CN116573680A - Lithium cobaltate material and preparation method and application thereof - Google Patents
Lithium cobaltate material and preparation method and application thereof Download PDFInfo
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- CN116573680A CN116573680A CN202310611527.7A CN202310611527A CN116573680A CN 116573680 A CN116573680 A CN 116573680A CN 202310611527 A CN202310611527 A CN 202310611527A CN 116573680 A CN116573680 A CN 116573680A
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- lithium
- lithium cobaltate
- cobalt oxide
- positive electrode
- lithium cobalt
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- 239000000463 material Substances 0.000 title claims abstract description 138
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 120
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 239000007774 positive electrode material Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 39
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 238000001354 calcination Methods 0.000 claims description 32
- 229910052799 carbon Inorganic materials 0.000 claims description 32
- 238000000576 coating method Methods 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 26
- 239000011159 matrix material Substances 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 20
- 229910052721 tungsten Inorganic materials 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 16
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 15
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 150000003754 zirconium Chemical class 0.000 claims description 12
- 229910052702 rhenium Inorganic materials 0.000 claims description 11
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000012716 precipitator Substances 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 230000008569 process Effects 0.000 abstract description 11
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 12
- 229940044175 cobalt sulfate Drugs 0.000 description 12
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 229910052726 zirconium Inorganic materials 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 6
- 229910021392 nanocarbon Inorganic materials 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 239000006104 solid solution Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 229940118662 aluminum carbonate Drugs 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 150000002772 monosaccharides Chemical class 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 3
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 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
- 230000003139 buffering effect Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- 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
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- 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
- C01P2006/10—Solid density
-
- 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
- C01P2006/11—Powder tap density
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium cobaltate material, a preparation method and application thereof. The lithium cobaltate material is hollow sphere-shaped, and contains doping element A. The lithium cobaltate material is hollow and spherical, has stable structure, and is used as the positive electrode material in the secondary battery, so that the structural stability of the positive electrode material in the working process of the battery is improved, and the cycle stability of the battery is improved.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a lithium cobaltate material, a preparation method and application thereof.
Background
Lithium cobaltate is one of the most commonly used positive electrode materials of current consumer electronic portable equipment, and has the advantages of higher theoretical specific capacity (274 mAh/g), good multiplying power performance, higher tap density and the like, but the gram capacity exerted by the current commercial battery adopting lithium cobaltate is 170-185mAh/g, and the main reason is that the crystal structure of lithium cobaltate gradually changes phase in the repeated expansion and contraction process in the continuous deintercalation process of lithium ions, and gradually changes from a layered structure suitable for reversible deintercalation of lithium ions to spinel with structural failure. Thus, the conventional lithium cobaltate materials are poor in stability.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the lithium cobaltate material provided by the invention is hollow and spherical, and has the characteristic of good stability.
The invention also provides a preparation method of the lithium cobaltate material.
The invention also provides a positive electrode material.
The invention also provides a secondary battery.
The invention also provides application of the lithium cobaltate material.
In a first aspect of the present invention, a lithium cobalt oxide material is provided, the lithium cobalt oxide material is hollow sphere, and the lithium cobalt oxide material contains a doping element a.
The lithium cobaltate material provided by the embodiment of the invention has at least the following beneficial effects:
the lithium cobaltate material is hollow and spherical, has stable structure, and is used as a positive electrode material in a secondary battery, so that the structural stability of the positive electrode material in the working process of the battery is improved, and the performances such as the cycle stability of the battery are improved. Specifically, the hollow structure provides a certain buffer space for expansion and contraction of the lithium cobaltate material in the working process, improves the structural stability, and is beneficial to the stability of battery circulation; the hollow structure improves the specific surface area of the lithium cobaltate material, increases the contact area of the electrolyte and the lithium cobaltate, improves the reaction kinetics of lithium ions, and has a certain improvement on the low-temperature performance of the battery.
Meanwhile, the lithium cobaltate material is suitable for high-voltage application environments. Aiming at the application voltages of 4.40V and 4.45V which are most commonly used in the current market, even when the application voltage reaches more than 4.5V (such as 4.50-4.53V), the lithium cobaltate material is not easy to take off and insert lithium ions in the circulating process, the material structure is not easy to collapse, and the high-voltage application stability is strong.
It should be noted that, a is a doping element, which means that the element a may be located at any position of the lithium cobaltate material, for example, the element a may be doped in the lithium cobaltate material or on the outer surface thereof, and for example, the element a (e.g. W) may also be used as a constituent element of the coating material for coating the outer surface of the lithium cobaltate matrix. Wherein the lithium cobaltate matrix refers to a substance component except for the outer surface in the hollow spherical lithium cobaltate material.
In some embodiments of the invention, the lithium cobaltate material has the general formula Li a Co b A c O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein a is more than or equal to 0.4 and less than or equal to 1.8,0.6, b is more than or equal to 1.5, and c is more than or equal to 0 and less than or equal to 0.08.
