CN115172713A - Low-residual-alkali cathode material and preparation method and application thereof - Google Patents
Low-residual-alkali cathode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a low residual alkali positive electrode material. According to the invention, residual lithium on the surface of the anode material is consumed through the synergistic action of the aluminum source and the fluoride containing metal, the fluoride has the same lattice constant as that of the matrix of the anode material and can form a good solid solution effect with the layered body structure of the lithium ion material, and an M-O-F surface film [ M is a metal element of the fluoride ] is formed on the surface of the metal, the fluoride is used as a good antifriction material and has excellent lubricating property and film forming property, the coated material has good compressive strength, and the fluoride and the aluminum source consume the residual alkali on the surface to form a stable composite coating layer, so that the residual alkali on the surface of the anode material can be effectively reduced, the direct contact between electrolyte and the anode material is reduced, the dissolution of metal ions of the anode material is effectively prevented, the generation of side reactions is inhibited, and the service life and gas generation performance of the material are improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a low-residual-alkali positive electrode material, and a preparation method and application thereof.
Background
With the popularization and application of portable electronic products and the development of power automobiles such as EVs and HEVs, the lithium ion battery anode material breaks through the bottleneck of the lithium ion battery anode material and develops towards high capacity, long service life, safety, stability and the like. High nickel positive electrode material Li (Ni) x M 1-x )O 2 The cost is lower, the capacity is high and the environment is friendly, and the method is concerned more and more. However, the materials have some problems to be solved in practical application: the surface pH value and the residual alkali content of the high nickel material are high, so that the processing and the storage are difficult, and the prepared battery has serious flatulence; along with the cyclic process, the microstructure of the material changes, finally leading to capacity fading and poor cyclic performance. Therefore, the reduction of the residual alkali on the surface of the nickel-rich material is the focus of research.
At present, the residual alkali on the surface of the high nickel material is reduced by adopting water washing and secondary sintering. The method can obviously reduce the residual alkali on the surface of the material, but the high nickel material treated by the method has the problems of increasing the specific surface area and aggravating the side reaction between the material and the electrolyte, thus reducing the capacity and the cycle performance of the battery. In view of the above, there is a need to provide a modified lithium ion battery cathode material, a preparation method thereof, and a lithium ion battery, wherein the modified lithium ion battery cathode material can significantly reduce the residual alkali on the surface of the material, and can avoid the increase of the specific surface area of the material.
Chinese patent CN 110054226A discloses a preparation method of a low surface residual alkali nickel cobalt manganese ternary positive electrode material, which comprises the specific steps and an implementation mode that boric acid or citric acid is dissolved in ethanol, then the nickel cobalt manganese ternary positive electrode material is added, and H is utilized + Acid-base neutralization reaction with residual alkali on the surface of the material is carried out, and the reaction strength is regulated and controlled by stirring time, so that the residual alkali on the surface of the material can be effectively reduced, and the pH value of the surface of the material is reduced; then using an ethanol solutionAnd washing to ensure that no residual borate ions or citrate ions exist on the surface of the material, and finally removing ethanol molecules possibly remaining on the surface by a secondary calcination method, thereby improving the consistency and stability of the material. However, this method is complicated, and a large amount of ethanol solution is used for washing, which causes waste and safety problems, and is not favorable for production. Chinese patent CN 107732199B discloses a fluorine-containing lithium ion battery anode material and a preparation method thereof, and the method comprises the specific steps and the implementation mode, wherein the high-nickel anode material and a polyfluoro compound-containing raw material (NH) 4 ) a MF b 、(H 3 O) a MF b Or (CSO) 3 ) a MF b Salt solution is mixed, polyfluoro compound raw material is added into solvent, evenly stirred to form aqueous solution, suspension or sol, high-nickel anode material is added into the aqueous solution, suspension or sol to form pasty solid-liquid mixture, then sintering is carried out in inert atmosphere, and high-nickel anode material coated by a coating layer containing polyfluoro compound is obtained, wherein the coating layer is distributed on the surface of the high-nickel anode material, or the polyfluoro compound-containing substance is distributed on the surface of the high-nickel anode material to form the coating layer, and a part of the polyfluoro compound-containing substance permeates into the high-nickel anode material, thereby effectively reducing the residual alkali quantity on the surface of the high-nickel anode material of the lithium ion battery, and improving the processing performance and the electrochemical performance of the high-nickel anode material. However, the method is used for sintering in an inert atmosphere, and the surface defects of the high-nickel material cannot be repaired.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a low residual alkali positive electrode material, and a preparation method and an application thereof.
