for 50min at the frequency of 5Hz at a low speed to obtain a second precursor A43 coated with sodium nitrate;
as comparative example 4, synchronously, 3kg of the same batch of precursor in the step 1) is taken, 0.18kg of sodium nitrate solid with the particle size of 80nm is mixed, and the mixture is treated for 50min at a low speed and the frequency of 5Hz to obtain a coated second precursor B43.
3) And (3) putting the treated second precursors A43 and B43 into a muffle furnace continuously filled with oxygen, calcining for 6h at 500 ℃ to obtain pre-oxidized third precursors A44 and B44, and cooling for later use.
4) Uniformly mixing the treated third precursors A44 and B44 with lithium hydroxide according to the molar ratio of 1: 1.10 of nickel-cobalt-manganese in the precursors to lithium in a lithium source, putting the mixture into a muffle furnace filled with oxygen, and calcining the mixture for 12 hours at 900 ℃ to obtain the single crystal LiNi 0.92 Co 0.06 Ti 0.02 O 2 Materials a45, B45.
5) Crushing the materials A45 and B45 obtained in the step 4) by using a mechanical mill to obtain crushed single crystal LiNi 0.92 Co 0.06 Ti 0.02 O 2 Materials a46, B46.
6) Mixing the monocrystalline materials A46 and B46 obtained in the step 5) with deionized water according to the liquid-material ratio of 2.5 to 1, washing, drying, and calcining in an oxygen furnace at 300 ℃ for 1h to obtain final finished products A47 and B47.
Example 5, comparative example 5
Provides a high nickel single crystal anode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 The preparation method comprises the following specific steps:
1) 3kg of Ni with a particle size D50 of 3 microns 0.8 Co 0.1 Mn 0.1 And (OH)2 secondary ball precursor A51 is placed in a universal pulverizer, and is treated for 120min at a high speed of 50Hz to obtain a crushed first precursor A52.
2) Taking 0.03kg of potassium chlorate solid with the granularity of 50nm, adding the potassium chlorate solid into the first precursor A52 treated at a high speed, and treating for 120min at a low speed of 5Hz to obtain a coated second precursor A53;
as comparative example 5, synchronously, 3kg of the precursor in the same batch in the step 1) is taken, 0.03kg of potassium chlorate solid with the particle size of 50nm is mixed, and the mixture is treated for 120min at the low speed of 5Hz to obtain a coated second precursor B53.
3) And (3) placing the treated second precursors A53 and B53 into a muffle furnace continuously filled with oxygen, calcining for 8 hours at 200 ℃ to obtain pre-oxidized third precursors A54 and B54, and cooling for later use.
4) Taking the treated third precursors A54 and B54, and mixing with lithium hydroxide according to the molar ratio of 1: 1.05, placing the mixture in a muffle furnace with oxygen, and calcining the mixture for 16 hours at 700 ℃ to obtain LiNi 0.8 Co 0.1 Mn 0.1 O 2 Materials a55, B55.
5) Crushing the materials A55 and B55 obtained in the step 4) by using a ball mill to obtain crushed single crystal materials A56 and B56.
6) Taking A56 and B56 materials, and mixing with deionized water according to the weight ratio of 5: the mixture is washed by water, dried and then placed in a muffle furnace with oxygen at 100 ℃ for calcination treatment for 6 hours to obtain the final finished products with the numbers of A57 and B57.
Example 6, comparative example 6
Provides a high nickel single crystal anode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 The preparation method comprises the following specific steps:
1) 3kg of Ni with a particle size D50 of 3 microns 0.8 Co 0.1 Mn 0.1 And (OH)2 secondary ball precursor A61 is placed in a universal pulverizer, and is treated for 10min at a high speed of 1000Hz to obtain a crushed first precursor A62.
2) Taking 0.6kg of potassium chlorate solid with the granularity of 50nm, adding the potassium chlorate solid into the first precursor A62 treated at a high speed, and treating for 10min at a low speed of 20Hz to obtain a coated second precursor A63;
as comparative example 6, synchronously, 3kg of the precursor in the same batch in the step 1) is taken, 0.6kg of potassium chlorate solid with the particle size of 50nm is mixed, and the mixture is treated for 10min at the low speed of 20Hz to obtain a coated second precursor B63.
3) And (3) putting the treated second precursors A63 and B63 into a muffle furnace continuously filled with oxygen, calcining for 2h at 600 ℃ to obtain pre-oxidized third precursors A64 and B64, and cooling for later use.
