HIGH-VOLTAGE TERNARY POSITIVE ELECTRODE MATERIAL FOR LITHIUM-ION BATTERY AND PREPARATION METHOD THEREOF

Abstract

The present invention discloses a high-voltage ternary positive electrode material for lithium-ion battery and preparation method thereof. The chemical formula of the material is LiNi.sub.0.6-xMg.sub.xCo.sub.0.2-yAl.sub.yMn.sub.0.2-zTi.sub.zO.sub.2-dF.sub.d, wherein 0<x,y,z,d0.05. The precursor of the positive electrode material is synthesized by gradient co-precipitation method and the positive electrode material is prepared by solid phase method. The content of nickel in the synthesized precursor particles has a gradient distribution from the inside to the outside. The obtained precursor is mixed and grinded evenly with the lithium source and the fluorine source at a certain ratio and put into the tube furnace. The obtained precursor is then pre-sintered in the oxygen-enriched air atmosphere and then heated up to be sintered, to obtain the target product. The positive electrode material for lithium-ion battery prepared by the method is free from impurity phase and has a good crystallinity, which is a high energy density positive electrode material.

Claims

1. A high-voltage ternary positive electrode material of a lithium-ion battery, wherein a molecular formula of the positive electrode material of the lithium-ion battery is LiNi.sub.0.6-xMg.sub.xCo.sub.0.2-yAl.sub.yMn.sub.0.2-zTizO.sub.2-dF.sub.d, wherein 0<x, y, z, d0.05.

2. A method for preparing a high-voltage ternary positive electrode material of a lithium-ion battery, wherein a molecular formula of the positive electrode material of the lithium-ion battery is LiNi.sub.0.6-xMg.sub.xCo.sub.0.2-yAl.sub.yMn.sub.0.2-zTizO.sub.2-dF.sub.d, wherein 0<x, y, z, d0.05; wherein the method comprises the following steps: step 1: weighing a sample including a nickel source material, a magnesium source material, a cobalt source material, an aluminum source material, a manganese source material and, a titanium source material at a molar ratio of Ni:Mg:Co:Al:Mn:Ti=(0.6-x):x:(0.2-y):y:(0.2-z):z; dividing the sample into two parts at molar ratios of (Ni+Mg):(Co+Al):(Mn+Ti)=5:2:3 and 7:2:1 respectively, and dissolving the two parts respectively in an appropriate amount of deionized water to obtain a solution a and a solution b; step 2, mixing a sodium hydroxide solution with ammonia to form a solution c, wherein the solution c is composed of the sodium hydroxide at a concentration of 2.0 mol/L and the ammonia at a concentration of 0.5 mol/L; step 3, slowly and uniformly dropping the solution a and the solution c into a beaker containing deionized water, and then slowly and uniformly dropping the solution b and the solution c into the beaker and placing the beaker in a water bath at a temperature of 50 to 80 C. and stirring continuously; step 4, adding the ammonia into a mixed solution obtained from the step 3, adjusting pH to be around 11, and stirring continuously for 5 hours, then raising the temperature to 70 C. and aging for 12 hours; step 5, filtering and washing a product obtained from the step 4 several times until no sulfate ion is detected using BaCl.sub.2 solution, and then drying the product in a blast oven and grinding the product evenly; step 6, mixing a precursor obtained from the step 5 with a lithium source and a fluorine source, grinding a mixture evenly and drying the mixture using absolute ethanol as a dispersant; step 7, grinding the mixture obtained from the step 6 evenly, and putting the mixture in a tube furnace, raising a temperature to 450-550 C. at 5 C./min in an oxygen-enriched air atmosphere, and pre-sintering the mixture for 5-10 hours; then raising the temperature to 700-850 C. at 2 C./min, and sintering the mixture for 10-24 hours; grinding the product after natural cooling in the oxygen-enriched atmosphere, and obtaining the positive electrode material LiNi.sub.0.6-xMg.sub.xCo.sub.0.2-yAl.sub.yMn.sub.0.2-zTizO.sub.2-dF.sub.d of the lithium-ion battery, wherein the positive electrode material has a layered structure, and nickel has gradient distribution in particles.

3. The method for preparing a high-voltage ternary positive electrode material of a lithium-ion battery according to claim 2, wherein in the step 6, a molar ratio of a lithium source material, the nickel source material, the magnesium source material, the cobalt source material, the aluminum source, the manganese source material, the titanium source material and a fluorine source material is (1-1.1):(0.6-x):x:(0.2-y):y:(0.2-z):z:d.

4. The method for preparing a high-voltage ternary positive electrode material of a lithium-ion battery according to claim 2, wherein in the step 1, the nickel source material is at least one material selected from the group consisting of nickel sulfate, nickel nitrate, nickel acetate, nickel chloride and nickel hydroxide.

5. The method for preparing a high-voltage ternary positive electrode material of a lithium-ion battery according to claim 2, wherein in the step 1, the magnesium source material is at least one material selected from the group consisting of magnesium sulfate, magnesium nitrate, magnesium acetate, magnesium chloride, magnesium oxide, and magnesium hydroxide.