In some preferred embodiments of the invention, 0.45.ltoreq.a.ltoreq. 1.75,0.65.ltoreq.b.ltoreq. 1.45,0.01.ltoreq.c.ltoreq.0.08.
In some embodiments of the present invention, the lithium cobaltate material has a mass fraction of Li element of 5-9%.
In some embodiments of the present invention, the mass fraction of Co element in the lithium cobaltate material is 56-64%.
In some embodiments of the invention, the element a comprises at least one of Re, al, zr, W, ga, hf, mg, sn, zn, ni, mn, V, mo, nb, cu, fe, in or Cr.
Through the embodiment, doping (such as Zr and Al) of the doping element A can be used for stabilizing the crystal phase structure of the lithium cobaltate, and preventing structural collapse, battery attenuation and water jump caused by cobalt dissolution of the lithium cobaltate in a high-release state under high voltage. In addition, the doping element A (such as W, re) can also be used as a constituent element of a coating substance, and the coating substance is used for coating the outer surface of the lithium cobalt oxide matrix so as to reduce side reactions of the lithium cobalt oxide and the electrolyte and protect the cathode material. The lithium cobalt oxide matrix refers to a hollow spherical lithium cobalt oxide material, and substances except for the outer surface of the material form the matrix.
For the element Re, the doping depth is weaker because the atomic radius of the Re element is larger and the Re element is not easy to enter the crystal lattice, so that the conventional lithium cobaltate cannot generally obtain higher Re doping amount. In the invention, the lithium cobaltate material is of a hollow structure, has larger specific surface area, is more suitable for doping Re, and the Re is more easily concentrated on the inner surface and the outer surface of the hollow lithium cobaltate matrix to obtain higher doping amount. The doping of Re element is favorable for improving the high-voltage cycle performance of the battery. When Re and W are used as doping elements, a solid solution is formed after the Re and W are coated, so that the overall ionic conductivity of the material is improved, and the effects of improving the polarization of a battery and reducing the internal resistance are achieved.
In some preferred embodiments of the invention, the element a comprises Re, and further comprises at least one of Al, zr, W, ga, hf, mg, sn, zn, ni, mn, V, mo, nb, cu, fe, in or Cr.
In some preferred embodiments of the invention, the element a comprises at least one of Re, al, W or Zr.
In some preferred embodiments of the invention, the element a comprises Re and W, and further comprises at least one of Al or Zr.
With the above embodiment, when Al, zr are doped as doping elements in lithium cobaltate, al or/and Zr elements may replace Co sites to stabilize the crystal phase structure. The doping of Al element is preferable because it is easy to prepare and inexpensive. The Re element has larger atomic radius and is easy to concentrate on the surface of the hollow lithium cobalt oxide matrix, for example, the Re element is positioned on the outer surface of the lithium cobalt oxide matrix, so that a solid solution can be formed after the W element is coated, the whole ion conductivity of the material is improved, and the effects of improving the polarization of a battery and reducing the internal resistance are achieved.
In some preferred embodiments of the present invention, the mass fraction of Re element in the lithium cobaltate material is 1000ppm to 4000ppm.
In some more preferred embodiments of the present invention, the mass fraction of Re element in the lithium cobaltate material is 2000ppm to 3000ppm.
In some preferred embodiments of the present invention, the mass fraction of Al element in the lithium cobaltate material is 5500-11000ppm.
In some more preferred embodiments of the present invention, the mass fraction of Al element in the lithium cobaltate material is 6500-8500ppm.
In some preferred embodiments of the present invention, the mass fraction of Zr element in the lithium cobaltate material is 50-450ppm.
In some more preferred embodiments of the present invention, the mass fraction of Zr element in the lithium cobaltate material is 150-350ppm.
In some preferred embodiments of the present invention, the mass fraction of the W element in the lithium cobaltate material is 1000-3000ppm.
In some more preferred embodiments of the present invention, the mass fraction of the W element in the lithium cobaltate material is 1500-2500ppm.
In the invention, the content of the element doping or the element coating is relatively small, preferably at ppm level, and trace element doping is realized, so that the material has the characteristics of structural stability, capacity per se, rate capability and the like of the lithium cobaltate material are not easy to lose.
In some preferred embodiments of the present invention, the lithium cobaltate material comprises lithium cobaltate matrix particles and a coating substance coated on the outer surface of the lithium cobaltate matrix particles, the coating substance comprising the element a.
In some more preferred embodiments of the invention, the coating substance comprises at least one of the elements Al, zr or W.
In some more preferred embodiments of the invention, the coating substance comprises at least one of the elements W or Zr.
Through the embodiment, the coating substance comprises the element W, so that residual alkali on the surface of the lithium cobaltate material can be reduced, the processability of the lithium cobaltate material is improved, and meanwhile, the formed lithium tungstate has good conductivity and corrosion resistance.