4) Taking the treated third precursors A64 and B64, and mixing with lithium hydroxide according to the molar ratio of 1: 1.05, placing the mixture in a muffle furnace with oxygen, and calcining the mixture for 8 hours at 900 ℃ to obtain LiNi 0.8 Co 0.1 Mn 0.1 O 2 Materials a65, B65.
5) Crushing the materials A65 and B65 obtained in the step 4) by using an air flow mill to obtain crushed single crystal materials A66 and B66.
6) Taking A66 and B66 materials, and mixing with deionized water according to the weight ratio of 1: 1, washing by adopting a water and alcohol mixed solution, drying, and then placing in a muffle furnace with oxygen at 600 ℃ for calcining for 1h to obtain the final finished products with the numbers of A67 and B67.
The high nickel single crystal materials obtained in examples 1 to 6 and comparative examples 1 to 6 were analyzed as follows:
1) as shown in FIG. 1, FIG. 1 shows Ni with a particle size D50 of 3 μm used in example 1 and comparative example 1 0.8 Co 0.1 Mn 0.1 SEM image of (OH)2 high nickel secondary sphere precursor, showing that the material is a secondary sphere composed of primary particles. The forms of the high nickel secondary ball precursors provided by other examples and comparative examples are also basically the same as the examplesThe secondary sphere precursors provided by 1 are similar in shape and are secondary spheres composed of primary particles.
2) The final products a17 and B17 obtained in example 1 and comparative example 1 were analyzed by scanning electron microscopy, as shown in fig. 2 and 3, and are SEM images of high nickel single crystal materials a17 and B17, respectively, from which it can be seen that: compared with the B17 (namely, the single crystal anode material A17 prepared by directly coating and sintering the precursor without crushing treatment), the single crystal anode material A17 prepared by the method provided by the embodiment 1 of the invention has the advantages of uniform particle distribution and better sintering uniformity.
3) Button cells were prepared from the high-nickel single crystal materials prepared in examples 1 to 6 and comparative examples 1 to 6 in the following manner, and the prepared button cells were numbered DA1 to DA6 and DB1 to DB6, and the assembled button cells were subjected to a battery cycle performance test in a blue test cabinet.
The button half-cell is prepared as follows:
in the preparation environment of the conventional lithium ion battery slurry (dew point-30 ℃), a high-nickel single crystal positive electrode material, superconducting carbon black (SP) and a PVDF binder are mixed according to the weight ratio of 94: 3, and NMP is used as a solvent to be made into the slurry according to the conventional process. And then coating the prepared slurry on an aluminum foil, and drying to obtain the positive plate. The electrochemical performance of the positive plate was tested by using a 2032 type button half cell, the negative electrode of the 2032 type button half cell was a metallic lithium plate, the electrolyte was an EC/DMC (volume ratio of 1: 1) solution with LiPF6 concentration of 1.0M, and the separator was a commercial polyolefin separator. The prepared button half cell is tested on a blue light test cabinet, the test voltage range is 3.0-4.4V, and the cycle multiplying power is 1C cycle. The test results are given in table 1 below:
TABLE 1 test results of electrical properties of lithium ion batteries DA 1-DA 6 and DB1
| Battery numbering | 1C Capacity per discharge (mAh/g) | Capacity retention at 200 weeks of 1C cycle |
| DA1 (Single crystal material A17) | 189.5 | 92.8％ |
| DB1 (Single crystal material B17) | 187.2 | 86.3％ |
| DA2 (Single crystal material A27) | 198.6 | 81.1％ |
| DB2 (Single crystal material B27) | 197.4 | 76.6％ |
| DA3 (Single crystal material A37) | 197.1 | 82.8％ |
| DB3 (Single crystal material B37) | 195.7 | 77.8％ |
| DA4 (Single crystal material A47) | 199.8 | 83.6％ |
| DB4 (Single crystal material B47) | 196.5 | 78.5％ |
| DA5 (Single crystal material A57) | 188.9 | 93.1％ |
| DB5 (Single crystal material B57) | 186.6 | 87.5％ |
| DA6 (Single crystal material A67) | 189.2 | 92.2％ |
| DB5 (Single crystal material B57) | 187.1 | 86.8％ |
In addition, performance data of the button cells DA1 and DB1 assembled corresponding to the single crystalline materials prepared in example 1 and comparative example 1 were plotted in an emphasis manner as shown in fig. 4.
