CN112002901A - Metal compound coated ternary cathode material and preparation method thereof - Google Patents
Metal compound coated ternary cathode material and preparation method thereof Download PDFInfo
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- 239000010406 cathode material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 150000002736 metal compounds Chemical class 0.000 title claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000010405 anode material Substances 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 12
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 239000011247 coating layer Substances 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000975 co-precipitation Methods 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001291 vacuum drying Methods 0.000 claims abstract description 4
- 239000007774 positive electrode material Substances 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910003678 NixCoyMnz(OH)2 Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000002344 surface layer Substances 0.000 claims description 2
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 43
- 229910052759 nickel Inorganic materials 0.000 description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
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- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
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- C01F17/00—Compounds of rare earth metals
- C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
- C01F17/32—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO
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- C01G53/40—Complex oxides containing nickel and at least one other metal element
- C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
- C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
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Abstract
A metal compound coated ternary anode material and a preparation method thereof. The chemical formula of the cathode material is LiNixCoyMnzO2·nCeO2&LiCeO2Wherein x, y, z,n is mole number, x is more than or equal to 0.6<1，0<y≤0.2，0<z≤0.2，x+y+z＝1，0<n≤0.05，CeO2Is active oxide, and the thickness of the coating layer is 3-5 nm. The preparation method comprises the following steps: firstly, synthesizing a ternary precursor by adopting coprecipitation; and mixing and sintering the ternary precursor and a lithium source to obtain the ternary cathode material LiNixCoyMnzO2(ii) a Then cerium source and ternary anode material LiNi are mixedxCoyMnzO2Uniformly dispersing into an organic solvent; stirring and evaporating most of the solvent to obtain black slurry; vacuum drying and grinding the black slurry to obtain pre-sintered powder; and sintering in an oxygen atmosphere to obtain the modified ternary cathode material. The material prepared by the invention has good cycling stability and excellent rate performance; the preparation method is simple and easy to operate, is suitable for large-scale production and has low cost.
Description
Technical Field
The invention relates to the field of battery materials, in particular to a metal compound coated ternary cathode material and a preparation method thereof.
Background
Global climate warming, the reduction of fossil fuels, and severe environmental problems. The lithium ion battery has high energy density, high open-circuit voltage, no memory effect, low self-discharge rate, greenness and no pollution, and thus becomes a hot point of current research. The lithium ions in the structure of the positive electrode material are the only source for maintaining the normal operation of the lithium ion battery, and the energy density of the lithium ion battery determines the energy density of one battery to a large extent. The high-nickel anode material becomes a novel lithium ion battery anode material due to the outstanding performance, has the advantages of cheap raw materials, obvious energy density and theoretical energy density and the like, and has great prospect in basic research and commercial popularization.
The nickel cobalt lithium manganate materials with different proportions have different performances, and along with the increase of the content of Ni, the capacity and the energy density of the lithium ion battery are correspondingly improved. Many researchers have therefore been working on developing positive electrode materials with large capacity, fast charge and discharge rates, and long life. In this regard, high nickel materials having reversible capacity and low cost have attracted increasing attention, but an increase in nickel content adversely affects the cycle performance and thermal stability of the battery, mainly manifested by a loss of charge-discharge capacity upon cycling and a large capacity fade in a high-temperature environment, which limits the application of high nickel cathode materials.
Therefore, aiming at the defects of the prior art, the provision of the ternary cathode material of the lithium ion battery and the preparation method thereof, which can simultaneously improve the cycle performance, the rate capability and the thermal stability of the ternary material, is particularly important.
Disclosure of Invention
The invention aims to provide a metal compound coated ternary positive electrode material. The battery assembled by the anode material has good cycle performance and rate capability.