In some more preferred embodiments of the present invention, the coating substance comprises at least one of tungsten oxide or zirconium oxide.
In some more preferred embodiments of the invention, the coating is an island coating.
In some preferred embodiments of the invention, the element A comprises element A 1 And element A 2 The lithium cobaltate material comprises lithium cobaltate matrix particles and a coating substance coated on the outer surface of the lithium cobaltate matrix particles, wherein the lithium cobaltate matrix particles comprise element A 1 The coating material comprises the element A 2 。
In some more preferred embodiments of the invention, the elementsElement A 1 Comprises at least one of Al, zr, W, ga, hf, mg, sn, zn, ni, mn, V, mo, nb, cu, fe, in or Cr; the element A 2 Including at least one of Re, al, zr, W, ga, hf, mg, sn, zn, ni, mn, V, mo, nb, cu, fe, in or Cr.
In some more preferred embodiments of the invention, the element A 1 Comprising at least one of Al or Zr, said element A 2 Including at least one of Re, al, W or Zr.
In some more preferred embodiments of the invention, the element A 1 Comprising at least one of Al or Zr, said element A 2 Comprises Re and at least one of Al, W or Zr.
In some embodiments of the invention, the lithium cobaltate material is a hollow sphere-shaped nano lithium cobaltate material.
Through the implementation mode, the nano lithium cobaltate material is a single crystal hollow nano microsphere, and has strong structural stability and good application prospect.
In some embodiments of the invention, the lithium cobaltate material has a particle size of 100-1500nm.
In some preferred embodiments of the invention, the lithium cobaltate material has a particle size of 500-800nm.
In some embodiments of the invention, the lithium cobaltate material has a wall thickness of 10-300nm.
In some preferred embodiments of the invention, the lithium cobaltate material has a wall thickness of 50-100nm.
In the invention, the control of the wall thickness can be related to the preparation process, and proper preparation process parameters can be regulated and selected according to actual needs to obtain the required wall thickness.
In some embodiments of the invention, the lithium cobaltate material has a tap density of 1.5-3.0g/cm 3 。
In some preferred embodiments of the invention, the lithium cobaltate material has a tap density of from 2.1 to 2.6g/cm 3 。
In some embodiments of the invention, the cobaltThe compacted density of the lithium acid material is 3.5-4.7g/cm 3 。
In some preferred embodiments of the invention, the lithium cobaltate material has a compacted density of 4.0-4.2g/cm 3 。
In some embodiments of the invention, the lithium cobaltate material has the chemical formula LiCoO 2 Re n Zr x W y Al z Wherein x is more than or equal to 0 and less than or equal to 0.05, y is more than or equal to 0 and less than or equal to 0.4, z is more than or equal to 0 and less than or equal to 0.9, and n is more than or equal to 0 and less than or equal to 0.4.
In a second aspect of the present invention, a method for preparing a lithium cobaltate material is provided, the method comprising the steps of:
s1, taking an aqueous solution containing template carbon spheres and cobalt salt, adding a precipitator, and calcining to obtain a hollow spherical cobaltosic oxide precursor;
s2, taking a mixture containing lithium salt and the precursor, and calcining to obtain a hollow spherical lithium cobalt oxide material;
in the step S1, the aqueous solution also comprises a raw material I containing A; or/and, in the step S2, the mixture also comprises a raw material II containing A.
The preparation method of the hollow spherical lithium cobaltate material provided by the embodiment of the invention has at least the following beneficial effects: according to the invention, the hollow-morphology lithium cobalt oxide material is synthesized by adopting a template method, so that the volume deformation of the material in the process of buffering circulation is facilitated, and the obtained material has a stable structure, so that the circulation stability of an applied battery is improved. In step S1, the precursor is a cobaltosic oxide precursor or an element a doped cobaltosic oxide precursor.
In some embodiments of the invention, in step S1, the cobalt salt comprises at least one of cobalt sulfate, cobalt nitrate, or cobalt chloride.
In some embodiments of the invention, in step S1, the precipitating agent comprises at least one of a carbonate or a base.
In some preferred embodiments of the present invention, in step S1, the precipitant includes at least one of sodium hydroxide or sodium carbonate.
In some embodiments of the invention, in step S1, the calcination temperature is 300-800 ℃.
In some embodiments of the invention, in step S1, the calcination time is 2h or more.
In some preferred embodiments of the invention, in step S1, the calcination time is 3 to 5 hours.
In some embodiments of the invention, in step S1, the aqueous solution further comprises a solution containing A 1 Raw material I; or/and, in step S2, the mixture further comprises a component A 2 Raw material II of (C).
In some preferred embodiments of the invention, the feedstock i comprises at least one of ammonium perrhenate, aluminum salt or zirconium salt; the raw material II comprises at least one of ammonium perrhenate, zirconium oxide, tungsten oxide, aluminum oxide or lithium tungstate.
