CN116314622A - Single crystal cobalt-free aluminum doped lithium nickelate positive electrode material with self-precipitation coating layer, and preparation method and application thereof - Google Patents
Single crystal cobalt-free aluminum doped lithium nickelate positive electrode material with self-precipitation coating layer, and preparation method and application thereof Download PDFInfo
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- CN116314622A CN116314622A CN202310295597.6A CN202310295597A CN116314622A CN 116314622 A CN116314622 A CN 116314622A CN 202310295597 A CN202310295597 A CN 202310295597A CN 116314622 A CN116314622 A CN 116314622A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 107
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 78
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 71
- 239000011247 coating layer Substances 0.000 title claims abstract description 64
- 239000013078 crystal Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000001556 precipitation Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000010406 cathode material Substances 0.000 claims abstract 3
- 239000010405 anode material Substances 0.000 claims description 35
- 235000002639 sodium chloride Nutrition 0.000 claims description 28
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 22
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 20
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 239000011780 sodium chloride Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000006258 conductive agent Substances 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000013067 intermediate product Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 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
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910018040 Li 1+x Ni Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 29
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
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- 239000000047 product Substances 0.000 description 17
- 229910052593 corundum Inorganic materials 0.000 description 15
- 239000010431 corundum Substances 0.000 description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
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- 239000012071 phase Substances 0.000 description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 7
- 239000012982 microporous membrane Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
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- 229910013870 LiPF 6 Inorganic materials 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 238000007605 air drying Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
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- 230000008018 melting Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000010416 ion conductor Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 238000001000 micrograph Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910016163 LiNi0.95Al0.05O2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract
The invention belongs to the field of electrochemical energy storage batteries and power batteries, and particularly discloses a monocrystal cobalt-free aluminum-doped lithium nickelate positive electrode material with a self-precipitation coating layer, and a preparation method and application thereof. The invention synthesizes the monocrystal cobalt-free aluminum doped lithium nickelate positive electrode material by a molten salt method, and after the molten salt is removed by water washing, the positive electrode material is mixed with a small amount of lithium source by a secondary lithiation method for rapid medium-temperature heat treatment, and the positive electrode material is induced by chemical actionIn-situ lattice precipitation of part of aluminum element in bulk phase, and beta-Li is formed on the surface of the material 5 AlO 4 And (3) coating to finally obtain the material. The cathode material has better cycle stability, rate capability and higher mechanical strength, avoids the damage of inter-crystal stress in the charge and discharge process, inhibits the formation of cracks, and is expected to promote the industrialized application of the cobalt-free aluminum doped lithium nickelate cathode material.
Description
Technical Field
The invention belongs to the field of electrochemical energy storage batteries and power batteries, and particularly relates to a cobalt-free aluminum-doped lithium nickelate positive electrode material with a self-precipitation coating layer, and a preparation method and application thereof.
Background
Lithium Ion Batteries (LIBs) are considered as a promising energy storage device, and have been applied in electric vehicles, renewable energy power stations, and smart grids. As one of the positive electrode materials of lithium ion batteries, cobalt-free aluminum-doped lithium nickelate (LiNi 0.95 Al 0.05 O 2 ) Has the advantages of high capacity, low cost and the like, and is widely focused. However, there are also some problems with cobalt-free aluminum doped lithium nickelate positive electrode materials, which restrict their application: ni in charged state 4+ The high oxidability of the catalyst causes side reactions on the surface of the material and the electrolyte, and the performance is degraded; the anode material is sensitive to water, and the requirements of the material preparation and battery manufacturing process are high; the polycrystalline particles have inter-crystal stress, so that cracks are easy to generate, and the stability of the material is reduced.
In order to improve the structural stability of the material, single crystal modification of cobalt-free aluminum-doped lithium nickelate is a novel strategy. Such as a ternary positive electrode material NCM811 for lithium ion batteries prepared by molten salt method (Centro, zhong Chengwen, lou Suo et al, china patent CN 111224089A). And synthesizing monocrystal particles with ideal morphology through molten salt assistance. The single crystal material overcomes the influence of inter-crystal stress and has higher stability than that of the polycrystalline material. However, single crystal modification does not improve the side reaction problem caused by the high activity of the surface of the material itself. Therefore, a modification means is sought, the cycle performance of the monocrystalline material is further improved, and the method is very important for the application of cobalt-free aluminum doped lithium nickelate.