The invention provides a low residual alkali positive electrode material, which has the following chemical formula:
Li (1+n) Ni (1-a-b-c) Co a M b Q c O 2
wherein a + b is more than 0 and less than or equal to 0.4, b is more than or equal to 0 and less than or equal to 0.2, c is more than 0 and less than or equal to 0.04, and n is more than 0 and less than or equal to 0.060;
m is one or more elements of Mn, al, zr, sr, mg, cr, zr, Y, ta, zn, V, W and B;
q is a coating on the surface of the positive electrode material matrix, the coating is prepared from an aluminum source compound and fluoride, and the fluoride has the same lattice constant as the positive electrode material matrix.
Preferably, the aluminum source compound is at least one selected from aluminum hydroxide, aluminum nitrate, nano-alumina and aluminum phosphate; the fluoride is selected from at least one of strontium fluoride, lanthanum fluoride, nickel fluoride, cobalt fluoride, magnesium fluoride, aluminum fluoride, calcium fluoride, cerium fluoride, yttrium fluoride and zirconium fluoride.
Preferably, the cathode material has a layered crystal structure belonging to space group R-3 m; the coating on the surface of the cathode material is in a discrete island structure.
Preferably, the median particle diameter D50 of the cathode material is in the range of 3.0-15.0 μm, and the specific surface area is 0.65 +/-0.3 m 2 (ii)/g, the compacted density is 3.4 +/-0.4 g/cm 3 。
Preferably, in the ternary cathode material, the aluminum source compound accounts for (0.2-0.8) wt% of the ternary cathode material: 1; the mass percentage of the fluoride in the ternary cathode material is (0.3-0.8) wt%:1.
preferably, the surface residual alkali content of the positive electrode material is less than 0.15%.
The invention also provides a preparation method of the cathode material, which comprises the following steps:
a) Mixing a lithium source compound, a nickel-cobalt-containing compound and a doping element compound, and then sequentially performing ball milling, sintering and crushing to obtain a positive electrode material substrate;
b) And mixing an aluminum source compound, a metal fluoride-containing compound and a positive electrode material matrix, and sintering to obtain the positive electrode material.
Preferably, the lithium source compound is selected from one of lithium hydroxide and lithium carbonate;
the nickel-cobalt-containing compound is selected from one or more of NCA, NCM and NC;
the doping element in the doping element compound is selected from one or more elements of Mn, al, zr, sr, mg, cr, zr, Y, ta, zn, V, W and B;
the aluminum source compound is at least one selected from aluminum hydroxide, aluminum nitrate, nano aluminum oxide and aluminum phosphate;
the metal-containing fluoride is at least one selected from the group consisting of strontium fluoride, lanthanum fluoride, nickel fluoride, cobalt fluoride, magnesium fluoride, aluminum fluoride, calcium fluoride, cerium fluoride, yttrium fluoride, and zirconium fluoride.
Preferably, in the step A), the sintering temperature is 700-950 ℃, and the time is 5-15 h;
in the step B), the sintering temperature is between 300 and 800 ℃, and the heat preservation time is 5 to 15 hours.
The invention also provides a lithium ion battery which comprises the cathode material.
Compared with the prior art, the invention provides a low residual alkali positive electrode material, which has the following chemical formula: li (1+n) Ni (1-a-b-c) Co a M b Q c O 2 Wherein a + b is more than 0 and less than or equal to 0.4, b is more than or equal to 0 and less than or equal to 0.2, c is more than 0 and less than or equal to 0.04, and n is more than 0 and less than or equal to 0.060; m is one or more elements of Mn, al, zr, sr, mg, cr, zr, Y, ta, zn, V, W and B; q is a coating on the surface of the positive electrode material matrix, the coating is an aluminum source compound and fluoride, and the fluoride has the same lattice constant as the positive electrode material matrix.
The fluoride has the same lattice constant as a matrix of the anode material, can form a good solid solution effect with a layered body structure of a lithium ion material, generates an M-O-F surface film on the metal surface [ M is a metal element of the fluoride ], has good lubricating property and film forming property as a good antifriction material, has good compressive strength after being coated, consumes surface residual alkali through the synergistic action of the fluoride and the aluminum source, generates a stable composite coating layer, can effectively reduce the surface residual alkali of the anode material, reduces the direct contact of electrolyte and the anode material, effectively prevents the dissolution of metal ions of the anode material, inhibits the generation of side reactions, and improves the service life and gas production performance of the material.
Drawings
FIG. 1 is an SEM image of magnesium fluoride provided in example 1;
FIG. 2 is an XRD pattern of the comparative and example 1 materials;
FIG. 3 is a SEM image of the surfaces of comparative example and example 1 materials;
FIG. 4 is a graph showing cumulative volume particle size distributions at different pressures for comparative example and example 1.