6. The method for preparing a high-voltage ternary positive electrode material of a lithium-ion battery according to claim 2, wherein in the step 1, the cobalt source material is at least one material selected from the group consisting of cobalt sulfate, cobalt nitrate, cobalt acetate, cobalt chloride and a hydroxide of cobalt and an oxide of cobalt.

7. The method for preparing a high-voltage ternary positive electrode material of a lithium-ion battery according to claim 2, wherein in the step 1, the aluminum source material is at least one material selected from the group consisting of aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum hydroxide and an oxide of aluminum.

8. The method for preparing a high-voltage ternary positive electrode material of a lithium-ion battery according to claim 2, wherein in the step 1, the manganese source material is at least one material selected from the group consisting of manganese sulfate, manganese nitrate, manganese acetate, manganese chloride and a hydroxide of manganese and an oxide of manganese, wherein the hydroxide of manganese and the oxide of manganese is any one of chemical manganese dioxide and electrolytic manganese dioxide.

9. The method for preparing a high-voltage ternary positive electrode material of a lithium-ion battery according to claim 2, wherein in the step 1, the titanium source material is at least one material selected from the group consisting of butyl titanate, titanyl sulfate and titanium dioxide.

10. The method for preparing a high-voltage ternary positive electrode material of a lithium-ion battery according to claim 2, wherein in the step 6, the lithium source material is at least one material selected from the group consisting of lithium carbonate, lithium nitrate, lithium acetate, lithium chloride and lithium hydroxide, and the fluorine source material is at least one material selected from the group consisting of lithium fluoride and ammonium fluoride.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the embodiments of the present invention or the technical solutions, the accompanying drawings needed in the embodiments or the description will be simply introduced as below. It will be apparent that the drawings in the following description are merely some examples of the present invention, and other drawings can be obtained by the ordinary person skilled in the art without creative work.

[0029] FIG. 1 is a process flow chart of preparing the precursor of the positive electrode material LiNi.sub.0.6-xMg.sub.xCo.sub.0.2-yAl.sub.yMn.sub.0.2-zTi.sub.zO.sub.2-dF.sub.d of lithium-ion batteries of the present invention.

[0030] FIG. 2 is a process flow chart of preparing the positive electrode material LiNi.sub.0.6-xMg.sub.xCo.sub.0.2-yAl.sub.yMn.sub.0.2-zTi.sub.zO.sub.2-dF.sub.d of lithium-ion batteries of the present invention.

[0031] FIG. 3 is an XRD diagram of preparing the positive electrode material LiNi.sub.0.6-xMg.sub.xCo.sub.0.2-yAl.sub.yMn.sub.0.2-zTi.sub.zO.sub.2-dF.sub.d of lithium-ion batteries of the present invention.

[0032] FIG. 4 is a SEM diagram of preparing the positive electrode material LiNi.sub.0.6-xMg.sub.xCo.sub.0.2-yAl.sub.yMn.sub.0.2-zTi.sub.zO.sub.2-dF.sub.d of lithium-ion batteries of the present invention.

[0033] FIG. 5 is an initial charge and discharge curve of preparing the positive electrode material LiNi.sub.0.6-xMg.sub.xCo.sub.0.2-yAl.sub.yMn.sub.0.2-zTi.sub.zO.sub.2-dF.sub.d of lithium-ion batteries of the present invention, wherein the batteries are charged and discharged with a 0.5 C ratio constant current within a voltage range of 2.7-4.5V at room temperature.

[0034] FIG. 6 is a cycling performance diagram of preparing the positive electrode material LiNi.sub.0.6-xMg.sub.xCo.sub.0.2-yAl.sub.yMn.sub.0.2-zTi.sub.zO.sub.2-dF.sub.d of lithium-ion batteries of the present invention, wherein the batteries are charged and discharged with a 0.5 C ratio constant current within a voltage range of 2.7-4.5V at room temperature.

DETAILED DESCRIPTION OF THE INVENTION

[0035] The technical solutions described in the embodiments of the present invention will now be clearly and completely described, with reference to the accompanying drawings in the embodiments of the present invention. It will be apparent that the described embodiments are merely a part of the embodiments of the invention and are not intended to be exhaustive. Based on embodiments in the present invention, all other embodiments obtained by the ordinary person skilled in the art without creative work fall within the scope of the present invention.