The invention further aims to solve the technical problem of overcoming the defects in the prior art and providing a preparation method of the metal compound coated ternary cathode material. The preparation method is simple and reasonable, and the cost is low.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a metal compound coated ternary anode material and a preparation method thereof. The chemical formula of the cathode material is LiNixCoyMnzO2·nCeO2&LiCeO2Wherein x is more than or equal to 0.6<1，0<y≤0.2，0<z≤0.2，x+y+z＝1，0<n is less than or equal to 0.05. The particle size of the material is about 2-4 μm, the surface layer has a uniform double-coating layer, and the thickness is 3-5 nm.
The technical scheme adopted for further solving the technical problems is as follows:
a metal compound coated ternary cathode material and a preparation method thereof are prepared by the following steps:
(1) in terms of molar ratio, firstly, 3-6 moL/L of NiSO4·6H2O、CoSO4·7H2O、MnSO4·H2O (Ni: Co: Mn ═ x: y: z) is uniformly mixed, and at the same time, a NaOH solution (5 to 7mol/L) and NH as a complexing agent are added3·H2And respectively adding the O solution (4-7 mol/L) into the reaction tanks. Adjusting the pH value to 10.5-11.0, and the concentration of ammonia water to 1.5-2 mol/L. Carrying out coprecipitation reaction, washing and drying by pure water to obtain precursor NixCoyMnz(OH)2。
(2) In terms of mole ratios, as per Li: weighing a lithium source according to the proportion of (Ni + Co + Mn) 1-1.2: 1, and mixing the precursor material Ni prepared in the step (1)xCoyMnz(OH)2Uniformly mixing with a lithium source, burning for 5-8 h at 400-600 ℃, and burning for 10-14 h at 800-1000 ℃ to obtain the ternary cathode material LiNixCoyMnzO2。
(3) Uniformly dispersing a cerium source into an organic solvent in a molar ratio, and slowly adding the ternary cathode material LiNi prepared in the step (2) into the organic solventxCoyMnzO2Stirring until the mixture is uniformly mixed, evaporating most of the solvent, and drying the obtained slurry in vacuum to obtain a presintered substance.
(4) Grinding the pre-sintered substance obtained in the step (3) according to the molar ratio and sintering the pre-sintered substance in an oxygen atmosphere to obtain the CeO2&LiCeO2A coated ternary positive electrode material;
wherein x is more than or equal to 0.6 and less than 1, y is more than 0 and less than or equal to 0.2, z is more than 0 and less than or equal to 0.2, x + y + z is 1, and n is more than 0 and less than or equal to 0.05.
Preferably, in the step (3), the lithium source is one or more selected from lithium hydroxide, lithium carbonate and lithium nitrate.
Preferably, in the step (3), the cerium source is cerium nitrate.
Preferably, in the step (3), the solvent is one or more of methanol, ethanol and propanol
Preferably, in the step (3), the positive electrode material LiNixCoyMnzO2The solid-liquid ratio of the organic solvent to the organic solvent is 1-2 g: 5-15 mL, and more preferably, the solid-liquid ratio is 1g:7 mL.
Preferably, in the step (3), the vacuum degree is-0.1 MPa.
Preferably, in the step (3), the temperature of vacuum drying is 60-120 ℃.
Preferably, in the step (3), the vacuum drying time is 8-14 h.
Preferably, in the step (3), the temperature of the evaporated solvent is 60-85 ℃, and the time is 2-8 hours; more preferably, the temperature of the evaporation solvent is 75-80 ℃ and the time is 3-4 h.
Preferably, in the step (4), the grinding time is 5-10 min.
Preferably, in the step (4), the sintering temperature is 600-900 ℃ and the time is 10-14 h.
The invention has the beneficial effects that:
(1) the invention obtains the metal compound coated ternary cathode material and the preparation method thereof through effective and feasible surface modification. The high-nickel cathode material has serious capacity reduction, and can play a great potential through the formed double-coating layer, thereby improving the electrochemical performance of the high-nickel layered oxide. The outer layer of the double coating layer can resist corrosion of HF, and the inner layer can capture lithium impurities on the surface of the high nickel material. The lithium ion transmission rate on the surface of the material can be improved, and the rate capability of the material is improved. Experimental data show that the rate capability and the cycle performance of the material can be greatly improved by the double coating layer. In addition, the preparation method is simple, low in cost, simple to operate and suitable for industrial production.