Detailed Description
The invention provides a low residual alkali positive electrode material, which has the following chemical formula:
Li (1+n) Ni (1-a-b-c) Co a M b Q c O 2
wherein a + b is more than 0 and less than or equal to 0.4, b is more than or equal to 0 and less than or equal to 0.2, and c is more than 0 and less than 0.04;
m is one or more elements of Mn, al, zr, sr, mg, cr, zr, Y, ta, zn, V, W and B;
q is a coating on the surface of the positive electrode material matrix, the coating is an aluminum source compound and fluoride, and the fluoride has the same lattice constant as the positive electrode material matrix.
In the chemical formula, n is more than 0 and less than or equal to 0.060, a + b is more than 0 and less than or equal to 0.4, b is more than or equal to 0 and less than or equal to 0.2, and c is more than 0 and less than 0.04.
M is one or more elements of Mn, al, zr, sr, mg, cr, zr, Y, ta, zn, V, W and B, and Mn is preferred.
Q is a coating on the surface of the positive electrode material, and the coating is prepared from an aluminum source compound and fluoride. Wherein the aluminum source compound is at least one selected from aluminum hydroxide, aluminum nitrate, nano-alumina and aluminum phosphate; the fluoride has a granular structure, and is selected from at least one of strontium fluoride, lanthanum fluoride, nickel fluoride, cobalt fluoride, magnesium fluoride, aluminum fluoride, calcium fluoride, cerium fluoride, yttrium fluoride, and zirconium fluoride. The fluoride has the same lattice constant as the matrix of the positive electrode material: lattice constant a = lattice constant b ≠ lattice constant c, α = β =90 ℃, γ =120 ℃, and can form a good solid solution effect with a lithium ion positive electrode material matrix.
The anode material has a layered crystal structure belonging to a space group R-3 m; the median particle diameter D50 of the cathode material is within the range of 3.0-15.0 μm, preferably any value between 3, 5, 7, 9, 10, 12 and 15 or 3.0-15.0 μm, and the specific surface area is 0.65 +/-0.3 m 2 (ii)/g, the compacted density is 3.4 +/-0.4 g/cm 3 。
In the ternary cathode material, the aluminum source compound is 0.2wt% to 0.8wt%, preferably 0.2wt%, 0.4wt%, 0.6wt%, 0.8wt%, or any value between 0.2wt% to 0.8 wt%; the mass percentage of the fluoride is 0.3wt% to 0.8wt%, preferably 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, or any value between 0.3wt% to 0.8 wt%.
In the invention, the coating on the surface of the cathode material is in a discrete island-shaped structure, and the residual alkali content on the surface of the cathode material is less than 0.15%.
The invention also provides a preparation method of the cathode material, which comprises the following steps:
a) Mixing a lithium source compound, a nickel-cobalt-containing compound and a doping element compound, and then sequentially performing ball milling, sintering and crushing to obtain a positive electrode material substrate;
b) An aluminum source compound, a metal fluoride-containing compound and a positive electrode material substrate are mixed and sintered to obtain a positive electrode material.
Specifically, the lithium source compound, the nickel-cobalt-containing compound and the doping element compound are mixed to obtain a mixture. Wherein the lithium source compound is selected from one of lithium hydroxide and lithium carbonate; the nickel-cobalt-containing compound is selected from one or more of NCA, NCM and NC; the doping element in the doping element compound is selected from one or more elements of Mn, al, zr, sr, mg, cr, zr, Y, ta, zn, V, W and B.
And performing ball milling, sintering and crushing on the mixture in sequence to obtain the anode material matrix. Wherein, the sintering temperature is 700-950 ℃, preferably 700, 750, 800, 850, 900, 950, or any value between 700-950 ℃, and the time is 5-15 h, preferably 5, 8, 10, 12, 15, or any value between 5-15 h. The method of ball milling and pulverizing is not particularly limited in the present invention, and may be a method known to those skilled in the art.
After the positive electrode material matrix is obtained, the positive electrode material matrix is mixed with an aluminum source compound and a metal fluoride-containing compound.
Wherein the aluminum source compound is at least one selected from aluminum hydroxide, aluminum nitrate, nano-alumina and aluminum phosphate; the metal-containing fluoride is at least one selected from the group consisting of strontium fluoride, lanthanum fluoride, nickel fluoride, cobalt fluoride, magnesium fluoride, aluminum fluoride, calcium fluoride, cerium fluoride, yttrium fluoride and zirconium fluoride.
And then, sintering the mixture in a box furnace, wherein the sintering temperature is 300-800 ℃, preferably 300, 400, 500, 600, 700, 800, or any value between 300-800 ℃, and the heat preservation time is 5-15 h, preferably 5, 8, 10, 12, 15, or any value between 5-15 h.
The invention also provides a lithium ion battery which comprises the cathode material.
