CN118183863A - Lithium cobalt oxide positive electrode material and preparation method and application thereof - Google Patents
Lithium cobalt oxide positive electrode material and preparation method and application thereof Download PDFInfo
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- CN118183863A CN118183863A CN202211591005.7A CN202211591005A CN118183863A CN 118183863 A CN118183863 A CN 118183863A CN 202211591005 A CN202211591005 A CN 202211591005A CN 118183863 A CN118183863 A CN 118183863A
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 23
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 title claims abstract description 22
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 238000001354 calcination Methods 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- 239000012298 atmosphere Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000012043 crude product Substances 0.000 claims abstract description 13
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
- 239000010405 anode material Substances 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 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 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229940071264 lithium citrate Drugs 0.000 claims description 2
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000047 product Substances 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 238000000227 grinding Methods 0.000 description 21
- 239000011888 foil Substances 0.000 description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 239000004743 Polypropylene Substances 0.000 description 14
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 12
- 239000002033 PVDF binder Substances 0.000 description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 11
- 239000003273 ketjen black Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 229910013870 LiPF 6 Inorganic materials 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000011267 electrode slurry Substances 0.000 description 7
- 239000012467 final product Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000004417 polycarbonate Substances 0.000 description 7
- 229920000515 polycarbonate Polymers 0.000 description 7
- -1 polypropylene Polymers 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 230000002441 reversible effect Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 229920002994 synthetic fiber Polymers 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 241001025261 Neoraja caerulea Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical group [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The application discloses a lithium cobaltate anode material, a preparation method and application thereof. The lithium cobalt oxide positive electrode material comprises the following steps: a) Mixing lithium salt, a cobalt source and an M metal source, calcining the mixture I in an oxygen-containing atmosphere, and crushing the mixture to obtain a crude product a; b) Calcining the crude product a in an oxygen-containing atmosphere to obtain a lithium cobaltate anode material by crushing; the metal element M of the M metal source is selected from at least one of Al, mg, ti, zr, la, mn, ni, sb, W, nb. The lithium cobaltate product is used as the positive electrode of a lithium ion battery, can be cycled for 500 circles at a 5C multiplying power under the condition of no less than 4.6V charging cut-off voltage, has the capacity retention rate of nearly 70 percent and has the ultra-high initial capacity. The product is an ultra-fast high-voltage positive electrode material with potential application.
Description
Technical Field
The application relates to a lithium cobaltate positive electrode material, a preparation method and application thereof, and belongs to the technical field of lithium ion batteries.
Background
As the first choice positive electrode material of the 3C product lithium ion battery, the lithium cobaltate has the advantages of mature and simple preparation process, high volume energy density and the like. Commercial lithium cobaltate with the current charge cut-off voltage of 4.5V can only provide 180-190mAh g -1 capacity which is far smaller than 274mAh g -1 theoretical specific capacity. The specific discharge capacity can be further improved by further improving the charge cutoff voltage to be more than 4.6V, but the problems of serious irreversible phase change, interface side reaction, cobalt dissolution, lattice oxygen loss and the like can be caused at the same time, and particularly, under the condition of ultra-fast charge high current (> 5C), the accelerated deterioration of the battery cycle stability is caused, and even the safety problems of thermal runaway and the like are caused. Researchers have mainly solved or improved the above problems by two strategies, bulk doping, surface coating, etc.
The method improves the electrochemical stability of the 4.6V-lithium cobalt oxide based composite material to a certain extent, but the used process has the defects that the capacity is limited by the doping amount at high multiplying power and the circulation is unstable at high multiplying power. Therefore, there is an urgent need to develop a method for producing high-performance ultra-fast charge 4.6V-lithium cobaltate in a simple process, at low cost, and rapidly in a large scale so as to obtain a lithium ion battery having a high energy density and capable of stabilizing an ultra-fast charge cycle.
Disclosure of Invention
In order to improve the performance of the lithium cobalt oxide positive electrode material, the M metal source is introduced to dope the lithium cobalt oxide, and the scalable production method provides a potential solution for the challenges of high-voltage instability and poor ultra-fast charge-length cycle of the high-end 4.6V-lithium cobalt oxide-based ultra-fast charge material in a lithium ion battery.