(2) The high-nickel anode material is of a single crystal structure and is uniformly coated with CeO with the thickness of 3-5 nm2&The LiCoO coating layer is characterized in that the anode material has excellent rate capability and cycle performance, and tests show that the battery assembled by the anode material has the first discharge gram capacity of 190.1mAh/g within the voltage range of 2.75-4.3V and the 1C rate, the battery is cycled for 200 circles at 1C, the capacity is 150.1mAh/g, and the capacity retention rate is 78.96%.
Drawings
FIG. 1 is an SEM image of a ternary cathode material obtained in example 1 of the present invention;
FIG. 2 is a TEM image of a ternary cathode material obtained in example 1 of the present invention;
FIG. 3 is an XRD pattern of a ternary cathode material obtained in example 1 of the present invention;
fig. 4 is a graph of cycle performance of the ternary cathode materials obtained in examples 1, 2, and 3 of the present invention and comparative example 1.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
Example 1
The preparation method of the metal compound coated ternary cathode material is described by combining specific examples, and the preparation method specifically comprises the following steps:
(1) in terms of molar ratio, 3moL/L of 8.8moL of NiSO4·6H2O, 0.6moL of CoSO4·7H2O, 0.6moL MnSO4·H2O (Ni: Co: Mn: 88:6:6) was uniformly mixed, and at the same time, a NaOH solution (5mol/L) and NH as a complexing agent were added3·H2O solution (6mol/L) was also added to the reaction tank separately. The pH was adjusted to 10.5 and the ammonia concentration was 1.5 mol/L. Carrying out coprecipitation reaction, washing and drying by pure water to obtain precursor Ni0.88Co0.06Mn0.06(OH)2。
(2) In terms of mole ratios, as per Li: weighing 1.05mol of lithium nitrate according to the proportion of (Ni + Co + Mn) ═ 1.05:1, and mixing 1mol of precursor material Ni prepared in the step (1)0.88Co0.06Mn0.06(OH)2Evenly mixing with lithium nitrate, burning for 6h at 500 ℃ and 14h at 810 to obtain the ternary cathode material LiNi0.88Co0.06Mn0.06O2。
(3) Uniformly dispersing 0.001mol of cerium nitrate into absolute ethyl alcohol in terms of molar ratio, and slowly adding 0.1mol of the positive electrode material LiNi prepared in the step (2) into the absolute ethyl alcohol0.88Co0.06Mn0.06O2The solid-to-liquid ratio was adjusted to 1g:7 mL. Stirring until the mixture is uniformly mixed and evaporating for 3 hours at 80 ℃ to obtain black slurry; and (3) drying the black slurry at 100 ℃ for 10h under the vacuum degree of-0.1 MPa to obtain a presintered substance.
(4) Grinding the pre-sintered substance obtained in the step (3) for 5min in molar ratio, and sintering at 700 ℃ for 11h in an oxygen atmosphere to obtain the LiNi0.88Co0.06Mn0.06O2·0.01CeO2&LiCeO2A ternary positive electrode material;
the obtained ternary positive electrode material coated with the metal compound is characterized and detected, and the composition of the ternary positive electrode material is LiNi0.88Co0.06Mn0.06O2·0.01CeO2&LiCeO2The electron microscope images of the high-nickel cathode material are shown in figures 1 and 2, the particle size of the high-nickel cathode material is 2-4 mu m, and a coating layer with uniform thickness is arranged on the surface of the high-nickel cathode material. The XRD junction of the high-nickel anode materialAs shown in FIG. 3, LiNi is present0.88Co0.06Mn0.06O2And CeO2&LiCeO2Two phases.