In the anode material provided by the invention, the fluoride has the same lattice constant as the matrix of the anode material, can form a good solid solution effect with a layered body structure of a lithium ion material, and generates an M-O-F surface film [ M is a metal element of the fluoride ] on the surface of a metal, the coating is stable, the fluoride is used as a good antifriction material and has good lubricating property and film forming property, the coated material has good compressive strength, the surface of the coating is subjected to acid corrosion resistance, the surface residual alkali is consumed by the synergistic action of the fluoride and an aluminum source, a stable composite coating layer is generated, the surface residual alkali of the anode material can be effectively reduced, the direct contact between an electrolyte and the anode material is reduced, the dissolution of metal ions of the anode material is effectively prevented, the generation of side reactions is inhibited, and the service life and the gas production performance of the material are improved.
In addition, the preparation method provided by the invention has the advantages of simple steps, low cost, easiness in operation, short time consumption in the preparation process and contribution to large-scale stable production.
The invention constructs the anode material with an island-shaped structure and a wear-resistant coating layer, which not only effectively consumes residual alkali on the surface, but also generates a layer of wear-resistant lubricating anode material on the surface of the material, is not easy to crack in the process of pole piece roll-to-roll, enhances the particle compressive strength of the material, and has good cycle and safety performance.
In order to further understand the present invention, the following examples are provided to illustrate the low residual alkali cathode material and the preparation method and application thereof, and the scope of the present invention is not limited by the following examples.
Comparative example 1:
(1) Ni prepared by coprecipitation method 0.8 Co 0.1 Mn 0.1 (OH) 2 In a ratio of Li/Me =1.03 with lithium hydroxide, 0.03mol% 2 Mixing uniformly, then sintering the mixture for 15h at the temperature of 750 ℃ in an oxygen atmosphere to obtain the final component Li 1.02 Ni 0.8 Co 0.1 Mn 0.1 O 2 A positive electrode material;
(2) Adding 0.3% of Al to the positive electrode material obtained in the step (1) at 30 ℃ 2 O 3 Uniformly stirring 0.1% of boric acid and an additive, placing the mixture in an oxygen atmosphere at 300 ℃, and sintering the mixture for 10 hours to obtain a surface modified high-nickel multi-element positive electrode material;
(3) The surface-modified high-nickel multi-element positive electrode material is prepared into a button cell taking a metal lithium sheet as a negative electrode for evaluation and test, and the first charge-discharge capacity of 0.2C under the voltage of 3.0-4.25V is shown in the table 1; the surface-modified high-nickel multi-element positive electrode material is prepared into a soft package battery with graphite as a negative electrode to evaluate and test the gas production performance of the battery, the test conditions are that the battery is tested at 70 ℃ for 7 days and 28 days, the volume change rate of the battery is tested, and the storage performance of the battery is shown in table 1;
example 1:
(1) Ni prepared by coprecipitation method 0.8 Co 0.1 Mn 0.1 (OH) 2 Proportion of lithium hydroxide in molar ratio Li/Me =1.03, 0.03mol% 2 Mixing uniformly, and then placing the mixture in an oxygen atmosphereSintering at 750 deg.c for 15 hr to obtain final Li component 1.02 Ni 0.8 Co 0.1 Mn 0.1 O 2 A positive electrode material;
(2) The method comprises the following steps of (1) obtaining a positive electrode material, an aluminum source and a fluoride, wherein the aluminum salt is aluminum hydroxide and is 0.4% by mass relative to the positive electrode material, and the fluoride is magnesium fluoride (see fig. 1, fig. 1 is an SEM image of the magnesium fluoride provided by example 1, wherein the magnesium fluoride is in a round granular structure and has a grain size of 250 +/-30 nm) and 0.35% by mass, uniformly stirring at 30 ℃, placing in an oxygen atmosphere at 500 ℃ and sintering for 10 hours to obtain a surface-modified high-nickel multi-element positive electrode material, and XRD of a comparative example and XRD of example 1 are shown in fig. 2, and the comparative example and the XRD have similar structures and are coated without affecting the structures; the XRD refinement result is shown in Table 1, the material unit cell parameter c/a is more than 4.9, and the material has a better space group R-3m laminated structure (I) 006 +I 102 )/I 101 Values are often used to judge the order of hexagonal close-packed structures, which indicate the order of hexagonal crystal structures, both having similar crystal structures. (ii) a
(3) The positive electrode material obtained in example 1 was coated at a coating area density of 0.018g/cm and an active material ratio of 96.5% 2 The negative electrode adopts artificial graphite, the diaphragm is a PP/PE/PP three-layer diaphragm, and the electrolyte is 1.0MLiPF 6 The electrolyte solution of EC/DMC/EMC (1; SEM of the materials of the control group and example 1 is shown in FIG. 3, and it can be seen from FIG. 3 that the control group is coated with Al as compared with example 1 in FIG. 3 2 O 3 And boric acid, the boric acid can be melted at a lower temperature and can be coated at the grain boundary, so that the boric acid has a better protection effect, a small amount of coating is arranged on the surface of the material, aluminum fluoride and aluminum hydroxide are coated in the embodiment 1, more white point-like substances are distributed on the surface, are positioned on the surface and the interface of the primary particles, and are distributed in a discrete island shape. The positive electrode material obtained in example 1 was coated at a coating surface density of 0.016g/cm with an active material ratio of 94.5% 2 The negative electrode is made of artificialGraphite, the diaphragm is a PP/PE/PP three-layer diaphragm, the electrolyte is an EC/DMC/EMC (1. The double coating of the comparative example group has stronger protection effect on the surface of the positive electrode material, but has weaker protection effect after long-term high-temperature storage, gas generation performance is poorer after long-term high-temperature storage, and the fluoride double-coating material forms a stable coating layer with stronger protection effect on the surface. From the comparative example and example data in table 1, it can be concluded that the first effect of the three positive electrode materials NCM, NCA and NC is improved and the long-term high-temperature storage is effectively improved after the coating improvement.