According to one aspect of the present application, there is provided a method for preparing a lithium cobalt oxide positive electrode material, comprising the steps of:
A) Mixing lithium salt, a cobalt source and an M metal source, calcining the mixture I in an oxygen-containing atmosphere, and crushing the mixture to obtain a crude product a;
B) Calcining the crude product a in an oxygen-containing atmosphere to obtain a lithium cobaltate anode material by crushing;
The metal element M of the M metal source is at least one selected from Al, mg, ti, zr, la, mn, ni, sb, W and Nb.
Optionally, the molar ratio of the cobalt source to the lithium salt and the M metal source is 1:1-1.1:0.0005-0.05, calculated by the mole number of the metal elements.
Optionally, the molar ratio of the cobalt source to the lithium salt and the M metal source is any ratio or range of values between the two ratios of 1:1:0.0005, 1:1:0.005, 1:1:0.01, 1:1.05:0.03, 1:1.1:0.05.
Optionally, the lithium salt is at least one selected from lithium hydroxide, lithium nitrate, lithium carbonate, lithium oxalate, lithium acetate, lithium oxide, and lithium citrate.
Optionally, the cobalt source is selected from at least one of cobaltosic oxide, cobalt carbonate, cobalt hydroxide, cobalt acetate, cobalt oxalate, cobalt nitrate, cobalt sulfate and cobalt chloride.
Optionally, the M metal source is selected from at least one of an oxide, hydroxide, sulfate, nitrate, carbonate of a metal element M.
Optionally, the conditions of calcination I are: heating to 800-1100 ℃ at a heating rate of 0.2-10 ℃/min, and calcining for 6-20 h.
Optionally, the temperature rise rate of the calcination I is any value or a range of values between any two values of 0.2 ℃/min, 1 ℃/min, 3 ℃/min, 5 ℃/min, 10 ℃/min.
Optionally, the temperature of the calcination I is any value or a range of values between two values in 800 ℃, 900 ℃, 1000 ℃, 1100 ℃.
Optionally, the time of calcining I is any value or range of values between 6h, 12h, 16h, 20 h.
Optionally, the temperature of the calcination II is 700-1100 ℃, and the time of the calcination II is 6-12 h.
Optionally, the temperature of the calcination II is any value or a range of values between two values in 700 ℃, 900 ℃, 1000 ℃, 1100 ℃.
Optionally, the time of calcination II is any value or a range of values between two values of 6h, 12h, 16h, 20 h.
According to still another aspect of the present application, there is provided a lithium cobalt oxide cathode material obtained according to the above-mentioned preparation method, wherein the M metal source accounts for 0.01% to 0.5% of the molar mass of lithium cobalt oxide;
the particle size of the lithium cobaltate is 1-10 mu m.
Optionally, the highest chargeable voltage of the lithium cobaltate positive electrode material is 4.6V-5V.
Optionally, the ultra-fast charge rate of the lithium cobaltate positive electrode material is 5-20 ℃.
Optionally, the capacity of the lithium cobaltate positive electrode material after 500 circles is greater than 70%.
According to a further aspect of the present application there is provided the use of a lithium cobalt oxide cathode material as described above in a battery cathode.
As a specific embodiment of the present application, a method for preparing a positive electrode comprises: coating slurry of an ultra-fast charging 4.6V-lithium cobalt oxide positive electrode material, a conductive agent and a binder on an aluminum foil substrate to obtain the positive electrode;
the conductive agent is ketjen black;
the binder is polyvinylidene fluoride (PVDF);
The mass ratio of the ultra-fast charge 4.6V-lithium cobalt oxide positive electrode material, the conductive agent and the binder in the slurry containing the ultra-fast charge 4.6V-lithium cobalt oxide positive electrode material, the conductive agent and the binder is 8:1:1.
The ultra-fast charging 4.6V-lithium cobaltate anode material and the Ketjen black and PVDF material are premixed to prepare slurry before the smear, the mixing mass ratio is 8:1:1, the thickness of the smear is 200-300 mu m, and the substrate is carbon-coated aluminum foil.
Alternatively, the positive plate has a diameter of 12mm and a monolithic mass of 3-4mg.
A battery adopting the positive electrode of the battery comprises a positive electrode, a negative electrode and an electrolyte, wherein the negative electrode is a lithium foil, the electrolyte is LB-111, and the electrolyte is purchased from Suzhou Duoduo chemical reagent Co.