Surface coating is an effective modification strategy, and can inhibit side reactions between the surface of the material and the electrolyte. In single crystal ternary material systems, certain coating modification work has been reported. For example, an MOF coated single crystal ternary positive electrode material is obtained by adding organic carboxylate into the synthesis process of the single crystal ternary material to obtain an MOF coating layer on the surface of the material. The coating layer effectively improves the thermal stability and the cycle stability of the single crystal material (Xu Kaihua, jiang Zhenkang, zhang Kun, etc., chinese patent CN 111129463 a). However, the conventional coating method requires additional introduction of coating materials or the use of a complicated coating process, increasing the manufacturing cost; some coating strategies are realized through liquid phase reaction, and the cobalt-free aluminum-doped lithium nickel oxide material is sensitive to water and is easy to induce the surface to form an inactive rock salt phase, so that the performance of the anode material is degraded; the coating layer is not matched with the bulk material in lattice, and the uniformity is insufficient; the coating layer is a non-fast ion conductor, can obstruct the diffusion of lithium ions in the charge and discharge process, and reduces the rate capability of the anode material. Therefore, there is a need to develop a low cost, hydrophobic and uniform coating strategy to achieve application of single crystal cobalt-free aluminum doped lithium nickel oxide positive electrode materials.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a self-precipitation beta-Li 5 AlO 4 The monocrystalline cobalt-free aluminum doped lithium nickelate anode material of the coating layer adopts the following technical scheme:
beta-Li self-precipitation 5 AlO 4 The preparation method of the monocrystal cobalt-free aluminum doped lithium nickelate positive electrode material of the coating layer comprises the following steps:
s1, ni is mixed with 0.95 Al 0.05 (OH) 2 Uniformly mixing the precursor, a first lithium source and chloride, reacting in an oxygen atmosphere by a molten salt method to obtain an intermediate product, washing the intermediate product with water, and drying to obtain the monocrystal cobalt-free aluminum-doped lithium nickelate layered anode material;
s2, uniformly mixing the monocrystal cobalt-free aluminum-doped lithium nickel oxide layered anode material obtained in the step S1 with a second lithium source, and then performing intermediate-temperature heat treatment in an oxygen atmosphere to obtain self-precipitated beta-Li 5 AlO 4 A single crystal cobalt-free aluminum doped lithium nickelate anode material of the coating layer;
the dosage of the first lithium source is Ni 0.95 Al 0.05 (OH) 2 105% -130% of the mole fraction of the precursor; the dosage of the second lithium source is less than 30% of the mass fraction of the single crystal cobalt-free aluminum doped lithium nickelate layered anode material obtained in the step S1; the temperature of the medium-temperature heat treatment is 650-750 ℃; with self-precipitating beta-Li 5 AlO 4 The molecular formula of the monocrystal cobalt-free aluminum-doped lithium nickelate positive electrode material of the coating layer is Li 1+x Ni 0.95-y Al 0.05-z O 2 X is more than 0 and less than 0.1, y is more than 0 and less than 0.1, z is more than 0 and less than 0.05, and the grain diameter is 100nm-1 mu m; beta-Li 5 AlO 4 In the presence of self-precipitated beta-Li 5 AlO 4 The mass fraction of the monocrystal cobalt-free aluminum doped lithium nickel oxide anode material of the coating layer is less than 5%.
In order to solve the problems in the prior art, the invention provides a two-step preparation method, which comprises the steps of firstly using Ni 0.95 Al 0.05 (OH) 2 The method comprises the steps of obtaining a monocrystal cobalt-free aluminum-doped lithium nickel oxide positive electrode material by adopting molten salt chemistry as a precursor, washing to remove molten salt, performing secondary lithiation, mixing the positive electrode material with a small amount of lithium source, performing rapid medium-temperature heat treatment, inducing in-situ lattice precipitation of part of aluminum element in a positive electrode material body phase through chemical action, and forming beta-Li on the material surface 5 AlO 4 A coating layer, finally obtaining the self-precipitated beta-Li 5 AlO 4 The monocrystal of the coating layer is free of cobalt and aluminum doped with lithium nickelate anode material.
The self-precipitated beta-Li prepared by the invention 5 AlO 4 Single crystal cobalt-free aluminum doped lithium nickelate anode with coating layerThe material can be sintered only by adding a lithium source without adding an additional aluminum source in the preparation process, thus obtaining the beta-Li 5 AlO 4 The coating layer greatly reduces the coating cost; beta-Li formed by combining in-situ self-precipitated aluminum and lithium 5 AlO 4 The crystal lattice is highly matched with the positive electrode material phase, so that the uniformity of the coating layer is ensured; the uniform coating layer effectively inhibits the side reaction of the material surface and the electrolyte. Furthermore, beta-Li 5 AlO 4 The fast ion conductor can improve the multiplying power performance of the positive electrode material. Thus having self-precipitating beta-Li 5 AlO 4 The monocrystal cobalt-free aluminum-doped lithium nickelate anode material of the coating layer has higher comprehensive performance and can be applied to lithium ion batteries.