In some preferred embodiments of the invention, the feedstock i comprises at least one of an aluminum salt or a zirconium salt; the raw material II comprises ammonium perrhenate and further comprises at least one of zirconium oxide, tungsten oxide, aluminum oxide or lithium tungstate. Preferably, the aluminum salt and zirconium salt are both soluble salts.
In the step S1, the aqueous solution includes aluminum salt or/and zirconium salt, and Al or/and Zr is doped in lithium cobaltate as doping element, where the Al or/and Zr element may replace Co site to stabilize crystalline phase structure. The doping of Al element is preferable because it is easy and inexpensive to prepare. Because the Re element has larger atomic radius, is easier to concentrate on the surface of the hollow lithium cobalt oxide matrix, forms solid solution after the W element is coated, improves the overall ionic conductivity of the material, and has the effects of improving the polarization of the battery and reducing the internal resistance.
In some preferred embodiments of the present invention, the aluminum salt comprises at least one of aluminum sulfate, aluminum nitrate, aluminum carbonate, or aluminum chloride.
In some preferred embodiments of the present invention, the zirconium salt comprises at least one of zirconium sulfate, zirconium nitrate, or zirconium chloride.
In some embodiments of the invention, in step S2, the precursor is mixed with a lithium salt, a raw material ii containing a, to obtain the mixture, and calcined, to obtain the hollow spherical lithium cobalt oxide material. Preferably, the raw material II containing A comprises ammonium perrhenate and further comprises at least one of zirconium oxide, tungsten oxide, aluminum oxide or lithium tungstate.
In some embodiments of the invention, in step S1, a surfactant is further included in the aqueous solution.
In some preferred embodiments of the invention, the surfactant comprises ethanol.
Through the embodiment, the ethanol is added into the aqueous solution to reduce the polarity of the solution, thereby being beneficial to the diffusion of ions and increasing the permeability of metal ions on the carbon sphere. Ethanol, also known as alcohol.
In some more preferred embodiments of the invention, the volume ratio of the ethanol to the water in the aqueous solution is 1:2 to 3:2, preferably (1.5-2): 1.
Through the embodiment, compared with the volume ratio of the ethanol to the water exceeding 3:2, the volume ratio of the ethanol to the water being 1:2-3:2 is not easy to reduce the solubility of the solute in the solvent, and is more beneficial to the concentration and diffusion of the metal ions.
In some embodiments of the present invention, in step S1, an aqueous solution containing template carbon spheres and cobalt salt is taken, a precipitant is added, and after standing, the precipitate is obtained by filtration, and the precursor in the form of a hollow sphere is obtained by calcination.
In some embodiments of the invention, in step S2, the lithium salt comprises lithium carbonate.
In some embodiments of the invention, in step S2, the calcining conditions include heat preservation at 600-900 ℃ for 2-4 hours and then heat preservation at 900-1200 ℃ for 4-6 hours.
In some preferred embodiments of the present invention, in step S2, the calcination conditions include heat preservation at 1100 ℃ for 5 hours after heat preservation at 750 ℃ for 3 hours.
In some preferred embodiments of the present invention, in step S2, the calcination is performed under conditions of 2-6deg.C/min up to 600-900deg.C for 2-4 hours, and then 2-6deg.C/min up to 900-1200deg.C for 4-6 hours.
In some embodiments of the invention, the method of making further comprises the preparation of a template carbon sphere comprising the operations of: and taking monosaccharide, and carrying out hydrothermal reaction to obtain the template carbon sphere.
In some preferred embodiments of the invention, the reaction temperature of the hydrothermal reaction is 160-200 ℃.
In some preferred embodiments of the invention, the hydrothermal reaction has a reaction time of 4 to 8 hours.
In some preferred embodiments of the invention, preparing the template carbon sphere comprises the following operations: and heating and filtering the aqueous solution containing the monosaccharide to obtain the template carbon sphere.
In some more preferred embodiments of the invention, the monosaccharide includes glucose.
In some more preferred embodiments of the invention, the heating temperature is 170-190 ℃.
In some more preferred embodiments of the invention, the heating time is from 5 to 7 hours.
In some more preferred embodiments of the invention, the template carbon spheres are obtained by heating, filtering, washing and drying. Preferably, the washing is performed with water.
In a third aspect of the present invention, a positive electrode material is provided, the positive electrode material comprising the above lithium cobaltate material.
In a fourth aspect of the present invention, a secondary battery is provided, the secondary battery comprising a positive electrode, wherein the raw materials for preparing the positive electrode comprise the positive electrode material.
In some embodiments of the invention, the secondary battery comprises at least one of a lithium ion battery or a sodium ion battery.
In a fifth aspect of the present invention, the use of the above-described lithium cobaltate material in the preparation of electrical devices is presented.
