CN111362307B - Preparation method of monocrystal lithium manganate positive electrode material for lithium ion battery - Google Patents
Preparation method of monocrystal lithium manganate positive electrode material for lithium ion battery Download PDFInfo
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 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 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 74
- 239000000463 material Substances 0.000 claims abstract description 35
- 239000013078 crystal Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 238000000498 ball milling Methods 0.000 claims abstract description 23
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 239000011572 manganese Substances 0.000 claims abstract description 12
- 238000005253 cladding Methods 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000004806 packaging method and process Methods 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- DHAHRLDIUIPTCJ-UHFFFAOYSA-K aluminium metaphosphate Chemical compound [Al+3].[O-]P(=O)=O.[O-]P(=O)=O.[O-]P(=O)=O DHAHRLDIUIPTCJ-UHFFFAOYSA-K 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 4
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 4
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 description 8
- 239000011029 spinel Substances 0.000 description 8
- 238000012876 topography Methods 0.000 description 4
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007952 growth promoter Substances 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- MRVHOJHOBHYHQL-UHFFFAOYSA-M lithium metaphosphate Chemical compound [Li+].[O-]P(=O)=O MRVHOJHOBHYHQL-UHFFFAOYSA-M 0.000 description 1
- LQKOJSSIKZIEJC-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+2].[Mn+2].[Mn+2] LQKOJSSIKZIEJC-UHFFFAOYSA-N 0.000 description 1
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
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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
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/41—Particle morphology extending in three dimensions octahedron-like
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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 preparation method of a monocrystal lithium manganate positive electrode material for a lithium ion battery, which comprises the following steps: step A: ball-milling and mixing a small-particle manganese source, lithium carbonate and an additive according to a proportion; and (B) step (B): sintering the ball-milled and mixed material at a low temperature; step C: ball-milling and mixing the low-temperature sintered material, the fine-grained lithium manganate seed crystal and the sintering aid according to a proportion; step D: loading the mixture containing the fine-grained lithium manganate crystal seeds after ball milling and mixing into a pot for sintering; step E: crushing the material sintered at high temperature, and then adding a coating agent for coating and sintering; step F: the materials after cladding and sintering are subjected to post-treatment procedures such as process grading, demagnetizing, batch mixing and packaging, and the like to prepare the finished product. Compared with the traditional process, the preparation method provided by the invention is simple, the process is more environment-friendly, and the obtained lithium manganate product has high capacity and long service life.
Description
Technical Field
The invention belongs to the fields of energy storage materials and electrochemistry, and relates to a preparation method of a monocrystal lithium manganate anode material for a lithium ion battery.
Background
Lithium ion batteries have become the first choice for power cells because of their high energy density, excellent cycle life, no memory effect, low self-discharge rate, low pollution, and the like. In the development process of lithium ion batteries, the positive electrode material is always a critical factor. In recent years, lithium manganate has become a promising substitute for lithium cobaltate due to the advantages of low cost, no toxicity, good safety and the like. However, capacity fade of lithium manganate in charge-discharge cycle, particularly cycle performance at high temperature (55 ℃) is an important issue impeding its application, aiming at causing spinel LiMn 2 O 4 The capacity attenuation mechanism expands a series of researches at home and abroad, and the currently accepted reasons for causing the capacity attenuation of spinel type lithium manganate mainly are as follows: (1) Spinel structure LiMn 2 O 4 The Jahn-Teller effect occurs during the circulation process, which causes the spinel lattice to be distorted, and the impedance of the electrode is increased along with the large volume change, thereby causing capacity attenuation, (2) during the circulation process, liMn is carried out under the action of electrolyte 2 O 4 The disproportionation reaction occurs on the electrode surface so that manganese is slowly dissolved in the electrolyte, resulting in a decrease in cycle performance. Therefore, the characteristics of spinel LiMn2O4 such as crystallinity, grain morphology, grain size, and grain size distribution are specific to LiMn 2 O 4 The performance of the positive electrode material is greatly affected.
In order to improve the performance of spinel lithium manganate, a great deal of research is put into practice, and certain effects are achieved. The single crystal lithium manganate is a new product which is pushed out by the lithium manganate industry for several years, and the cycle performance is greatly improved. However, single crystal lithium manganate has not been applied on a large scale in the lithium battery industry, and the preparation technology of single crystal lithium manganate has yet to be further innovated.