In the present invention, the amount of lithium source required for the molten salt method is limited to Ni 0.95 Al 0.05 (OH) 2 105% -130% of the mole fraction of the precursor; the lithium source consumption required by the secondary lithiation method is less than 30% of the mass fraction of the monocrystal cobalt-free aluminum-doped lithium nickel oxide layered positive electrode material with the rock salt phase on the surface. The above limitation is on the one hand to realize the technical conception/technical principle so as to successfully prepare the self-precipitated beta-Li 5 AlO 4 A single crystal cobalt-free aluminum doped lithium nickelate anode material of the coating layer; on the other hand, too high or too low an amount may affect the formation of the coating layer, and may reduce the specific capacity of the positive electrode material. Preferably, however, the amount of chloride required is limited to less than Ni 0.95 Al 0.05 (OH) 2 The molar fraction of the precursor is also because too low or too high an addition amount of the chloride may decrease the specific capacity of the positive electrode material.
Wherein in the molten salt method process, the chloride is at least one of sodium chloride, potassium chloride, lithium chloride, ferric chloride, calcium chloride and cupric chloride; the chloride is preferably lithium chloride or sodium chloride. The inventor finds that the combination of lithium chloride and sodium chloride can effectively reduce the melting point of molten salt, and the melting point is lower than 300 ℃ under the condition of the optimal ratio of 3:2, which is favorable for the formation of single crystal particles in the molten salt synthesis process, because the low-melting-point molten salt can ensure better formation of a layered structure, and if the melting point is high, more energy is used for melting the molten salt.
β-Li 5 AlO 4 The specific process of forming the coating layer is as follows: adding a second lithium source with the dosage less than 30% of the mass fraction of the monocrystal cobalt-free aluminum doped lithium nickel oxide layered anode material, heating to 650-750 ℃ at the speed of 1-10 ℃/min, and then preserving heat for 1-6 h. If the temperature rise rate is too high or the temperature is too high, the amount of aluminum precipitated on the surface becomes insufficient, and uniform self-precipitated beta-Li cannot be obtained 5 AlO 4 And a coating layer.
Preferably, the lithium source is at least one of lithium hydroxide, lithium carbonate, lithium nitrate, and lithium acetate.
Self-precipitated beta-Li based on the preparation method 5 AlO 4 The invention provides a single crystal cobalt-free aluminum doped lithium nickelate positive electrode material of a coating layer, which can be applied to the preparation of a lithium ion battery, and the invention provides a battery positive electrode plate based on the material, and the preparation process comprises the following steps: will have self-precipitated beta-Li 5 AlO 4 The single crystal cobalt-free aluminum doped lithium nickel oxide anode material of the coating layer, the conductive agent, the binder and the solvent are uniformly mixed (with self-precipitation beta-Li) 5 AlO 4 The mass ratio of the monocrystal cobalt-free aluminum doped lithium nickel oxide positive electrode material, the conductive agent and the binder of the coating layer is preferably 8:1: 1) And coating the positive electrode plate on a metal matrix, and drying to obtain the battery positive electrode plate. The positive electrode sheet of the battery is used as a positive electrode, the lithium metal sheet is used as a negative electrode, and an electrolyte (1M LiPF can be selected 6 And EC/DMC/EMC; the volume ratio is 1:1: 1) And a separator (optionally Celgard 2500 microporous membrane), to obtain a lithium electronic battery (button battery can be formed).
The beneficial effects of the invention are as follows:
(1) The invention synthesizes the monocrystal cobalt-free aluminum doped lithium nickelate positive electrode material by a molten salt method, washes to remove molten salt, then adds a lithium source by a secondary lithiation method, carries out quick medium-temperature heat treatment, induces in-situ lattice precipitation of part of aluminum element in the positive electrode material body phase by chemical action, and forms beta-Li on the material surface 5 AlO 4 A coating layer, finally obtaining the self-precipitated beta-Li 5 AlO 4 The monocrystal of the coating layer is free of cobalt and aluminum doped with lithium nickelate anode material.
(2) The coating process does not need to additionally add an aluminum source, and the beta-Li can be obtained only by adding a lithium source for sintering 5 AlO 4 The coating layer greatly reduces the coating cost; beta-Li formed by combining in-situ self-precipitated aluminum and lithium 5 AlO 4 The crystal lattice is highly matched with the positive electrode material phase, so that the uniformity of the coating layer is ensured; the uniform coating layer effectively inhibits the side reaction of the material surface and the electrolyte. Furthermore, beta-Li 5 AlO 4 The fast ion conductor can improve the multiplying power performance of the positive electrode material. In conclusion, the self-precipitated beta-Li prepared by the invention 5 AlO 4 The monocrystal cobalt-free aluminum-doped lithium nickelate anode material with the coating layer is expected to promote the industrialized application of the cobalt-free aluminum-doped lithium nickelate anode material.