The application has the beneficial effects that:
according to the preparation method provided by the application, the M metal source doping is introduced to simply and rapidly prepare the lithium cobalt oxide anode material, so that the multiplying power specific capacity of the 4.6V-lithium cobalt oxide material under high current density is improved, the dissolution of cobalt under high voltage is effectively inhibited, the side reaction with electrolyte is carried out, and the ultra-fast charge and circulation stability of the battery under high voltage is improved.
Drawings
FIG. 1 is an XRD structure diagram of an ultra-fast charge 4.6V-lithium cobalt oxide positive electrode material obtained in example 1 of the present application;
FIG. 2 is a scanning electron microscope topography of the lithium cobaltate cathode material obtained in example 1 of the present application at 5 μm;
FIG. 3 is a graph showing the performance test of lithium cobaltate cathode materials prepared in example 1 and comparative example 1 according to different multiplying powers in lithium ion batteries;
fig. 4 is a 5C cycle life curve of a lithium ion battery employing the lithium cobaltate cathode material prepared in example 1 and comparative example 1 according to the present application.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
SEM analysis was performed using a Quanta-200F scanning electron microscope.
And (3) performing electrical performance analysis in a 3-4.6V interval by using a CT2001A blue-ray battery test system.
Example 1
Weighing 0.05mol of cobaltosic oxide, 0.075mol of lithium carbonate, and 0.1% of LiCoO 2, which are respectively 0.15mol of magnesium oxide, aluminum oxide and niobium pentoxide, uniformly mixing and grinding; under the air atmosphere, the calcining temperature is 1000 ℃, and the synthesis is carried out for 10 hours; crushing agglomerates in the synthetic material to obtain a LiCoO 2 crude product; then, the mixture was synthesized at 900℃for 10 hours in an air atmosphere to break up the agglomerates in the synthesized material, and the final product was designated as sample 1.
Grinding and mixing the prepared sample 1, ketjen black and PVDF uniformly according to the mass ratio of 8:1:1, dripping a proper amount of NMP (1.5 mL) to prepare electrode slurry, then coating and grinding the slurry on aluminum foil uniformly, placing the aluminum foil in a vacuum drying oven at 120 ℃ for full drying, compacting by a pair roller, and cutting into a wafer electrode with the diameter of 12 mm. The prepared positive electrode sheet was used as a positive electrode, a lithium metal sheet was used as a negative electrode, a polycarbonate solution of 1mol/L LiPF 6 was used as an electrolyte, a PP (polypropylene) separator was used as a separator, and a CR2016 type button cell was mounted in a glove box (moisture and oxygen content were both less than 0.01 ppm) filled with dry high-purity argon gas. The button cell is placed on a blue cell test system, the charge and discharge performance of the button cell at room temperature is tested, when the current density is 5C (1370 mA/g) and the charge and discharge voltage range is 3.6V (vs. Li+/Li), the first reversible discharge capacity is 198mAh/g, and after 500 times of circulation, the capacity is 140mAh/g.
Example 2
Other operations are the same as in example 1, except that the M metal source is lanthanum oxide, magnesium oxide, aluminum oxide in a molar amount of 0.1% based on 0.15mol LiCoO 2: 0.1%:0.3 percent, and evenly mixing and grinding; under the air atmosphere, the calcining temperature is 1050 ℃, and the synthesis is carried out for 8 hours; crushing agglomerates in the synthetic material to obtain a LiCoO 2 crude product; then, the mixture was synthesized at 950℃for 12 hours in an air atmosphere, and the agglomerate in the synthesized material was broken up to give a final product designated as sample 2.
Grinding and mixing the prepared sample 2, ketjen black and PVDF uniformly according to the mass ratio of 8:1:1, dripping a proper amount of NMP (1.5 mL) to prepare electrode slurry, then coating and grinding the slurry on aluminum foil uniformly, placing the aluminum foil in a vacuum drying oven at 120 ℃ for full drying, compacting by a pair roller, and cutting into a wafer electrode with the diameter of 12 mm. The prepared positive electrode sheet was used as a positive electrode, a lithium metal sheet was used as a negative electrode, a polycarbonate solution of 1mol/L LiPF 6 was used as an electrolyte, a PP (polypropylene) separator was used as a separator, and a CR2016 type button cell was mounted in a glove box (moisture and oxygen content were both less than 0.01 ppm) filled with dry high-purity argon gas. The button cell is placed on a blue cell test system, the charge and discharge performance of the button cell at room temperature is tested, and when the current density is 5C (1370 mA/g) and the charge and discharge voltage range is 3.6V (vs. Li+/Li), the first reversible discharge capacity is 190mAh/g, and after 500 times of circulation, the capacity is 135mAh/g.