Combining table 1 above and fig. 4, it can be seen that:
the content of Ni is high, the capacity is high, but the retention rate is low. Under the same conditions, compared with the corresponding comparative examples, the button cell assembled correspondingly to the high-nickel single-crystal positive electrode material prepared by the method of the embodiment of the invention has a better cycle battery than the button cell assembled correspondingly to the high-nickel single-crystal positive electrode material prepared by the method of the comparative example.
The method can obtain the high-nickel precursor with smaller particles and more uniform distribution by crushing the high-nickel secondary ball precursor and then coating and fusing the high-nickel precursor with the solid oxidant, and the crushed high-nickel precursor can be pre-oxidized more thoroughly and can react with lithium more uniformly and more thoroughly in the subsequent lithium mixing and sintering process, so that the high-nickel single crystal material with uniform particle size distribution and better sintering uniformity is obtained, and better electrochemical performance is expressed.
The foregoing is a detailed description of the invention and is not intended to limit the invention to the particular forms disclosed, but on the basis of the present invention, it is expressly intended that all such modifications and improvements are within the scope of the invention.
Claims (5)
1. The preparation method of the high-nickel single crystal cathode material is characterized by comprising the following steps:
s1, crushing the high-nickel secondary ball precursor: crushing the small-particle high-nickel secondary ball precursor to obtain a first precursor; the high nickel secondary ball precursor is Ni x CoyM 1-x-y (OH) 2 Wherein: x is more than or equal to 0.7, M is one or two or more of Mn, Al, Mg and Ti; the crushing treatment method specifically comprises the steps of treating for 10-120 min by adopting crushing equipment; the crushing equipment is one of a ball mill, a mechanical mill and an air flow mill;
s2, coating the surface of the solid oxidant: carrying out surface coating treatment on the first precursor obtained in the step S1 by using a solid oxidant to obtain a second precursor; the surface coating treatment method is dry coating, and the specific treatment condition is that one or the combination of two or more of a ball mill, a high-speed mixer and a VC machine is adopted for low-speed treatment for 10-120 min at 5-20 Hz; the solid oxidant is one of potassium chlorate, sodium chlorate and potassium permanganate, and the granularity of the solid oxidant is less than 100 nm; the addition amount of the solid oxidant is 1-20% of the mass fraction of the first precursor; s3, pre-oxidizing a precursor: performing primary high-temperature calcination treatment on the second precursor obtained in the step S2 to obtain a third precursor; the primary high-temperature calcination temperature is 200-600 ℃, and the calcination time is 2-8 h;
s4, sintering of mixed lithium precursor: mixing the third precursor obtained in the step S3 with a lithium source according to a certain molar ratio, and then carrying out secondary high-temperature calcination treatment; the secondary high-temperature calcination temperature is 700-900 ℃, and the calcination time is 8-16 h;
s5, crushing treatment: crushing the material subjected to high-temperature treatment in the S4;
s6, washing and sintering: washing the material crushed in the step S5 to remove impurities introduced in the oxidation process, and then performing high-temperature treatment again to remove impurities such as water and the like to obtain the final high-nickel single crystal material; the calcination temperature of the second high-temperature sintering is 100-600 ℃, and the calcination time is 1-6 h; the high-nickel single crystal positive electrode material is LiNi x CoyM 1-x-y O 2 Wherein: x is more than or equal to 0.7, and M is one or two or more of Mn, Al, Mg and Ti.
2. The method for producing a high nickel single crystal positive electrode material according to claim 1,
in step S1, the particle size D50 of the high-nickel secondary ball precursor is less than 5 μm.
3. The method for producing a high nickel single crystal positive electrode material according to claim 1,
in step S5, the crushing treatment is performed by using one or a combination of two or more of a ball mill, a mechanical mill, and a jet mill.
4. The method for producing a high nickel single crystal positive electrode material according to any one of claims 1 to 3,
in step S4, the molar ratio of the lithium element in the lithium source to the sum of the molar numbers of the three elements, i.e., nickel, cobalt, and M in the third precursor is (1.0 to 1.2): 1.
5. the method for producing a high nickel single crystal positive electrode material according to any one of claims 1 to 3,
in step S6, the washing treatment specifically adopts water washing, alcohol washing or water-alcohol mixed liquor washing, wherein the liquid-material ratio is (1-5): 1.
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