Drawings
FIG. 1 shows the product of example 1 of the present invention with self-precipitating beta-Li 5 AlO 4 Single crystal cobalt-free aluminum doped lithium nickelate positive electrode material with coating layer and Ni used for all products 0.95 Al 0.05 (OH) 2 Scanning electron microscope images of the precursor;
FIG. 2 shows the product of example 1 of the present invention with self-precipitating beta-Li 5 AlO 4 An elemental analysis diagram of a transmission electron microscope of a monocrystal cobalt-free aluminum-doped lithium nickelate positive electrode material of the coating layer;
FIG. 3 shows the product of example 1 of the present invention with self-precipitated beta-Li 5 AlO 4 X-ray diffraction fine-tuning graphs of the single crystal cobalt-free aluminum doped lithium nickelate positive electrode material of the coating layer and the single crystal cobalt-free aluminum doped lithium nickelate positive electrode material of the product of the example 2;
FIG. 4 shows the product of example 1 of the present invention with self-precipitating beta-Li 5 AlO 4 The single crystal cobalt-free aluminum doped lithium nickelate positive electrode material of the coating layer and the single crystal cobalt-free aluminum doped lithium nickelate positive electrode material of the product of the example 2 have charge and discharge curves at 0.1C;
FIG. 5 shows the product of example 1 of the present invention with self-precipitating beta-Li 5 AlO 4 Single crystal cobalt-free aluminum doped lithium nickelate with coating layerCycling performance curves of the positive electrode material and the single crystal cobalt-free aluminum doped lithium nickelate positive electrode material of example 2 at 1C;
FIG. 6 shows the product of example 1 of the present invention with self-precipitated beta-Li 5 AlO 4 Differential capacitance maps of the single crystal cobalt-free aluminum doped lithium nickelate positive electrode material of the coating layer and the single crystal cobalt-free aluminum doped lithium nickelate positive electrode material of the product of the example 2 at 1C;
FIG. 7 shows the product of example 1 of the present invention with self-precipitating beta-Li 5 AlO 4 The single crystal cobalt-free aluminum doped lithium nickelate positive electrode material of the coating layer and the single crystal cobalt-free aluminum doped lithium nickelate positive electrode material of the example 2 product have the rate performance curves under different rates.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described below with reference to the embodiments and the drawings to fully understand the objects, aspects and effects of the present invention.
Example 1:
beta-Li self-precipitation 5 AlO 4 The preparation method of the single crystal cobalt-free aluminum doped lithium nickelate anode material with the coating layer is shown in figure 1, and specifically comprises the following steps:
s1, respectively weighing 1.00g Ni 0.95 Al 0.05 (OH) 2 Uniformly grinding the precursor, 0.55g of lithium hydroxide, 0.30g of lithium chloride and 0.20g of sodium chloride in a mortar, placing the mixture into a corundum crucible, placing the corundum crucible into a tube furnace filled with oxygen, heating to 650 ℃ at a speed of 5 ℃/min, preserving heat for 12h, and naturally cooling; dispersing the obtained material in 100mL of deionized water, stirring, filtering, and carrying out forced air drying at 80 ℃ for 2 hours to obtain a monocrystal cobalt-free aluminum-doped lithium nickelate positive electrode material;
s2, respectively weighing 0.50g of the monocrystal cobalt-free aluminum-doped lithium nickelate positive electrode material prepared by S1 and 0.04g of lithium hydroxide, grinding uniformly in a mortar, placing in a corundum crucible, placing in a tube furnace filled with oxygen, heating to 650 ℃ at a speed of 5 ℃/min, preserving heat for 4h, and naturally cooling to obtain monocrystal Li 1.045 Ni 0.911 Al 0.044 O 2 And a positive electrode material. Figure 3 shows the XRD refinement of the S2 product,the coating layer was about 1.05% by mass of the positive electrode material.
A preparation method of the button cell comprises the following steps: the prepared anode material, super-p conductive agent and polyvinylidene fluoride binder are mixed according to the mass ratio of 8:1:1, adding N-methyl-2-pyrrolidone, mixing to obtain uniform slurry, uniformly coating on aluminum foil by a coating method, drying, rolling, punching into round electrode slices, and vacuum drying at 120 ℃ for 12h; taking the lithium metal plate as a positive electrode and a metal lithium sheet as a negative electrode, and 1M LiPF 6 And EC (ethylene carbonate)/DMC (dimethyl carbonate)/EMC (methyl ethyl carbonate) (volume ratio of 1:1:1) as electrolyte, celgard 2500 microporous membrane as separator, assembled into coin cell in glove box.