The beneficial effects of the invention include:
according to the invention, the stability of the material is controlled in structural morphology, so that the stability of the lithium cobalt oxide material is improved, and the hollow spherical lithium cobalt oxide material is used as a positive electrode material in a secondary battery, so that the cycle stability of the battery can be improved. The lithium cobaltate material is suitable for high-voltage application environments. Doping of doping element A (such as Zr and Al) can be used for stabilizing the crystal phase structure of lithium cobaltate, preventing structural collapse caused by cobalt dissolution of lithium cobaltate in a high-release state under high voltage, and battery attenuation and water jump. In addition, the doping element A (such as W) can also be used as a constituent element of a coating substance, and the coating substance is used for coating the outer surface of the lithium cobalt oxide matrix so as to reduce side reactions of the lithium cobalt oxide and electrolyte and protect the positive electrode material. When the doped element A contains Re, a solid solution can be formed after the W element is coated, so that the overall ion conductivity of the material is improved, and the effects of improving the polarization of a battery and reducing the internal resistance are achieved.
According to the invention, the hollow-morphology lithium cobalt oxide material is synthesized by adopting a template method, so that the volume deformation of the material in the process of buffering circulation is facilitated, and the obtained material has a stable structure, so that the circulation stability of an applied battery is improved.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is a graph showing the microstructure test results of hollow sphere-shaped lithium cobaltate material in example 1 of the present invention;
FIG. 2 is a graph showing the comparison of the buckling data at 45℃for the hollow sphere-shaped lithium cobaltate materials of example 1 and comparative example 1 according to the present invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
The experimental procedures, which are not specific to the particular conditions noted in the examples below, are generally performed under conditions conventional in the art or according to manufacturer's recommendations; the raw materials, reagents and the like used, unless otherwise specified, are those commercially available from conventional markets and the like.
Example 1
The embodiment discloses a hollow spherical lithium cobaltate material, which comprises the following preparation processes:
and (I) synthesizing a carbon nanosphere sacrificial template, which comprises the following steps:
dissolving a certain amount of glucose in water, uniformly stirring to obtain an aqueous solution with the glucose concentration of 0.12g/mL, performing hydrothermal reaction at the heating temperature of 180 ℃ for 6 hours, repeatedly cleaning and filtering with deionized water after the reaction is finished to obtain a product (a nano carbon sphere template), and drying for later use.
(II) preparing a hollow spherical nano lithium cobaltate material, which comprises the following steps:
dispersing the nano carbon sphere template prepared in the step (I) in deionized water (the dosage ratio of the carbon sphere to the deionized water is 1g:100 mL), adding cobalt sulfate and aluminum sulfate (aluminum carbonate can be adopted), adding sodium hydroxide (sodium carbonate can be adopted) as a precipitator, adding ethanol as a surfactant to increase the permeability of metal ions on the carbon sphere (the volume ratio of the ethanol to the deionized water is 1.5:2, wherein the volume ratio is (1.5-2): 1). And (3) standing, filtering the precipitate, and calcining at a high temperature of 500 ℃ (calcining time is 3-5 h), and removing the carbon sphere template to obtain the aluminum-doped spherical hollow cobaltosic oxide precursor. Wherein the ratio of the amounts of carbon spheres, cobalt sulfate and aluminum sulfate is 1g to 3mol to 0.75mol, and the ratio of the sum of the molar amounts of cobalt sulfate and aluminum sulfate to the molar amount of sodium hydroxide is about 1:3.
mixing the cobaltosic oxide precursor with lithium carbonate (wherein the molar ratio of the lithium carbonate to the cobaltosic oxide contained in the cobaltosic oxide precursor is 3:2), adding ammonium perrhenate, zirconium oxide and tungsten oxide, and calcining at high temperature (calcining conditions are changed from 4 ℃/min to 750 ℃ for 3 hours, and then from 4 ℃/min to 1100 ℃ for 5 hours), thereby synthesizing the hollow sphere-shaped nano lithium cobaltate material. Wherein, the molar ratio of ammonium perrhenate, zirconium oxide, tungsten oxide and cobaltosic oxide contained in the cobaltosic oxide precursor is 0.2:0.025:0.2:2. The prepared hollow sphere-shaped nano lithium cobaltate material comprises aluminum-doped lithium cobaltate matrix particles and coating substances (comprising tungsten oxide) coated on the outer surfaces of the lithium cobaltate matrix particles, wherein the coating forms of the coating substances comprise island-shaped coatings.
The obtained nano lithium cobaltate material is measured:
particle size 500-800nm; the wall thickness is 50-100nm;
elemental content (mass fraction): li:7% ± 2%, co:60% ± 4%, al:7500 ppm.+ -. 1000ppm, zr:250 ppm.+ -.100 ppm, W:2000 ppm.+ -.500 ppm, re:2000ppm to 3000ppm;
the total content of Al, zr and W is 8000-10000ppm;
tap density: 2.1-2.6g/cm 3 Compaction density: 4.0-4.2g/cm 3 ；
The embodiment also provides a positive electrode material, which comprises the hollow spherical lithium cobalt oxide material prepared by the embodiment.