Example 3
Other operations are the same as in example 1, except that the M metal source is antimony oxide, magnesium oxide, and 0.1% of 0.15mol LiCoO 2: 0.1 percent, and evenly mixing and grinding; under the air atmosphere, the calcining temperature is 1050 ℃, and the synthesis is carried out for 8 hours; crushing agglomerates in the synthetic material to obtain a LiCoO 2 crude product; then, the mixture was synthesized at 950℃for 12 hours in an air atmosphere, and the agglomerate in the synthesized material was broken up to give a final product, which was designated as sample 3.
Grinding and mixing the prepared sample 3, ketjen black and PVDF uniformly according to the mass ratio of 8:1:1, dripping a proper amount of NMP (1.5 mL) to prepare electrode slurry, then coating and grinding the slurry on aluminum foil uniformly, placing the aluminum foil in a vacuum drying oven at 120 ℃ for full drying, compacting by a pair roller, and cutting into a wafer electrode with the diameter of 12 mm. The prepared positive electrode sheet was used as a positive electrode, a lithium metal sheet was used as a negative electrode, a polycarbonate solution of 1mol/L LiPF 6 was used as an electrolyte, a PP (polypropylene) separator was used as a separator, and a CR2016 type button cell was mounted in a glove box (moisture and oxygen content were both less than 0.01 ppm) filled with dry high-purity argon gas. The button cell is placed on a blue cell testing system, the charging and discharging performance of the button cell at room temperature is tested, when the current density is 5C (1370 mA/g) and the charging and discharging voltage range is 3.6V (vs. Li+/Li), the first reversible discharge capacity is 183mAh/g, and after 500 times of circulation, the capacity is 139mAh/g.
Example 4
Other operations are the same as in example 1, except that the M metal source is titanium oxide, magnesium oxide, aluminum oxide in a molar amount of 0.1% of 0.15mol LiCoO 2: 0.1%:0.1 percent, and evenly mixing and grinding; under the air atmosphere, the calcining temperature is 1050 ℃, and the synthesis is carried out for 10 hours; crushing agglomerates in the synthetic material to obtain a LiCoO2 crude product; then, the mixture was synthesized at 1000℃for 10 hours under an air atmosphere, and the agglomerate in the synthesized material was broken up to give a final product, which was designated as sample 4.
Grinding and mixing the prepared sample 4, ketjen black and PVDF uniformly according to the mass ratio of 8:1:1, dripping a proper amount of NMP (1.5 mL) to prepare electrode slurry, then coating and grinding the slurry on aluminum foil uniformly, placing the aluminum foil in a vacuum drying oven at 120 ℃ for full drying, compacting by a pair roller, and cutting into a wafer electrode with the diameter of 12 mm. The prepared positive electrode sheet was used as a positive electrode, a lithium metal sheet was used as a negative electrode, a polycarbonate solution of 1mol/L LiPF 6 was used as an electrolyte, a PP (polypropylene) separator was used as a separator, and a CR2016 type button cell was mounted in a glove box (moisture and oxygen content were both less than 0.01 ppm) filled with dry high-purity argon gas. The button cell is placed on a blue cell test system, the charge and discharge performance of the button cell at room temperature is tested, and when the current density is 5C (1370 mA/g) and the charge and discharge voltage range is 3.6V (vs. Li+/Li), the first reversible discharge capacity is 195mAh/g, and after 500 times of circulation, the capacity is 141mAh/g.
Example 5
Other operations are the same as in example 1, except that the M metal source is titanium oxide, magnesium oxide, aluminum oxide, niobium oxide, zirconium oxide in a molar amount of 0.1% of 0.15mol LiCoO 2: 0.3%:0.1%:0.2%:0.1 percent, and evenly mixing and grinding; under the air atmosphere, the calcining temperature is 1050 ℃, and the synthesis is carried out for 10 hours; crushing agglomerates in the synthetic material to obtain a LiCoO 2 crude product; then, the mixture was synthesized at 1000℃for 10 hours under an air atmosphere, and the agglomerate in the synthesized material was broken up to give a final product, which was designated as sample 5.