Example 2:
the preparation method of the monocrystal cobalt-free aluminum doped lithium nickelate positive electrode material comprises the following steps:
s1, respectively weighing Ni 0.95 Al 0.05 (OH) 2 Uniformly grinding the precursor, 0.55g of lithium hydroxide, 0.30g of lithium chloride and 0.20g of sodium chloride in a mortar, placing the mixture into a corundum crucible, placing the corundum crucible into a tube furnace filled with oxygen, heating to 650 ℃ at a speed of 5 ℃/min, preserving heat for 12h, and naturally cooling; dispersing the obtained material in 100mL of deionized water, stirring, filtering, and carrying out forced air drying at 80 ℃ for 2 hours to obtain a monocrystal cobalt-free aluminum-doped lithium nickelate positive electrode material;
s2, respectively weighing 0.50g of the monocrystal cobalt-free aluminum-doped lithium nickelate positive electrode material prepared by S1 and 0.01g of lithium hydroxide, grinding uniformly in a mortar, placing in a corundum crucible, placing in a tube furnace filled with oxygen, heating to 650 ℃ at a speed of 5 ℃/min, preserving heat for 4h, and naturally cooling to obtain monocrystal Li 0.962 Ni 0.988 Al 0.050 O 2 And a positive electrode material.
A preparation method of the button cell comprises the following steps: the prepared anode material, super-p conductive agent and polyvinylidene fluoride binder are mixed according to the mass ratio of 8:1:1, adding N-methyl-2-pyrrolidone, mixing to obtain uniform slurry, uniformly coating on aluminum foil by a coating method, drying, rolling, punching into round electrode slices, and vacuum drying at 120 ℃ for 12h; taking the lithium metal as positive electrode and the lithium metal as negative electrodePole, 1M LiPF 6 And EC/DMC/EMC (volume ratio of 1:1:1) as electrolyte, celgard 2500 microporous membrane as separator, assembled into coin cell in glove box.
Example 3:
beta-Li self-precipitation 5 AlO 4 The preparation method of the monocrystalline cobalt-free aluminum doped lithium nickelate anode material with the coating layer comprises the following steps:
s1, respectively weighing 1.00g Ni 0.95 Al 0.05 (OH) 2 Uniformly grinding the precursor, 0.55g of lithium hydroxide, 0.30g of lithium chloride and 0.20g of sodium chloride in a mortar, placing the mixture into a corundum crucible, placing the corundum crucible into a tube furnace filled with oxygen, heating to 650 ℃ at a speed of 5 ℃/min, preserving heat for 12h, and naturally cooling; dispersing the obtained material in 100mL of deionized water, stirring, filtering, and carrying out forced air drying at 80 ℃ for 2 hours to obtain a monocrystal cobalt-free aluminum-doped lithium nickelate positive electrode material;
s2, respectively weighing 0.50g of the monocrystal cobalt-free aluminum-doped lithium nickel oxide positive electrode material prepared by S1 and 0.08g of lithium hydroxide, grinding uniformly in a mortar, placing in a corundum crucible, placing in a tube furnace filled with oxygen, heating to 650 ℃ at a speed of 5 ℃/min, preserving heat for 3h, and naturally cooling to obtain monocrystal Li 1.062 Ni 0.899 Al 0.039 O 2 And a positive electrode material.
A preparation method of the button cell comprises the following steps: the prepared anode material, super-p conductive agent and polyvinylidene fluoride binder are mixed according to the mass ratio of 8:1:1, adding N-methyl-2-pyrrolidone, mixing to obtain uniform slurry, uniformly coating on aluminum foil by a coating method, drying, rolling, punching into round electrode slices, and vacuum drying at 120 ℃ for 12h; taking the lithium metal plate as a positive electrode and a metal lithium sheet as a negative electrode, and 1M LiPF 6 And EC/DMC/EMC (volume ratio of 1:1:1) as electrolyte, celgard 2500 microporous membrane as separator, assembled into coin cell in glove box.