(4) Method for characterization of particle pressure resistance of control and example 1 materials: the cumulative volume particle size distribution plot is obtained from the external super-particle size measurements after application of 0/150/250/300MPa pressure on the powder compaction instrument, as shown in FIG. 4. As can be seen from FIG. 4, the small particle size ratio in the cumulative volume particle size distribution of the comparative example increased with an increase in pressure, indicating that the particles in the comparative example were crushed with an increase in pressure, the overall particle size distribution shifted toward the small particle size, and the small particles increased, indicating that the compressive strength of the particles in the comparative example was poor; in example 1, the pressure was increased, and the cumulative volume particle size distribution did not change much, indicating that although there were small particles, the small particles did not increase with the increase in pressure, indicating that the compressive strength of the particles in example 1 was high.
Example 2:
(1) Ni prepared by coprecipitation method 0.9 Co 0.05 Mn 0.05 (OH) 2 Mixing with lithium hydroxide at a molar ratio of Li/Me =1.03 and 0.04mol% of ZrO2, and sintering the mixture at 720 deg.C in oxygen atmosphere for 10h to obtain the final composition of Li 1.02 Ni 0.9 Co 0.05 Mn 0.05 O 2 A positive electrode material;
(2) Uniformly stirring the positive electrode material obtained in the step (1), an aluminum source and a fluoride, wherein the aluminum salt is nano aluminum oxide and accounts for 0.3 mass percent, the fluoride is lanthanum fluoride and accounts for 0.5 mass percent at the temperature of 30 ℃, and then, placing the mixture in an oxygen atmosphere at the temperature of 600 ℃ for sintering for 10 hours to obtain a surface-modified high-nickel multi-element positive electrode material;
(3) The surface-modified high-nickel multi-element cathode material is prepared into a button cell taking a metal lithium sheet as a cathode for evaluation test, and the first charge-discharge capacity of 0.2C under the voltage of 3.0-4.25V is shown in the table 1; the surface-modified high-nickel multi-element positive electrode material is prepared into a soft package battery taking graphite as a negative electrode for evaluation and test, and the storage performance of the battery is greatly improved after the coating modification.
Example 3:
(1) Ni prepared by coprecipitation method 0.8 Co 0.1 Mn 0.1 (OH) 2 Ratio with lithium hydroxide in mol ratio Li/Me =1.04, 0.025mol% 3 Uniformly mixing, then sintering the mixture for 12h at 820 ℃ in an oxygen atmosphere to obtain the final component Li 1.03 Ni 0.8 Co 0.1 Mn 0.1 O 2 A positive electrode material;
(2) Uniformly stirring the positive electrode material obtained in the step (1), an aluminum source and fluoride, wherein the aluminum salt is nano aluminum oxide with the mass percent of 0.4%, the fluoride is yttrium fluoride with the mass percent of 0.35%, at the temperature of 30 ℃, placing the mixture in an oxygen atmosphere at the temperature of 550 ℃, and sintering the mixture for 10 hours to obtain a surface-modified high-nickel multi-element positive electrode material;
(3) The surface-modified high-nickel multi-element cathode material is prepared into a button cell taking a metal lithium sheet as a cathode for evaluation test, and the first charge-discharge capacity of 0.2C under the voltage of 3.0-4.25V is shown in the table 1; the surface-modified high-nickel multi-element positive electrode material is prepared into a soft package battery with graphite as a negative electrode for evaluation and test, and the storage performance of the battery is greatly improved after the coating modification.