The embodiment also provides a lithium ion battery, which comprises a positive electrode, wherein the preparation raw materials of the positive electrode comprise the positive electrode material of the embodiment.
Example 2
This example discloses a hollow spherical lithium cobaltate material which differs from example 1 only in that: the preparation step (II) is different, and the preparation of the hollow spherical nano lithium cobaltate material in the step (II) of the embodiment comprises the following operations:
dispersing the nano carbon sphere template prepared in the step (I) in deionized water, adding cobalt sulfate, soluble aluminum salt and zirconium salt, adding sodium hydroxide as a precipitator, and adding ethanol as a surfactant to increase the permeability of metal ions on the carbon sphere (wherein the volume ratio of the ethanol to the deionized water is 1:2). And (3) standing, filtering the precipitate, and calcining at a high temperature of 500 ℃ (calcining time is 3-5 h) to remove the carbon sphere template, thereby obtaining the aluminum-doped spherical hollow cobaltosic oxide precursor. Wherein the ratio of the carbon sphere to the cobalt sulfate can be 1g (0.5-3.5) mol.
Mixing the cobaltosic oxide precursor with lithium carbonate (wherein the molar ratio of the lithium carbonate to the cobaltosic oxide contained in the cobaltosic oxide precursor is 3:2), adding ammonium perrhenate and tungsten oxide, and performing high-temperature calcination (the calcination condition is specifically that the calcination is carried out at a temperature of 4 ℃/min to 750 ℃ for 3 hours, and then the calcination is carried out at a temperature of 4 ℃/min to 1100 ℃ for 5 hours), so as to obtain the hollow sphere-shaped nano lithium cobaltate material.
Wherein, the aluminum salt in the embodiment can be selected from one or more of aluminum sulfate, aluminum nitrate, aluminum carbonate or aluminum chloride, and the zirconium salt can be selected from one or more of zirconium sulfate, zirconium nitrate or zirconium chloride; the specific addition amount of ammonium perrhenate, aluminum salt, zirconium salt and tungsten oxide can be selected according to the actual production requirements.
The embodiment also provides a positive electrode material, which comprises the hollow spherical lithium cobalt oxide material prepared by the embodiment.
The embodiment also provides a lithium ion battery, which comprises a positive electrode, wherein the preparation raw materials of the positive electrode comprise the positive electrode material of the embodiment.
Example 3
This example discloses a hollow spherical lithium cobaltate material which differs from example 1 only in that: the preparation step (II) is different, and the preparation of the hollow spherical nano lithium cobaltate material in the step (II) of the embodiment comprises the following operations:
dispersing the nano carbon sphere template prepared in the step (I) in deionized water (the dosage ratio of the carbon sphere to the deionized water is 1g:100 mL), adding cobalt sulfate and soluble zirconium salt, adding sodium hydroxide as a precipitator, and adding ethanol as a surfactant to increase the permeability of metal ions on the carbon sphere (wherein the volume ratio of the ethanol to the deionized water is 1:2). And (3) standing, filtering the precipitate, and calcining at a high temperature of 500 ℃ (calcining time is 3-5 h), and removing the carbon sphere template to obtain the aluminum-doped spherical hollow cobaltosic oxide precursor. Wherein the ratio of the carbon sphere to the cobalt sulfate can be 1g (0.5-3.5) mol.
Mixing the cobaltosic oxide precursor with lithium carbonate (wherein the molar ratio of the lithium carbonate to the cobaltosic oxide contained in the cobaltosic oxide precursor is 3:2), adding ammonium perrhenate, aluminum oxide and tungsten oxide, and calcining at high temperature (calcining conditions are changed from 4 ℃/min to 750 ℃ for 3 hours, and then from 4 ℃/min to 1100 ℃ for 5 hours), thus obtaining the hollow sphere-shaped nano lithium cobaltate material.
The zirconium salt in the embodiment can be one or more selected from zirconium sulfate, zirconium nitrate or zirconium chloride; the specific addition amount of ammonium perrhenate, zirconium salt, aluminum oxide and tungsten oxide can be selected according to the actual production requirements.
The embodiment also provides a positive electrode material, which comprises the hollow spherical lithium cobalt oxide material prepared by the embodiment.
The embodiment also provides a lithium ion battery, which comprises a positive electrode, wherein the preparation raw materials of the positive electrode comprise the positive electrode material of the embodiment.