Example 4:
the preparation method of the monocrystal cobalt-free aluminum doped lithium nickelate positive electrode material comprises the following steps:
s1, respectively weighing 1.00g Ni 0.95 Al 0.05 (OH) 2 Uniformly grinding the precursor, 0.70g of lithium carbonate, 0.30g of lithium chloride and 0.20g of sodium chloride in a mortar, placing the mixture into a corundum crucible, placing the corundum crucible into a tube furnace filled with oxygen, heating to 650 ℃ at a speed of 5 ℃/min, preserving heat for 12h, and naturally cooling; dispersing the obtained material in 100mL of deionized water, stirring, filtering, and carrying out forced air drying at 80 ℃ for 2 hours to obtain a monocrystal cobalt-free aluminum-doped lithium nickelate positive electrode material;
s2, respectively weighing 0.50g of the monocrystal cobalt-free aluminum-doped lithium nickelate positive electrode material prepared by S1 and 0.02g of lithium hydroxide, grinding uniformly in a mortar, placing in a corundum crucible, placing in a tubular furnace filled with oxygen, heating to 700 ℃ at a speed of 10 ℃/min, preserving heat for 2h, and naturally cooling to obtain monocrystal Li 0.996 Ni 0.954 Al 0.050 O 2 And a positive electrode material.
A preparation method of the button cell comprises the following steps: the prepared anode material, super-p conductive agent and polyvinylidene fluoride binder are mixed according to the mass ratio of 8:1:1, adding N-methyl-2-pyrrolidone, mixing to obtain uniform slurry, uniformly coating on aluminum foil by a coating method, drying, rolling, punching into round electrode slices, and vacuum drying at 120 ℃ for 12h; taking the lithium metal plate as a positive electrode and a metal lithium sheet as a negative electrode, and 1M LiPF 6 And EC/DMC/EMC (volume ratio of 1:1:1) as electrolyte, celgard 2500 microporous membrane as separator, assembled into coin cell in glove box.
Example 5:
beta-Li self-precipitation 5 AlO 4 The preparation method of the monocrystalline cobalt-free aluminum doped lithium nickelate anode material with the coating layer comprises the following steps:
s1, respectively weighing 1.00g Ni 0.95 Al 0.05 (OH) 2 Uniformly grinding the precursor, 1.00g of lithium nitrate, 0.40g of lithium chloride and 0.10g of sodium chloride in a mortar, placing the mixture into a corundum crucible, placing the corundum crucible into a tube furnace filled with oxygen, heating to 700 ℃ at a speed of 10 ℃/min, preserving heat for 11h, and naturally cooling; dispersing the obtained material in 100mL of deionized water, stirring, filtering, and carrying out forced air drying at 80 ℃ for 2 hours to obtain a monocrystal cobalt-free aluminum-doped lithium nickelate positive electrode material;
s2, respectively weighing 0.50g of S1 to obtainThe single crystal cobalt-free aluminum doped lithium nickel oxide positive electrode material and 0.04g of lithium nitrate are evenly ground in a mortar, then are placed in a corundum crucible, are placed in a tube furnace filled with oxygen, are heated to 700 ℃ at the speed of 10 ℃/min, are kept for 1h, and are naturally cooled to obtain single crystal Li 1.016 Ni 0.938 Al 0.046 O 2 And a positive electrode material.
A preparation method of the button cell comprises the following steps: the prepared anode material, super-p conductive agent and polyvinylidene fluoride binder are mixed according to the mass ratio of 8:1:1, adding N-methyl-2-pyrrolidone, mixing to obtain uniform slurry, uniformly coating on aluminum foil by a coating method, drying, rolling, punching into round electrode slices, and vacuum drying at 120 ℃ for 12h; taking the lithium metal plate as a positive electrode and a metal lithium sheet as a negative electrode, and 1M LiPF 6 And EC/DMC/EMC (volume ratio of 1:1:1) as electrolyte, celgard 2500 microporous membrane as separator, assembled into coin cell in glove box.
The invention was also subjected to related characterization experiments and performance tests for example 1 and example 2, the specific results are as follows (wherein example 1 appearing in the drawings is example 1, and example 2 is example 2):
FIG. 1 shows the product of example 1 of the present invention with self-precipitating beta-Li 5 AlO 4 Single crystal cobalt-free aluminum doped lithium nickelate positive electrode material with coating layer and Ni used for same 0.95 Al 0.05 (OH) 2 Scanning electron microscopy of the precursor. As can be seen from FIG. 1, the precursor is spherical secondary agglomerate having a particle size of about 5. Mu.m, and has self-precipitating beta-Li 5 AlO 4 The monocrystal cobalt-free aluminum-doped lithium nickel oxide anode material of the coating layer is submicron-sized monocrystal particles with small particle size.