Example 4:
(1) Ni prepared by coprecipitation method 0.7 Co 0.1 Mn 0.2 (OH) 2 Mixing with lithium hydroxide at a ratio of Li/Me =1.03 by mol of 0.025mol% SrO, and sintering the mixture at high temperature in an oxygen atmosphere for 15h to obtain a final composition of Li 1.02 Ni 0.7 Co 0.1 Mn 0.2 O 2 A positive electrode material;
(2) Uniformly stirring the positive electrode material obtained in the step (1), an aluminum source and fluoride, wherein the aluminum salt is nano aluminum oxide with the mass percent of 0.4%, the fluoride is cerium fluoride with the mass percent of 0.35%, at the temperature of 30 ℃, placing the mixture in an oxygen atmosphere at the temperature of 300 ℃, and sintering the mixture for 10 hours to obtain a surface-modified high-nickel multi-element positive electrode material;
(3) The surface-modified high-nickel multi-element cathode material is prepared into a button cell taking a metal lithium sheet as a cathode for evaluation test, and the first charge-discharge capacity of 0.2C under the voltage of 3.0-4.25V is shown in the table 1; the surface-modified high-nickel multi-element positive electrode material is prepared into a soft package battery with graphite as a negative electrode for evaluation and test, and the storage performance of the battery is greatly improved after the coating modification.
Example 5:
(1) Ni prepared by coprecipitation method 0.6 Co 0.1 Mn 0.3 (OH) 2 Mixing with lithium hydroxide at a molar ratio of Li/Me =1.03, 0.035mol% ZrO2, and sintering the mixture at 850 deg.C for 10h in oxygen atmosphere to obtain the final component Li 1.02 Ni 0.6 Co 0.1 Mn 0.3 O 2 A positive electrode material;
(2) Uniformly stirring the positive electrode material obtained in the step (1), an aluminum source and fluoride, wherein the aluminum salt is alumina and accounts for 0.3 mass percent, the fluoride is cerium fluoride and accounts for 0.4 mass percent relative to the positive electrode material at the temperature of 30 ℃, and then, placing the positive electrode material in an oxygen atmosphere at the temperature of 400 ℃ and sintering the positive electrode material for 10 hours to obtain a surface-modified high-nickel multi-element positive electrode material;
(3) The surface-modified high-nickel multi-element positive electrode material is prepared into a button cell taking a metal lithium sheet as a negative electrode for evaluation and test, and the first charge-discharge capacity of 0.2C under the voltage of 3.0-4.25V is shown in the table 1; the surface-modified high-nickel multi-element positive electrode material is prepared into a soft package battery taking graphite as a negative electrode for evaluation and test, and the storage performance of the battery is greatly improved after the coating modification.
Example 6:
(1) Co-precipitationNi prepared by the method 0.6 Co 0.2 Mn 0.2 (OH) 2 Mixing with lithium hydroxide at a molar ratio of Li/Me =1.03 and 0.035mol% ZrO2, and sintering the mixture at 840 deg.C in an oxygen atmosphere for 10h to obtain the final composition of Li 1.02 Ni 0.6 Co 0.1 Mn 0.3 O 2 A positive electrode material;
(2) Uniformly stirring the positive electrode material obtained in the step (1), an aluminum source and fluoride, wherein the aluminum salt is alumina and the fluoride is zirconium fluoride, the aluminum salt is 0.3 percent by mass and the fluoride is 0.4 percent by mass relative to the positive electrode material, and then placing the mixture in an oxygen atmosphere at 600 ℃ for sintering for 10 hours to obtain a surface-modified high-nickel multi-element positive electrode material;
(3) The surface-modified high-nickel multi-element cathode material is prepared into a button cell taking a metal lithium sheet as a cathode for evaluation test, and the first charge-discharge capacity of 0.2C under the voltage of 3.0-4.25V is shown in the table 1; the surface-modified high-nickel multi-element positive electrode material is prepared into a soft package battery with graphite as a negative electrode for evaluation and test, and the storage performance of the battery is greatly improved after the coating modification.
NCA comparative example 2:
(1) Ni prepared by coprecipitation method 0.9 Co 0.05 Al 0.05 (OH) 2 Proportion of lithium hydroxide in mol ratio Li/Me =1.03, 0.035mol% 2 Mixing uniformly, then sintering the mixture for 10h in an oxygen atmosphere at 835 ℃ to obtain the final component Li 1.02 Ni 0.9 Co 0.05 Al 0.05 O 2 A positive electrode material;
(2) Uniformly stirring the positive electrode material obtained in the step (1) and an aluminum source, wherein the aluminum salt is aluminum oxide and accounts for 0.3 percent of the mass of the positive electrode material at 30 ℃, and then, placing the mixture in an oxygen atmosphere at 500 ℃ for sintering for 10 hours to obtain a surface-modified high-nickel multi-element positive electrode material;
(3) The surface-modified high-nickel multi-element positive electrode material is prepared into a button cell taking a metal lithium sheet as a negative electrode for evaluation and test, and the first charge-discharge capacity of 0.2C under the voltage of 3.0-4.25V is shown in the table 1; the surface-modified high-nickel multi-element positive electrode material is prepared into a soft package battery with graphite as a negative electrode for evaluation and test, and the storage performance of the battery is greatly improved after the coating modification.