Grinding and mixing the prepared sample 5, ketjen black and PVDF uniformly according to the mass ratio of 8:1:1, dripping a proper amount of NMP (1.5 mL) to prepare electrode slurry, then coating and grinding the slurry on aluminum foil uniformly, placing the aluminum foil in a vacuum drying oven at 120 ℃ for full drying, compacting by a pair roller, and cutting into a wafer electrode with the diameter of 12 mm. The prepared positive electrode sheet was used as a positive electrode, a lithium metal sheet was used as a negative electrode, a polycarbonate solution of 1mol/L LiPF 6 was used as an electrolyte, a PP (polypropylene) separator was used as a separator, and a CR2016 type button cell was mounted in a glove box (moisture and oxygen content were both less than 0.01 ppm) filled with dry high-purity argon gas. The button cell is placed on a blue cell test system, the charge and discharge performance of the button cell at room temperature is tested, and when the current density is 5C (1370 mA/g) and the charge and discharge voltage range is 3.6V (vs. Li+/Li), the first reversible discharge capacity is 191mAh/g, and after 500 times of circulation, the capacity is 133mAh/g.
Example 6
Other operations are the same as in example 1, except that the M metal source is titanium oxide, magnesium oxide, aluminum oxide, nickel oxide, manganese oxide in a molar amount of 0.1% of 0.15mol LiCoO 2: 0.3%:0.1%:0.3%:0.1 percent, and evenly mixing and grinding; under the air atmosphere, the calcining temperature is 1050 ℃, and the synthesis is carried out for 10 hours; crushing agglomerates in the synthetic material to obtain a LiCoO 2 crude product; then, the mixture was synthesized at 1000℃for 10 hours under an air atmosphere, and the agglomerate in the synthesized material was broken up to give a final product designated as sample 6.
Grinding and mixing the prepared sample 6, ketjen black and PVDF uniformly according to the mass ratio of 8:1:1, dripping a proper amount of NMP (1.5 mL) to prepare electrode slurry, then coating and grinding the slurry on aluminum foil uniformly, placing the aluminum foil in a vacuum drying oven at 120 ℃ for full drying, compacting by a pair roller, and cutting into a wafer electrode with the diameter of 12 mm. The prepared positive electrode sheet was used as a positive electrode, a lithium metal sheet was used as a negative electrode, a polycarbonate solution of 1mol/L LiPF 6 was used as an electrolyte, a PP (polypropylene) separator was used as a separator, and a CR2016 type button cell was mounted in a glove box (moisture and oxygen content were both less than 0.01 ppm) filled with dry high-purity argon gas. The button cell is placed on a blue cell test system, the charge and discharge performance of the button cell at room temperature is tested, when the current density is 5C (1370 mA/g) and the charge and discharge voltage range is 3.6V (vs. Li+/Li), the first reversible discharge capacity is 194mAh/g, and after 500 times of circulation, the capacity is 136mAh/g.
Comparative example 1
Other operations are the same as those of example 1 except that no doping of M metal source is performed, and the mixing and grinding are uniform; under the air atmosphere, the calcining temperature is 1050 ℃, and the synthesis is carried out for 10 hours; crushing agglomerates in the synthetic material to obtain a LiCoO 2 crude product; then, the mixture was synthesized at a calcination temperature of 1000℃for 10 hours under an air atmosphere, and the agglomerate in the synthesized material was broken up to give a final product designated as sample 7.
Grinding and mixing the prepared sample 7, ketjen black and PVDF uniformly according to the mass ratio of 8:1:1, dripping a proper amount of NMP (1.5 mL) to prepare electrode slurry, then coating and grinding the slurry on aluminum foil uniformly, placing the aluminum foil in a vacuum drying oven at 120 ℃ for full drying, compacting by a pair roller, and cutting into a wafer electrode with the diameter of 12 mm. The prepared positive electrode sheet was used as a positive electrode, a lithium metal sheet was used as a negative electrode, a polycarbonate solution of 1mol/L LiPF 6 was used as an electrolyte, a PP (polypropylene) separator was used as a separator, and a CR2016 type button cell was mounted in a glove box (moisture and oxygen content were both less than 0.01 ppm) filled with dry high-purity argon gas. The button cell is placed on a blue cell testing system, the charging and discharging performance of the button cell at room temperature is tested, when the current density is 5C (1370 mA/g) and the charging and discharging voltage range is 3.6V (vs. Li+/Li), the first reversible discharge capacity is 171mAh/g, and after 500 times of circulation, the capacity is 8mAh/g.