Example 4
This example discloses a hollow spherical lithium cobaltate material which differs from example 1 only in that: the preparation step (II) is different, and the preparation of the hollow spherical nano lithium cobaltate material in the step (II) of the embodiment comprises the following operations:
dispersing the nano carbon sphere template prepared in the step (I) in deionized water (the dosage ratio of the carbon sphere to the deionized water is 1g:100 mL), adding cobalt sulfate, adding sodium hydroxide as a precipitator, adding alcohol as a surfactant to increase the permeability of metal ions on the carbon sphere (wherein the volume ratio of the ethanol to the deionized water is 1:2). And (3) standing, filtering the precipitate, and calcining at a high temperature of 500 ℃ (calcining time is 3-5 h), and removing the carbon sphere template to obtain the aluminum-doped spherical hollow cobaltosic oxide precursor. Wherein the ratio of the carbon sphere to the cobalt sulfate can be 1g (0.5-3.5) mol.
Mixing the cobaltosic oxide precursor with lithium carbonate (wherein the molar ratio of the lithium carbonate to the cobaltosic oxide contained in the cobaltosic oxide precursor is 3:2), adding ammonium perrhenate, zirconia, alumina and tungsten oxide for high-temperature calcination (calcining conditions are specifically that the temperature is raised to 750 ℃ at 4 ℃/min for 3 hours, and then the temperature is raised to 1100 ℃ at 4 ℃/min for 5 hours), so as to obtain the hollow sphere-shaped nano lithium cobaltate material.
The specific addition amounts of ammonium perrhenate, zirconia, alumina and tungsten oxide in this embodiment may be selected according to actual production requirements.
The embodiment also provides a positive electrode material, which comprises the hollow spherical lithium cobalt oxide material prepared by the embodiment.
The embodiment also provides a lithium ion battery, which comprises a positive electrode, wherein the preparation raw materials of the positive electrode comprise the positive electrode material of the embodiment.
Example 5
This example discloses a hollow spherical lithium cobaltate material which differs from example 1 only in that: in this example, lithium tungstate was used in the preparation step (ii) in place of tungsten oxide in example 1.
Comparative example 1
The comparative example discloses a hollow spherical lithium cobalt oxide material with a chemical formula of LiCoO 2 It differs from example 1 only in that: the hollow spherical lithium cobalt oxide material in this comparative example was not doped with Al, zr, and W, and the hollow spherical lithium cobalt oxide material was prepared in this comparative example, specifically comprising the steps of:
and (I) synthesizing a carbon nanosphere sacrificial template: as in example 1;
(II) preparing a hollow spherical nano lithium cobaltate material, which comprises the following steps:
dispersing the nano carbon sphere template prepared in the step (I) in deionized water (the dosage ratio of the carbon sphere to the deionized water is 1g:100 mL), adding cobalt sulfate, adding sodium hydroxide as a precipitator, and adding ethanol as a surfactant to increase the permeability of metal ions on the carbon sphere (wherein the volume ratio of the ethanol to the deionized water is 1:2). And (3) standing, filtering the precipitate, and calcining at a high temperature of 500 ℃ (calcining time is 3-5 h), and removing the carbon sphere template to obtain the spherical hollow cobaltosic oxide precursor. Wherein the ratio of the dosage of the carbon sphere to the dosage of the cobalt sulfate is 1g to 3mol.
Mixing the cobaltosic oxide precursor with lithium carbonate (wherein the molar ratio of the lithium carbonate to the cobaltosic oxide contained in the cobaltosic oxide precursor is 3:2), and calcining at high temperature (calcining conditions are specifically that the temperature is raised to 750 ℃ at 4 ℃/min for 3 hours, and then raised to 1100 ℃ at 4 ℃/min for 5 hours), so as to obtain the hollow sphere-shaped nano lithium cobaltate material.
Test examples
The lithium cobaltate materials obtained in the examples and the comparative examples are subjected to performance test in the test example, and specifically include:
1. the microstructure of the lithium cobaltate material prepared in example 1 was tested, and the test results are shown in fig. 1.
2. The lithium cobaltate material prepared in example 1 was tested for electrochemical performance (performance test was performed on a button cell, wherein the positive electrode material of the button cell was the lithium cobaltate material prepared in example 1):
1) Gram Capacity test, measured gram Capacity: 190-194mAh/g; the specific testing steps comprise: 0.1C to 4.55V cut-off current 0.02C,0.1C to 3V, charge-discharge reference gram capacity 195mAh/g.
2) The first effect is measured to be 94% +/-2%, and the first effect calculating method comprises the following steps: first discharge capacity/first charge capacity;
3) And (3) a discharge platform: 3.8-3.95V, the specific steps include: the plateau discharges energy Wh divided by capacity Ah with the 2-3 week curve.
3. The comparison of the high-temperature cyclic buckling data at 45 ℃ specifically comprises the following steps: the snap capacitance 3C was charged to 4.55V, the off current was 200mA, and the discharge was 3C discharged to 3V, calculated as a reference capacitance of 195mAh/g.