NCA example 7:
(1) Ni prepared by coprecipitation method 0.9 Co 0.05 Al 0.05 (OH) 2 Proportion of lithium hydroxide in mol ratio Li/Me =1.03, 0.035mol% 2 Uniformly mixing, then sintering the mixture for 10 hours at 840 ℃ in an oxygen atmosphere to obtain the final component Li 1.02 Ni 0.9 Co 0.05 Al 0.05 O 2 A positive electrode material;
(2) Uniformly stirring the positive electrode material obtained in the step (1), an aluminum source and fluoride, wherein the aluminum salt is alumina and the fluoride is cerium fluoride, the mass percent of the aluminum salt is 0.2%, and the mass percent of the fluoride is 0.4% relative to that of the positive electrode material at 30 ℃, then placing the positive electrode material in an oxygen atmosphere at 500 ℃ and sintering the positive electrode material for 10 hours to obtain a surface-modified high-nickel multi-element positive electrode material;
(3) The surface-modified high-nickel multi-element cathode material is prepared into a button cell taking a metal lithium sheet as a cathode for evaluation test, and the first charge-discharge capacity of 0.2C under the voltage of 3.0-4.25V is shown in the table 1; the surface-modified high-nickel multi-element positive electrode material is prepared into a soft package battery taking graphite as a negative electrode for evaluation and test, and the storage performance of the battery is greatly improved after the coating modification.
NC comparative example 3:
(1) Ni prepared by coprecipitation method 0.85 Co 0.15 (OH) 2 At a ratio of Li/Me =1.03 to lithium hydroxide, 0.035mol% 2 Uniformly mixing, then sintering the mixture for 10h at 850 ℃ in an oxygen atmosphere to obtain the final component Li 1.02 Ni 0.85 Co 0.15 O 2 A positive electrode material;
(2) Uniformly stirring the positive electrode material obtained in the step (1) and an aluminum source, wherein the aluminum salt is aluminum oxide and accounts for 0.3 percent of the mass of the positive electrode material at 30 ℃, and then, placing the mixture in an oxygen atmosphere at 500 ℃ for sintering for 10 hours to obtain a surface-modified high-nickel multi-element positive electrode material;
(3) The surface-modified high-nickel multi-element cathode material is prepared into a button cell taking a metal lithium sheet as a cathode for evaluation test, and the first charge-discharge capacity of 0.2C under the voltage of 3.0-4.25V is shown in the table 1; the surface-modified high-nickel multi-element positive electrode material is prepared into a soft package battery with graphite as a negative electrode for evaluation and test, and the storage performance of the battery is greatly improved after the coating modification.
NC example 8:
(1) Ni prepared by coprecipitation method 0.85 Co 0.15 (OH) 2 Mixing with lithium hydroxide at a molar ratio of Li/Me =1.03 and 0.035mol% ZrO2, and sintering the mixture at 840 deg.C in an oxygen atmosphere for 10h to obtain the final composition of Li 1.02 Ni 0.85 Co 0.15 O 2 A positive electrode material;
(2) Uniformly stirring the positive electrode material obtained in the step (1), an aluminum source and fluoride, wherein the aluminum salt is alumina and the mass percent of the aluminum salt is 0.3%, the fluoride is cobalt fluoride and the mass percent of the aluminum salt is 0.4% relative to the positive electrode material at 30 ℃, then placing the mixture in an oxygen atmosphere at 450 ℃ and sintering the mixture for 10 hours to obtain a surface-modified high-nickel multi-element positive electrode material;
(3) The surface-modified high-nickel multi-element positive electrode material is prepared into a button cell taking a metal lithium sheet as a negative electrode for evaluation and test, and the first charge-discharge capacity of 0.2C under the voltage of 3.0-4.25V is shown in the table 1; the surface-modified high-nickel multi-element positive electrode material is prepared into a soft package battery taking graphite as a negative electrode for evaluation and test, and the storage performance of the battery is greatly improved after the coating modification.
TABLE 1 results of RieTveld refinement of example 1 and the comparative groups
TABLE 2 table of physicochemical and electrical properties data for comparative and examples
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A low residual alkali positive electrode material is characterized by having the following chemical formula:
Li (1+n) Ni (1-a-b-c) Co a M b Q c O 2
wherein a + b is more than 0 and less than or equal to 0.4, b is more than or equal to 0 and less than or equal to 0.2, c is more than 0 and less than or equal to 0.04, and n is more than 0 and less than or equal to 0.060;
m is one or more elements of Mn, al, zr, sr, mg, cr, zr, Y, ta, zn, V, W and B;
q is a cladding material on the surface of the matrix of the cathode material, the cladding material is prepared from an aluminum source compound and fluoride, and the fluoride has the same lattice constant with the matrix of the cathode material.