Disclosure of Invention
The invention aims to overcome the defects of the existing lithium manganate positive electrode material, synthesizes single crystal lithium manganate by improving the preparation process, and compared with the traditional lithium manganate material, the single crystal lithium manganate has the shape of primary particles, regular octahedron shape, smaller particles, D50 of about 3 microns, spinel structure and compaction density of 3.1g/cm 3 The capacity can reach 110-120 mAh/g, and the cycle times can reach 1000-2000 times. The monocrystal structure can further improve the capacity of the lithium manganate material, reduce the internal resistance, reduce the polarization loss and prolong the cycle life of the battery; meanwhile, high compaction can be obtained, the phenomenon of particle breakage caused by rolling similar secondary particles in battery manufacturing can be avoided by the higher compaction, and the cycle performance of the material is further improved.
The invention provides a preparation method of single crystal lithium manganate for lithium ion batteries, which is characterized in that a small particle manganese source is adopted as a raw material, fine crystal lithium manganate crystal seeds are used as crystal nucleation and growth inducers, a low-melting-point sintering aid is used as a crystal nucleus growth promoter to prepare power single crystal lithium manganate, compared with the traditional process, the preparation method is simple, the process is more environment-friendly, the morphology of the obtained lithium manganate single crystal is more complete, the monocrystal lithium manganate with regular octahedral morphology can be obtained, the obtained product has high capacity and long service life.
The preparation method of the monocrystal lithium manganate positive electrode material for the lithium ion battery comprises the following steps:
step A: ball-milling and mixing a small-particle manganese source, lithium carbonate and an additive according to a proportion;
and (B) step (B): sintering the ball-milled and mixed material at a low temperature;
step C: ball-milling and mixing the low-temperature sintered material, the fine-grained lithium manganate seed crystal and the sintering aid according to a proportion;
step D: loading the mixture containing the fine-grained lithium manganate after ball milling and mixing into a pot for sintering at 700-900 ℃ for 10-20 hours;
step E: crushing the material subjected to high-temperature sintering, and then adding a coating agent to carry out coating sintering at 500-700 ℃ for 5-10 hours;
step F: the materials after cladding and sintering are subjected to post-treatment procedures such as process grading, demagnetizing, batch mixing and packaging, and the like to prepare the finished product.
Preferably, the small particle manganese source in step A is mainly at least one of manganous oxide, manganese dioxide, manganous oxide, manganous hydroxide and manganous carbonate with D50 of 1.7-4.7 microns.
Preferably, the additive is one or two of niobium oxide, titanium oxide, silicon oxide, aluminum oxide, magnesium oxide and aluminum fluoride, and the content of the additive is 0.1-1% of the mass fraction of the whole single-crystal lithium manganate.
Preferably, the molar ratio of lithium to manganese in the step A is 1:1.9-2.0.
Preferably, in the step B, the sintering temperature is 400-700 ℃, the heating speed is 1-5 ℃/min, the sintering time is 5-10 hours, and the atmosphere is air or oxygen.
Preferably, in the step C, the fine-grained lithium manganate seed crystal is monocrystalline lithium manganate with a grain size of 1 micrometer, the content is 1-5% of the mass of the system, and the sintering aid is one or two of yttrium oxide, aluminum fluoride, aluminum metaphosphate and lithium fluoride, and the mass content of the sintering aid is 0.2% -1% of the mass of the system. The sintering aid has the function of reducing the sintering temperature and promoting the growth of crystal grains.
Preferably, in the step D, the sintering temperature is 700-850 ℃ and the sintering time is 10-20 hours, and the sintering atmosphere is air or oxygen.
Preferably, in the step E, the coating agent adopts one or two of aluminum oxide, titanium oxide and aluminum metaphosphate, and the dosage of the coating agent is 0.2% -1% of the mass of the system.
The invention adopts the small-particle manganese source and lithium carbonate as raw materials, utilizes the fine-grain lithium manganate crystal seed as an induction forming agent, and utilizes the low-melting point sintering aid as a crystal nucleus growth promoter to prepare the power type single crystal lithium manganate.
Drawings
Fig. 1 is a surface topography of a single crystal lithium manganate positive electrode material according to one embodiment of the invention.
Fig. 2 is a surface topography of a conventional lithium manganate cathode material.
Fig. 3 is a surface topography of a conventional lithium manganate cathode material.
Fig. 4 is a graph of charge and discharge performance of a single crystal lithium manganate cathode material according to an embodiment of the invention.
Fig. 5 is a graph of the cycling performance of a single crystal lithium manganate positive electrode material according to an embodiment of the invention.