The high-nickel cathode material obtained in the embodiment is adopted to assemble a button cell of CR 2025. When the battery is used in a voltage range of 2.75-4.3V and at a multiplying power of 1C, the first discharge capacity reaches 190.5mAh/g, the capacity is 149.3mAh/g after 200 cycles at 1C, and the capacity retention rate reaches 78.37% (see a curve shown in figure 4 specifically).
Example 2
(1) Firstly, 4moL/L of 8.8moL of NiSO4·6H2O, 0.6moL of CoSO4·7H2O, 0.6moL MnSO4·H2O (Ni: Co: Mn: 88:6:6) was uniformly mixed, and at the same time, a NaOH solution (5.6mol/L) and NH as a complexing agent were added3·H2O solution (6.5mol/L) was also added to the reaction tank separately. The pH was adjusted to 10.8 and the ammonia concentration was 1.7 mol/L. Carrying out coprecipitation reaction, washing and drying by pure water to obtain precursor Ni0.88Co0.06Mn0.06(OH)2。
(2) In terms of mole ratios, as per Li: weighing 1.1mol of lithium hydroxide according to the proportion of (Ni + Co + Mn) ═ 1.1:1, and mixing 1mol of precursor material Ni prepared in the step (1)0.88Co0.06Mn0.06(OH)2Mixing with lithium hydroxide uniformly, burning at 550 ℃ for 7h, and burning at 820 ℃ for 13h to obtain the ternary cathode material LiNi0.88Co0.06Mn0.06O2。
(3) Uniformly dispersing 0.002mol of cerium nitrate into methanol in terms of molar ratio, and slowly adding 0.1mol of the positive electrode material LiNi prepared in the step (2) into the methanol0.88Co0.06Mn0.06O2The solid-to-liquid ratio was adjusted to 1g:7 mL. Stirring until the mixture is uniformly mixed, and evaporating at 75 ℃ for 3.5h to obtain black slurry; and (3) drying the black slurry in vacuum at the vacuum degree of-0.1 MPa and at the temperature of 110 ℃ for 12h to obtain a presintered substance.
(4) Grinding the pre-sintered substance obtained in the step (3) for 7min in a molar ratio, and sintering at 680 ℃ for 12h in an oxygen atmosphere to obtain the LiNi0.88Co0.06Mn0.06O2·0.02CeO2&LiCeO2A ternary positive electrode material;
the obtained ternary positive electrode material coated with the metal compound is characterized and detected, and the composition of the ternary positive electrode material is LiNi0.88Co0.06Mn0.06O2·0.02CeO2&LiCeO2The particle size of the high-nickel anode material is 2-4 mu m, a coating layer with uniform thickness exists on the surface, and LiNi exists0.88Co0.06Mn0.06O2And CeO2&LiCeO2Two phases.
The high-nickel cathode material obtained in the embodiment is adopted to assemble a button cell of CR 2025. When the battery is used in a voltage range of 2.75-4.3V and under a multiplying power of 1C, the first discharge gram capacity reaches 190.1mAh/g, the battery is circulated for 200 circles under 1C, the capacity is 150.1mAh/g, and the capacity retention rate reaches 78.96% (particularly, refer to a curve shown in FIG. 4).
Example 3
(1) In terms of molar ratio, 5moL/L of 8.8moL of NiSO4·6H2O, 0.6moL of CoSO4·7H2O, 0.6moL MnSO4·H2O (Ni: Co: Mn: 88:6:6) was uniformly mixed, and at the same time, a NaOH solution (5.2mol/L) and NH as a complexing agent were added3·H2O solution (5.5mol/L) was also added to the reaction tank separately. The pH was adjusted to 10.5 and the ammonia concentration was 1.8 mol/L. Carrying out coprecipitation reaction, washing and drying by pure water to obtain precursor Ni0.88Co0.06Mn0.06(OH)2。
(2) In terms of mole ratios, as per Li: weighing 0.6mol of lithium carbonate according to the proportion of (Ni + Co + Mn) ═ 1.2:1, and mixing 1mol of precursor material Ni prepared in the step (1)0.88Co0.06Mn0.06(OH)2Uniformly mixing with lithium carbonate, burning for 6h at 600 ℃ and burning for 11h at 830 ℃ to obtain the ternary cathode material LiNi0.88Co0.06Mn0.06O2。
(3) Uniformly dispersing 0.003mol of cerium nitrate into propanol, and slowly adding 0.1mol of the positive electrode material LiNi prepared in the step (2) into the propanol0.88Co0.06Mn0.06O2The solid-to-liquid ratio was adjusted to 1g:7 mL. Stirring until the mixture is uniformly mixed, and evaporating at 78 ℃ for 3.6h to obtain black slurry; and (3) drying the black slurry at 115 ℃ for 8.5h under the vacuum degree of-0.1 MPa to obtain a presintered substance.