The 45 ℃ high temperature cycle buckling data of the lithium cobaltate materials in example 1 and comparative example 1 were measured, as shown in fig. 2, wherein the holow LCO represents the test curve of example 1 and the normal LCO represents the test curve of comparative example 1.
In conclusion, the monocrystalline hollow nano microsphere with stable structure is synthesized by designing the structure of the material, and meanwhile, transition metal is doped in a sintering process to stabilize the microstructure, so that the structural stability of the lithium cobalt oxide positive electrode material in the battery operation is improved.
According to the invention, the hollow-morphology lithium cobalt oxide material is synthesized by using a template method, so that the volume deformation of the material in the buffer circulation process is facilitated, and more reactive sites are provided. The cobalt oxide precursor is synthesized by doping Al and Zr elements to replace Co positions for stabilizing the unit cell structure, W, re elements are introduced in the subsequent calcination process, the residual lithium content on the surface of the material is reduced, the workability of the material is improved, the manufacturability of the material is enhanced, and Re and W elements are coated to form a solid solution, so that the overall ion conductivity of the material is improved, and the effects of improving the polarization of a battery and reducing the internal resistance are achieved.
Meanwhile, the wall thickness of the lithium cobaltate material can be preferably controlled and adjusted according to the contact time of metal ions and a carbon template in an adsorption stage and/or the compounding proportion of deionized water and ethanol in the solution (wherein the main effect of adding ethanol is to reduce the polarity of the solution so that ions in the solution better permeate into the surface layer of a carbon sphere), so that the lithium cobaltate material which is more preferable and more in line with the actual specific production needs is obtained.
The "room temperature" and "normal temperature" herein are about 25 ℃ unless otherwise specified; the meaning of "about" with respect to a numerical value herein is an error of + -2%.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A lithium cobaltate material, characterized in that the lithium cobaltate material is hollow sphere-shaped, and the lithium cobaltate material contains a doping element a.
2. The lithium cobalt oxide material of claim 1, wherein the element a comprises at least one of Re, al, zr, W, ga, hf, mg, sn, zn, ni, mn, V, mo, nb, cu, fe, in or Cr.
3. The lithium cobalt oxide material according to claim 2, wherein the lithium cobalt oxide material comprises lithium cobalt oxide base particles and a coating substance coated on the outer surfaces of the lithium cobalt oxide base particles, the coating substance comprising the element a.
4. The lithium cobaltate material of claim 2,wherein the element A includes the element A 1 And element A 2 The lithium cobaltate material comprises lithium cobaltate matrix particles and a coating substance coated on the outer surface of the lithium cobaltate matrix particles, wherein the lithium cobaltate matrix particles comprise element A 1 The coating material comprises the element A 2 ；
Preferably, the element A 1 Comprises at least one of Al, zr, W, ga, hf, mg, sn, zn, ni, mn, V, mo, nb, cu, fe, in or Cr; the element A 2 Including at least one of Re, al, zr, W, ga, hf, mg, sn, zn, ni, mn, V, mo, nb, cu, fe, in or Cr.
5. The lithium cobaltate material according to claim 2, wherein the mass fraction of Re element in the lithium cobaltate material is 1000ppm to 4000ppm;
preferably, the mass fraction of Al element is 5500-11000ppm;
preferably, the mass fraction of Zr element is 50-450ppm;
preferably, the mass fraction of the W element is 1000-3000ppm.
6. The lithium cobalt oxide material according to claim 1, wherein the particle size of the lithium cobalt oxide material is 100-1500nm;
preferably, the wall thickness of the lithium cobaltate material is 10-300nm.
7. The lithium cobalt oxide material according to claim 1, wherein the lithium cobalt oxide material has a tap density of 1.5-3.0g/cm 3 ；
Preferably, the lithium cobaltate material has a compacted density of 3.5-4.7g/cm 3 。
8. A method of preparing a lithium cobaltate material according to any one of claims 1-7, wherein the method of preparing comprises the steps of:
s1, taking an aqueous solution containing template carbon spheres and cobalt salt, adding a precipitator, and calcining to obtain a hollow spherical precursor;
s2, taking a mixture containing lithium salt and the precursor, and calcining to obtain a hollow spherical lithium cobalt oxide material;
in the step S1, the aqueous solution also comprises a raw material I containing A; or/and, in the step S2, the mixture also comprises a raw material II containing A;
preferably, the raw material I comprises at least one of aluminum salt or zirconium salt; the raw material II comprises ammonium perrhenate and further comprises at least one of zirconium oxide, tungsten oxide, aluminum oxide or lithium tungstate.
9. A positive electrode material comprising the lithium cobalt oxide material according to any one of claims 1 to 7 or the lithium cobalt oxide material produced by the method according to claim 8.
10. A secondary battery, characterized in that the secondary battery comprises a positive electrode, the raw material for producing the positive electrode comprising the positive electrode material according to claim 9.
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