FIG. 2 shows the product of example 1 of the present invention with self-precipitating beta-Li 5 AlO 4 Elemental analysis diagram of a transmission electron microscope of a single crystal cobalt-free aluminum doped lithium nickelate positive electrode material of the coating layer. In fig. 2, a transmission electron microscope image, a superimposed image of Ni and Al spectra, a Ni spectrum and an Al spectrum are sequentially shown from left to right. As can be seen from FIG. 2, a uniform aluminum enriched coating layer was observed on the surface, with a thickness of about 10nm.
FIG. 3 shows the product of example 1 of the present inventionWith self-precipitation of beta-Li 5 AlO 4 X-ray diffraction fine-tuning diagrams of the single crystal cobalt-free aluminum doped lithium nickelate positive electrode material of the coating layer and the single crystal cobalt-free aluminum doped lithium nickelate positive electrode material of the product of the example 2. As can be seen from FIG. 3, the self-precipitated beta-Li 5 AlO 4 The single crystal cobalt-free aluminum doped lithium nickelate anode material of the coating layer has a more ordered layered structure than the single crystal cobalt-free aluminum doped lithium nickelate anode material. In addition, has self-precipitated beta-Li 5 AlO 4 beta-Li is observed in the single crystal cobalt-free aluminum doped lithium nickel oxide positive electrode material of the coating layer 5 AlO 4 The phase, through finishing calculation, the coating layer is 1.05% of the mass fraction of the positive electrode material.
FIGS. 4-7 respectively compare the self-precipitating beta-Li 5 AlO 4 The single crystal cobalt-free aluminum doped lithium nickelate positive electrode material and the single crystal cobalt-free aluminum doped lithium nickelate positive electrode material of the coating layer have the first charge-discharge capacity at 0.1C, the cycle performance curve at 1C, the differential capacitance map at 1C and the multiplying power performances at different multiplying powers. The results show that: with self-precipitating beta-Li 5 AlO 4 The single crystal cobalt-free aluminum doped lithium nickelate positive electrode material of the coating layer has a first charge specific capacity of 242.8mAh g under the current density of 0.1C -1 The specific capacity of the first discharge is 220.2mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the The specific discharge capacity of 100 cycles at 1C is 179.1mAh g -1 The capacity retention was 90.0%; specific discharge capacities at current densities of 2C, 5C and 10C were 196.4, 188.9 and 182.5mAh g, respectively -1 The first charge specific capacity of the monocrystal cobalt-free aluminum doped lithium nickelate positive electrode material under the current density of 0.1C is 239.7mAh g -1 The specific capacity of the first discharge is 201.9mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the The specific discharge capacity of 100 cycles at 1C is 93.7mAh g -1 The capacity retention was 50.9%; in addition, differential capacitance curves indicate that there is self-precipitation of beta-Li 5 AlO 4 The single crystal cobalt-free aluminum doped lithium nickelate positive electrode material of the coating layer can still keep good phase change stability after 100 circles, and the single crystal cobalt-free aluminum doped lithium nickelate positive electrode material observes sharp shift of a phase change peak, which can cause reduction of material stability. Specific discharge capacities at current densities of 2C, 5C and 10C were 180.4, 170.4 and 151.2mAh g, respectively -1 . Compared with a monocrystal cobalt-free aluminum doped lithium nickelate positive electrode material, the self-precipitation beta-Li is provided 5 AlO 4 The monocrystal cobalt-free aluminum-doped lithium nickel oxide positive electrode material of the coating layer has higher specific discharge capacity, cycle stability and rate capability.
In summary, in the preparation method provided by the invention, ni in the molten salt method is changed 0.95 Al 0.05 (OH) 2 The mixing proportion of the precursor, the lithium source and the chloride can obtain the monocrystal cobalt-free lithium nickel oxide anode materials with different lithium/nickel metering ratios and different morphologies. By changing the mixing proportion of the monocrystal cobalt-free aluminum doped lithium nickelate positive electrode material and the lithium source in the secondary lithiation method, the self-precipitation beta-Li with different lithium/nickel metering ratios can be obtained 5 AlO 4 The monocrystal of the coating layer is free of cobalt and aluminum doped with lithium nickelate anode material.
The present invention is not limited to the above embodiments, but is merely preferred embodiments of the present invention, and the present invention should be construed as being limited to the above embodiments as long as the technical effects of the present invention are achieved by the same means. Various modifications and variations are possible in the technical solution and/or in the embodiments within the scope of the invention.