(4) Grinding the pre-sintered substance obtained in the step (3) for 8min, and sintering at 710 ℃ for 10.5h in an oxygen atmosphere to obtain the LiNi0.88Co0.06Mn0.06O2·0.03CeO2&LiCeO2A ternary positive electrode material;
the obtained ternary positive electrode material coated with the metal compound is characterized and detected, and the composition of the ternary positive electrode material is LiNi0.88Co0.06Mn0.06O2·0.03CeO2&LiCeO2The particle size of the high-nickel anode material is 2-4 mu m, a coating layer with uniform thickness exists on the surface, and LiNi exists0.88Co0.06Mn0.06O2And CeO2&LiCeO2Two phases.
The high-nickel cathode material obtained in the embodiment is adopted to assemble a button cell of CR 2025. When the battery is used in a voltage range of 2.75-4.3V and at a multiplying power of 1C, the first discharge gram capacity reaches 189.2mAh/g, the capacity is still 143mAh/g after the battery is circulated for 200 circles at 1C, and the capacity retention rate reaches 75.58% (particularly, refer to a curve shown in FIG. 4).
Comparative example 1
(1) In terms of molar ratio, 6moL/L of 8.8moL of NiSO4·6H2O, 0.6moL of CoSO4·7H2O, 0.6moL MnSO4·H2O (Ni: Co: Mn: 88:6:6) was uniformly mixed, and at the same time, a NaOH solution (6mol/L) and NH as a complexing agent were added3·H2O solution (6mol/L) was also added to the reaction tank separately. The pH was adjusted to 10.7 and the ammonia concentration was 1.9 mol/L. Carrying out coprecipitation reaction, washing and drying by pure water to obtain precursor Ni0.88Co0.06Mn0.06(OH)2。
(2) In terms of mole ratios, as per Li: weighing 1.05mol of lithium nitrate according to the proportion of (Ni + Co + Mn) ═ 1.05:1, and mixing 1mol of precursor material Ni prepared in the step (1)0.88Co0.06Mn0.06(OH)2Evenly mixing with lithium nitrate, burning at 540 ℃ for 7h, and burning at 825 ℃ for 11.5h to obtain the ternary cathode material LiNi0.88Co0.06Mn0.06O2。
(3) 0.1mol of LiNi which is the positive electrode material obtained in the step (2) is calculated according to the molar ratio0.88Co0.06Mn0.06O2Slowly adding into absolute ethyl alcohol, and adjusting the solid-liquid ratio to 1g:7 mL. Stirring until the mixture is uniformly mixed, and evaporating at 80 ℃ for 3.5h to obtain black slurry; and (3) drying the black slurry at the vacuum degree of-0.1 MPa and the temperature of 90 ℃ for 12h in vacuum to obtain a presintered substance.
(4) Grinding the pre-sintered substance obtained in the step (3) for 8.5min, and sintering at 710 ℃ for 10.5h in an oxygen atmosphere to obtain the LiNi0.88Co0.06Mn0.06O2A ternary positive electrode material.
The ternary positive electrode material obtained in this example was characterized and detected, and its composition was LiNi0.88Co0.06Mn0.06O2The high-nickel cathode material is single crystal particles with the particle size of 4 mu m, and LiNi exists0.88Co0.06Mn0.06O2A phase of the mixture.