2. The positive electrode material as claimed in claim 1, wherein the aluminum source compound is at least one selected from the group consisting of aluminum hydroxide, aluminum nitrate, nano-alumina, and aluminum phosphate; the fluoride is selected from at least one of strontium fluoride, lanthanum fluoride, nickel fluoride, cobalt fluoride, magnesium fluoride, aluminum fluoride, calcium fluoride, cerium fluoride, yttrium fluoride and zirconium fluoride.
3. The positive electrode material according to claim 1, characterized in that the positive electrode material has a layered crystal structure belonging to space group R-3 m; the coating on the surface of the cathode material is in a discrete island structure.
4. According to claim 1The positive electrode material is characterized in that the median particle diameter D50 of the positive electrode material is within a range of 3.0 to 15.0 [ mu ] m, and the specific surface area is 0.65 +/-0.3 m 2 Per g, the compacted density is 3.4 +/-0.4 g/cm 3 。
5. The positive electrode material according to claim 1, wherein the aluminum source compound is contained in the ternary positive electrode material in an amount of (0.2 to 0.8) wt%:1; the mass percentage of the fluoride in the ternary cathode material is (0.3-0.8) wt%:1.
6. the positive electrode material according to claim 1, wherein the amount of residual alkali on the surface of the positive electrode material is less than 0.15%.
7. A method for producing a positive electrode material according to any one of claims 1 to 6, comprising the steps of:
a) Mixing a lithium source compound, a nickel-containing compound and a doping element compound, and then sequentially performing ball milling, sintering and crushing to obtain a positive electrode material matrix;
b) And mixing an aluminum source compound, a metal fluoride-containing compound and a positive electrode material matrix, and sintering to obtain the positive electrode material.
8. The production method according to claim 7, wherein the lithium source compound is one selected from lithium hydroxide and lithium carbonate;
the nickel-containing compound is selected from nickel-cobalt-containing compounds selected from one or more of NCA, NCM and NC three types of materials;
the doping element in the doping element compound is selected from one or more elements of Mn, al, zr, sr, mg, cr, zr, Y, ta, zn, V, W and B;
the aluminum source compound is at least one selected from aluminum hydroxide, aluminum nitrate, nano aluminum oxide and aluminum phosphate;
the metal-containing fluoride is at least one selected from the group consisting of strontium fluoride, lanthanum fluoride, nickel fluoride, cobalt fluoride, magnesium fluoride, aluminum fluoride, calcium fluoride, cerium fluoride, yttrium fluoride and zirconium fluoride.
9. The method according to claim 7, wherein in step A), the sintering temperature is 700-950 ℃ and the sintering time is 5-15 h;
in the step B), the sintering temperature is between 300 and 800 ℃, and the heat preservation time is 5 to 15 hours.
10. A lithium ion battery comprising the positive electrode material according to any one of claims 1 to 6.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115745021A (en) * | 2022-11-15 | 2023-03-07 | 乳源东阳光新能源材料有限公司 | Method for removing residual lithium in high-nickel ternary cathode material |
| CN116332250A (en) * | 2023-05-29 | 2023-06-27 | 四川新能源汽车创新中心有限公司 | Positive electrode material, preparation method thereof and solid-state battery |
| CN117117110A (en) * | 2023-01-03 | 2023-11-24 | 宁夏汉尧富锂科技有限责任公司 | Modification method of ternary positive electrode material, modified ternary positive electrode material and lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115745021A (en) * | 2022-11-15 | 2023-03-07 | 乳源东阳光新能源材料有限公司 | Method for removing residual lithium in high-nickel ternary cathode material |
| CN115745021B (en) * | 2022-11-15 | 2024-05-31 | 乳源东阳光新能源材料有限公司 | Method for removing residual lithium in high-nickel ternary cathode material |
| CN117117110A (en) * | 2023-01-03 | 2023-11-24 | 宁夏汉尧富锂科技有限责任公司 | Modification method of ternary positive electrode material, modified ternary positive electrode material and lithium ion battery |
| CN117117110B (en) * | 2023-01-03 | 2024-06-11 | 宁夏汉尧富锂科技有限责任公司 | Modification method of ternary positive electrode material, modified ternary positive electrode material and lithium ion battery |
| CN116332250A (en) * | 2023-05-29 | 2023-06-27 | 四川新能源汽车创新中心有限公司 | Positive electrode material, preparation method thereof and solid-state battery |
| CN116332250B (en) * | 2023-05-29 | 2023-09-08 | 四川新能源汽车创新中心有限公司 | Positive electrode material, preparation method thereof and solid-state battery |
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