Detailed Description
Preferred embodiments of the present invention will be described in further detail below with reference to the attached drawings:
example 1
Step (1): the manganese tetraoxide with the grain diameter D50 of 1.7-3 microns and lithium carbonate are mixed according to the molar ratio of lithium to manganese of 1:1.9, adding niobium oxide accounting for 0.1 percent of the mass fraction of the system, and performing ball milling for 2 hours;
step (2): sintering the ball-milled and mixed material for 5 hours at 400 ℃ in the air atmosphere at the heating rate of 1-5 ℃/min;
step (3): mixing the low-temperature sintered material with 1 mass percent of fine-grain lithium manganate with the grain diameter of 1 micron and 1 mass percent of sintering aid yttrium oxide with the mass percent of 0.2 mass percent for 2 hours in a ball milling way;
step (4): loading the mixture after ball milling into a bowl for high-temperature sintering at 700 ℃ for 10 hours;
step (5): crushing the material subjected to high-temperature sintering, and then adding a coating agent titanium oxide with the mass of 0.2% of the system to carry out coating sintering at the sintering temperature of 500 ℃ for 10 hours;
step (6): the materials after cladding and sintering are subjected to post-treatment procedures such as process grading, demagnetizing, batch mixing and packaging, and the like to prepare the finished product.
Example 2
Step (1): manganese dioxide and lithium oxide with the particle size D50 of 2-4.7 microns are mixed according to the molar ratio of lithium to manganese of 1:2, adding titanium oxide accounting for 1% of the mass fraction of the system, and performing ball milling for 4 hours;
step (2): sintering the ball-milled and mixed material for 10 hours at a low temperature of 700 ℃ in an air atmosphere, wherein the heating rate is 1-5 ℃/min;
step (3): mixing the low-temperature sintered material with fine-grain lithium manganate with the grain diameter of 1 micron and the system content of 5% and sintering aid alumina with the system content of 1% in proportion by ball milling for 4 hours;
step (4): loading the mixture after ball milling into a bowl for high-temperature sintering at 900 ℃ for 20 hours;
step (5): crushing the material subjected to high-temperature sintering, and then adding a coating agent alumina accounting for 1% of the mass of the system to carry out coating sintering at a sintering temperature of 700 ℃ for 5 hours;
step (6): the materials after cladding and sintering are subjected to post-treatment procedures such as process grading, demagnetizing, batch mixing and packaging, and the like to prepare the finished product.
Example 3
Step (1): mixing manganese sesquioxide with the particle size D50 of 2-4 microns and lithium carbonate according to the proportion of 1/1.95 of the molar ratio of lithium to manganese, and then adding silicon oxide with the mass fraction of 0.5% of the system for ball milling for 3 hours;
step (2): sintering the ball-milled and mixed material for 6 hours at a low temperature of 500 ℃ in an oxygen atmosphere, wherein the heating rate is 1-5 ℃/min;
step (3): mixing the low-temperature sintered material with fine-grain lithium manganate with the grain diameter of 1 micron and the system content of 2% and sintering aid aluminum fluoride with the system content of 0.3% in proportion by ball milling for 3 hours;
step (4): loading the mixture after ball milling into a pot for sintering, wherein the sintering temperature is 800 ℃ and the sintering time is 15 hours;
step (5): crushing the material subjected to high-temperature sintering, and then adding a coating agent aluminum metaphosphate accounting for 0.5% of the system mass for coating sintering, wherein the sintering temperature is 600 ℃ and the sintering time is 8 hours;
step (6): the materials after cladding and sintering are subjected to post-treatment procedures such as process grading, demagnetizing, batch mixing and packaging, and the like to prepare the finished product.
Example 4
Step (1): mixing manganese monoxide with the particle size D50 of 1.7-4 microns and lithium carbonate according to the proportion of 1/1.93 of the molar ratio of lithium to manganese, and then adding aluminum oxide with the mass fraction of 0.7% of the system for ball milling for 2.5 hours;
step (2): sintering the ball-milled and mixed material for 7 hours at a low temperature of 600 ℃ in an oxygen atmosphere, wherein the heating rate is 1-5 ℃/min;
step (3): mixing the low-temperature sintered material with 3% of fine-grain lithium manganate with the particle size of 1 micron and 3% of sintering aid lithium metaphosphate with the system mass content of 0.6% in proportion for 2.5 hours;
step (4): loading the mixture after ball milling into a bowl for high-temperature sintering at 750 ℃ for 15 hours;
step (5): crushing the material subjected to high-temperature sintering, and then adding a coating agent titanium oxide with the mass of 0.6% of the system to carry out coating sintering, wherein the sintering temperature is 550 ℃, and the sintering time is 9 hours;
step (6): the materials after cladding and sintering are subjected to post-treatment procedures such as process grading, demagnetizing, batch mixing and packaging, and the like to prepare the finished product.