Claims (10)
1. The preparation method of the monocrystal cobalt-free aluminum-doped lithium nickelate positive electrode material with the self-precipitation coating layer is characterized by comprising the following steps of:
s1, ni is mixed with 0.95 Al 0.05 (OH) 2 Uniformly mixing a precursor, a first lithium source and chloride, reacting in an oxygen atmosphere by a molten salt method to obtain an intermediate product, washing the intermediate product with water, and drying to obtain the monocrystal cobalt-free aluminum-doped lithium nickel oxide layered anode material;
s2, uniformly mixing the monocrystal cobalt-free aluminum-doped lithium nickel oxide layered anode material obtained in the step S1 with a second lithium source, and then performing medium-temperature heat treatment in an oxygen atmosphere to obtain the self-precipitation beta-Li 5 AlO 4 A single crystal cobalt-free aluminum doped lithium nickelate anode material of the coating layer;
the dosage of the first lithium source is Ni 0.95 Al 0.05 (OH) 2 105% -130% of the mole fraction of the precursor; the dosage of the second lithium source is less than 30% of the mass fraction of the single crystal cobalt-free aluminum doped lithium nickel oxide layered cathode material obtained in the step S1; the temperature of the medium-temperature heat treatment is 650-750 ℃; said self-precipitating beta-Li 5 AlO 4 The molecular formula of the monocrystal cobalt-free aluminum-doped lithium nickelate positive electrode material of the coating layer is Li 1+x Ni 0.95-y Al 0.05-z O 2 X is more than 0 and less than 0.1, y is more than 0 and less than 0.1, z is more than 0 and less than 0.05, and the grain diameter is 100nm-1 mu m; beta-Li 5 AlO 4 The coating layer is arranged on the self-precipitation beta-Li 5 AlO 4 The mass fraction of the monocrystal cobalt-free aluminum doped lithium nickel oxide anode material of the coating layer is less than 5%.
2. The method according to claim 1, wherein the chloride is at least one of sodium chloride, potassium chloride, lithium chloride, ferric chloride, calcium chloride, and copper chloride.
3. The method of claim 2, wherein the chloride is lithium chloride or sodium chloride.
4. The method according to claim 1, wherein the molten salt method reaction comprises the following specific steps: heating to 650-750 ℃ at a speed of 1-10 ℃/min, and then preserving heat for 10-20 h.
5. The method according to claim 1, wherein the medium temperature heat treatment in S2 is performed by: heating to 650-750 ℃ at a speed of 1-10 ℃/min, and then preserving heat for 1-6 h.
6. The method according to claim 1, wherein the lithium source is at least one of lithium hydroxide, lithium carbonate, lithium nitrate, and lithium acetate.
7. A single crystal cobalt-free aluminum-doped lithium nickelate positive electrode material having a self-precipitating coating layer, characterized by being produced by the production method according to any one of claims 1 to 6.
8. The use of the single crystal cobalt-free aluminum doped lithium nickelate positive electrode material with a self-precipitating coating layer as claimed in claim 7 for preparing a lithium ion battery.
9. A battery positive electrode sheet, characterized in that it is prepared from the single crystal cobalt-free aluminum-doped lithium nickelate positive electrode material with self-precipitation coating layer according to claim 7.
10. The battery positive electrode sheet according to claim 9, wherein the process of manufacturing comprises the steps of: and uniformly mixing the monocrystal cobalt-free aluminum doped lithium nickel oxide anode material with the self-precipitation coating layer, a conductive agent, a binder and a solvent, coating the mixture on a metal matrix, and drying the mixture to obtain the battery anode plate.
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| CN113517424A (en) * | 2021-04-27 | 2021-10-19 | 湖南杉杉能源科技股份有限公司 | Cobalt-free positive electrode material of high-voltage lithium ion battery and preparation method thereof |
| CN114927777A (en) * | 2022-06-10 | 2022-08-19 | 中国科学院化学研究所 | Ultrahigh lithium content material and self-supplementing lithium composite positive electrode material |
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| CN108123105A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of manganese-base oxide positive electrode of electrode layer modification and preparation and application |
| CN113517424A (en) * | 2021-04-27 | 2021-10-19 | 湖南杉杉能源科技股份有限公司 | Cobalt-free positive electrode material of high-voltage lithium ion battery and preparation method thereof |
| CN114927777A (en) * | 2022-06-10 | 2022-08-19 | 中国科学院化学研究所 | Ultrahigh lithium content material and self-supplementing lithium composite positive electrode material |
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| CN117525333A (en) * | 2023-11-16 | 2024-02-06 | 南开大学 | Titanium molten salt-assisted cladding doped monocrystal cobalt-free lithium nickel oxide positive electrode material, and preparation method and application thereof |
| CN117525333B (en) * | 2023-11-16 | 2024-05-28 | 南开大学 | Titanium molten salt-assisted cladding doped monocrystal cobalt-free lithium nickel oxide positive electrode material, and preparation method and application thereof |
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