Example 1 structural morphology characterization
Sample 1 was characterized for morphology and a typical SEM image as shown in figure 1, with a typical particle size range of 1-10 μm. Typical XRD patterns are shown in FIG. 2, and correspond in structure to PDF#50-0653.
Example 1 characterization of Performance
And (3) battery assembly: 80mg of sample 1 positive electrode material, 10mg of ketjen black and 10mg of PVDF are weighed, ground and mixed, and slurry preparation is carried out by taking NMP as a solvent. The battery was assembled using a carbon-coated aluminum foil as a substrate, a 300 μm doctor blade as a smear, vacuum-dried at 100deg.C, a cut-off piece (diameter 12 mm) as a positive electrode, and a lithium foil (diameter 14 mm) as a negative electrode, with a commercial high-voltage electrolyte (secret formulation) as LB-372 (Suzhou Duoduo chemical Co., ltd.).
The battery assembled in sample 1 was subjected to an electrical performance test. The multiplying power test conditions are as follows: the voltage interval is 3-4.6V, wherein 1 C=274 mAh/g.
Fig. 3 is a typical lithium ion battery rate capability, a 0.2C first charge-discharge curve, and fig. 4 is a 5C long cycle life curve, corresponding to the assembled battery of sample 1.
As can be seen from fig. 3, the doped sample 1 has significantly improved rate capability compared to the sample 7 of the comparative example.
As can be seen from fig. 4, the long-cycle stability at the 7,5C magnification of the doped sample 1 is significantly enhanced compared to the sample of the comparative example.
The performance of the assembled cells of the other samples was similar to the cell curves shown in fig. 3-4.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (10)
1. The preparation method of the lithium cobalt oxide positive electrode material is characterized by comprising the following steps of:
A) Mixing lithium salt, a cobalt source and an M metal source, calcining the mixture I in an oxygen-containing atmosphere, and crushing the mixture to obtain a crude product a;
B) Calcining the crude product a in an oxygen-containing atmosphere to obtain a lithium cobaltate anode material by crushing;
The metal element M of the M metal source is selected from at least one of Al, mg, ti, zr, la, mn, ni, sb, W, nb.
2. The method according to claim 1, wherein the molar ratio of the cobalt source to the lithium salt and the M metal source is 1:1 to 1.1:0.0005 to 0.05 in terms of the number of moles of the metal elements.
3. The method according to claim 1, wherein the lithium salt is at least one selected from the group consisting of lithium hydroxide, lithium nitrate, lithium carbonate, lithium oxalate, lithium acetate, lithium oxide, and lithium citrate.
4. The method according to claim 1, wherein the cobalt source is at least one selected from the group consisting of cobaltosic oxide, cobalt carbonate, cobalt hydroxide, cobalt acetate, cobalt oxalate, cobalt nitrate, cobalt sulfate, and cobalt chloride.
5. The method according to claim 1, wherein the M metal source is selected from at least one of an oxide, hydroxide, sulfate, nitrate, and carbonate of a metal-containing element M.
6. The method according to claim 1, wherein the conditions for calcination I are: heating to 800-1100 ℃ at a heating rate of 0.2-10 ℃/min, and calcining for 6-20 h.
7. The method according to claim 1, wherein the temperature of the calcination II is 700 to 1100 ℃, and the time of the calcination II is 6 to 12 hours.
8. A lithium cobaltate positive electrode material obtained by the production method according to any one of claims 1 to 7, characterized in that the M metal source accounts for 0.01% to 0.5% of the molar mass of lithium cobaltate;
the particle size of the lithium cobaltate is 1-10 mu m.
9. The lithium cobalt oxide positive electrode material according to claim 8, wherein the highest chargeable voltage of the lithium cobalt oxide positive electrode material is 4.6V to 5V;
preferably, the ultra-fast charge rate of the lithium cobalt oxide positive electrode material is 5-20 ℃;
preferably, the capacity of the lithium cobaltate positive electrode material after 500 circles is more than 70%.
10. Use of a lithium cobalt oxide positive electrode material according to claim 8 or 9 in a positive electrode of a battery.
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