Example 5
Step (1): mixing micro manganese carbonate with the particle size D50 of 3-4.5 and lithium oxide according to the proportion of 1/1.98 of the molar ratio of lithium to manganese, and then adding magnesium oxide with the mass fraction of 0.4% of the system for ball milling for 3.8 hours;
step (2): sintering the ball-milled and mixed material for 8 hours at a low temperature of 550 ℃ in an air atmosphere, wherein the heating rate is 1-5 ℃/min;
step (3): mixing the low-temperature sintered material with 4% of fine-grain lithium manganate with the particle size of 1 micron and 4% of sintering aid lithium fluoride with the system mass content of 0.8% in a ball milling way for 3.5 hours;
step (4): loading the mixture after ball milling into a pot for sintering, wherein the sintering temperature is 850 ℃ and the sintering time is 12 hours;
step (5): crushing the material subjected to high-temperature sintering, and then adding a coating agent alumina accounting for 0.8% of the system mass for coating sintering at a sintering temperature of 650 ℃ for 6.5 hours;
step (6): the materials after cladding and sintering are subjected to post-treatment procedures such as process grading, demagnetizing, batch mixing and packaging, and the like to prepare the finished product.
FIGS. 1-2 are surface topography diagrams of a single crystal lithium manganate positive electrode material according to one embodiment of the invention. In the figure, the morphology of the monocrystal lithium manganate is primary particles, the monocrystal lithium manganate is in a regular octahedron morphology, the particles are smaller, the D50 crystal structure characteristics are obvious at about 3 microns, and the structure is a spinel structure; compared with the common lithium manganate morphology shown in fig. 3, the product particles prepared by the method are far smaller than the conventional product and the crystal form characteristics are obvious.
Fig. 4-5 are electrochemical performance tests performed by using the product prepared by the embodiment as an anode active material, and it can be seen from the graph that the capacity of the product prepared by the method can reach more than 110mAh/g, and the capacity can be maintained to be more than 99% after 200 times of cyclic charge and discharge, so that the problem of capacity reduction caused by dissolution of lithium manganate in the charge and discharge process is further effectively solved.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (3)
1. The preparation method of the monocrystal lithium manganate positive electrode material for the lithium ion battery is characterized by comprising the following steps of:
step A: ball-milling and mixing a small-particle manganese source, lithium carbonate and an additive according to a proportion;
and (B) step (B): sintering the ball-milled and mixed material at a low temperature;
step C: ball-milling and mixing the low-temperature sintered material, the fine-grained lithium manganate seed crystal and the sintering aid according to a proportion;
step D: loading the mixture containing the fine-grained lithium manganate after ball milling and mixing into a pot for sintering at 700-900 ℃ for 10-20 hours;
step E: crushing the material subjected to high-temperature sintering, and then adding a coating agent to carry out coating sintering at 500-700 ℃ for 5-10 hours;
step F: carrying out post-treatment procedures such as process grading, demagnetizing, batch mixing and packaging on the material after cladding and sintering to prepare a finished product; in the step A, the small-particle manganese source mainly refers to at least one of small-particle manganous oxide, manganese dioxide, manganous oxide, manganese monoxide, manganese hydroxide and manganese carbonate with the D50 of 1.7-4.7 microns; in the step B, the sintering temperature is 400-700 ℃, the heating speed is 1-5 ℃/min, the sintering time is 5-10 hours, and the atmosphere is air or oxygen; the additive adopts one or two of niobium oxide, titanium oxide, silicon oxide, aluminum oxide, magnesium oxide and lithium fluoride, and the content of the additive is 0.1-1% of the mass fraction of the whole positive electrode material; the fine-grain lithium manganate seed crystal is monocrystalline lithium manganate with the grain diameter of 1 micron, and the content is 1-5% of the mass of the whole positive electrode material; in the step C, the sintering aid is one or two of yttrium oxide, aluminum fluoride, aluminum metaphosphate and lithium fluoride, and the mass content of the sintering aid accounts for 0.2% -1% of the content of the whole positive electrode material; in the step D, the sintering atmosphere is air or oxygen.
2. The method according to claim 1, wherein the molar ratio of lithium/manganese in step a is 1:1.9-2.0.
3. The preparation method according to claim 1, wherein in the step E, the coating agent is one or two of aluminum oxide, titanium oxide and aluminum metaphosphate, and the dosage of the coating agent is 0.2% -1% of the mass of the system.
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