The high-nickel cathode material obtained in the embodiment is adopted to assemble a button cell of CR 2025. When the battery is used in a voltage range of 2.75-4.3V and under a multiplying power of 1C, the first discharge gram capacity reaches 190.2mAh/g, the battery is circulated for 200 circles under 1C, the capacity is 140.8mAh/g, and the capacity retention rate reaches 74.02% (particularly, refer to a curve shown in FIG. 4).
In conclusion, the cycle and rate performance of the ternary cathode material coated by the metal compound are greatly improved.
Claims (4)
1. A metal compound coated ternary anode material and a preparation method thereof. The chemical formula of the cathode material is LiNixCoyMnzO2·nCeO2&LiCeO2Wherein x, y, z and n are mole numbers, and x is more than or equal to 0.6<1，0<y≤0.2，0<z≤0.2，x+y+z＝1，0<n≤0.05。
2. The positive electrode material according to claim 1, wherein the positive electrode material is a single crystal particle having a particle size of about 2 to 4 μm, and the surface layer forms a uniform double coating layer having a thickness of 3 to 5 nm.
3. A metal compound coated ternary cathode material and a preparation method thereof are prepared by the following steps:
(1) in terms of molar ratio, firstly, 3-6 moL/L of NiSO4·6H2O、CoSO4·7H2O、MnSO4·H2O (Ni: Co: Mn ═ x: y: z) is uniformly mixed, and at the same time, a NaOH solution (5 to 7mol/L) and NH as a complexing agent are added3·H2And respectively adding the O solution (4-7 mol/L) into the reaction tanks. Adjusting the pH value to 10.5-11.0, and the concentration of ammonia water to 1.5-2 mol/L. Carrying out coprecipitation reaction, washing and drying by pure water to obtain precursor NixCoyMnz(OH)2。
(2) In terms of mole ratios, as per Li: weighing a lithium source according to the proportion of (Ni + Co + Mn) 1-1.2: 1, and mixing the precursor material Ni prepared in the step (1)xCoyMnz(OH)2Uniformly mixing with a lithium source, burning for 5-8 h at 400-600 ℃, and burning for 10-14 h at 800-1000 ℃ to obtain the ternary cathode material LiNixCoyMnzO2。
(3) Uniformly dispersing a cerium source into an organic solvent in a molar ratio, and slowly adding the ternary cathode material LiNi prepared in the step (2) into the organic solventxCoyMnzO2Stirring until the mixture is uniformly mixed, evaporating most of the solvent, and drying the obtained slurry in vacuum to obtain a presintered substance.
(4) Grinding the pre-sintered substance obtained in the step (3) according to the molar ratio and sintering the pre-sintered substance in an oxygen atmosphere to obtain the CeO2&LiCeO2A coated ternary positive electrode material;
wherein x is more than or equal to 0.6 and less than 1, y is more than 0 and less than or equal to 0.2, z is more than 0 and less than or equal to 0.2, x + y + z is 1, and n is more than 0 and less than or equal to 0.05.
4. The metal compound coated ternary cathode material of claim 3And the preparation method is characterized in that in the step (3), the lithium source is selected from one or more of lithium hydroxide, lithium carbonate and lithium nitrate; the cerium source is cerium nitrate; the solvent is one or more of methanol, ethanol and propanol; the positive electrode material LiNixCoyMnzO2The solid-liquid ratio of the organic solvent to the organic solvent is 1-2 g: 5-15 mL, preferably 1g:7 mL; the vacuum degree of vacuum drying is-0.1 MPa, the temperature is 60-120 ℃, and the time is 8-14 h; the temperature of the evaporating solvent is 60-85 ℃, and the time is 2-8 h; more preferably, the temperature of the evaporation solvent is 75-80 ℃ and the time is 3-4 h. In the step (4), the grinding time is 5-10 min, the sintering temperature is 600-900 ℃, and the sintering time is 10-14 h.
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