Embodiment 1

[0036] When doping amounts of Mg, Al, Ti, and F are 0.02, 0.03, 0.02 and 0.02 respectively, a sample including the nickel source material, the magnesium source material, the cobalt source material, the aluminum source material, the manganese source material and the titanium source material is weighed at a molar ratio of Ni:Mg:Co:Al:Mn:Ti=(0.6-x):x:(0.2-y):y:(0.2-z):z, and divided into two parts. And then, the two parts are respectively dissolved at molar ratios of (Ni+Mg):(Co+Al):(Mn+Ti)=5:2:3 and 7:2:1 in an appropriate amount of deionized water to prepare 1 mol/L of the mixed sulfate solutions a and b. Sodium hydroxide solution and ammonia are mixed into a mixed solution referred to as a solution c, wherein the solution c is composed of the sodium hydroxide at a concentration of 2.0 mol/L and ammonia at a concentration of 0.5 mol/L. The prepared solutions a and b are respectively slowly dropped into a reaction vessel with the solution c and stirred continuously. The pH is adjusted to be around 11 by adding the ammonia. The reaction temperature is 50 C., and the co-precipitation is conducted for 5 hours, and then aging is conducted for 12 hours at 70 C. The product is then filtered and washed several times until no sulfate ion is detected using BaCl.sub.2 solution, and then the product is dried and grinded to obtain spherical precursor powder. 0.108 mol of LiOH.H.sub.2O, 9.1102 g of the precursor powder and 0.055 g of LiF are weighed and mixed together with absolute ethanol which acts as a dispersant, and fully ground evenly, and then placed in a blast oven to be dried and finely grind, and finally placed in a tube furnace. Temperature is raised to 500 C. at a rate of 5 C./min in an oxygen-enriched air atmosphere (flow rate 500 ml/min), so that pre-sintering is conducted for 5 hours under the temperature of 500 C., and then temperature is raised to 725 C. at a rate of 2 C./min and sintering is conducted for 15 hours. Finally, natural cooling is conducted in the oxygen-enriched atmosphere, and the product is taken out and grinded finely, to obtain the target product LiNi.sub.0.58Mg.sub.0.02Co.sub.0.17Al.sub.0.03Mn.sub.0.18Ti.sub.0.02O.sub.1.98F.sub.0.02 of the positive electrode material.

[0037] A constant current charge and discharge test is conducted on the prepared positive electrode material LiNi.sub.0.58Mg.sub.0.02Co.sub.0.17Al.sub.0.03Mn.sub.0.18Ti.sub.0.02O.sub.1.98F.sub.0.02 of lithium-ion batteries. According to the test results, it shows that the positive electrode material has an excellent discharge specific capacity. At room temperature, when the charge and discharge voltage range is 2.7-4.5V and the constant current charge and discharge ratio is 0.5 C, the initial discharge specific capacity of the positive electrode material for lithium-ion batteries can reach 250.9 mAh.Math.g.sup.1. Further, the discharge specific capacity is still 186.3 mAh.Math.g.sup.1 after 50 times of charging and discharging cycles, and the capacity retention rate is 74.3%.

Embodiment 2

[0038] When doping amounts of Mg, Al, Ti, and F are 0.01, 0.04, 0.01 and 0.05 respectively, a sample including the nickel source material, the magnesium source material, the cobalt source material, the aluminum source material, the manganese source material and the titanium source material is weighed at a molar ratio of Ni:Mg:Co:Al:Mn:Ti=(0.6-x):x:(0.2-y):y:(0.2-z): z, and divided into two parts. And then, the two parts are respectively dissolved at molar ratios of (Ni+Mg):(Co+Al):(Mn+Ti)=5:2:3 and 7:2:1 in an appropriate amount of deionized water to prepare the 1 mol/L of the mixed sulfate solutions a and b. Sodium hydroxide solution and ammonia are mixed into a mixed solution referred to as a solution c, wherein the solution c is composed of the sodium hydroxide at a concentration of 2.0 mol/L and ammonia at a concentration of 0.5 mol/L. The prepared solutions a and b are respectively slowly dropped into a reaction vessel with the solution c and stirred continuously. The pH is adjusted to be around 11 by adding the ammonia. The reaction temperature is 60 C., and the co-precipitation is conducted for 5 hours, and then aging is conducted for 12 hours at 70 C. The product is then filtered and washed several times until no sulfate ion is detected using BaCl.sub.2 solution, and then the product is dried and grinded to obtain spherical precursor powder. 0.105 mol of LiOH.H.sub.2O, 9.1062 g of the precursor powder and 0.128 g of LiF are weighed and mixed together with absolute ethanol which acts as a dispersant, and fully grinded evenly, and then placed in a blast oven to be dried and finely grind, and finally placed in a tube furnace. Temperature is raised to 500 C. at a rate of 5 C./min in an oxygen-enriched air atmosphere (flow rate 500 ml/min), so that pre-sintering is conducted for 5 hours under 500 C. And then temperature is raised to 725 C. at a rate of 2 C./min and sintering is conducted for 15 hours. Finally, natural cooling is conducted in the oxygen-enriched atmosphere, the product is taken out and grinded finely, to obtain the target product LiNi.sub.0.59Mg.sub.0.01Co.sub.0.16Al.sub.0.04Mn.sub.0.19Ti.sub.0.01O.sub.1.95F.sub.0.05 of the positive electrode material.

[0039] A constant current charge and discharge test is conducted on the prepared positive electrode material LiNi.sub.0.59Mg.sub.0.01Co.sub.0.16Al.sub.0.04Mn.sub.0.19Ti.sub.0.01O.sub.1.95F.sub.0.05 of lithium-ion batteries. According to the test results, it shows that the positive electrode material still has an excellent discharge specific capacity and better cycling performance.

Embodiment 3

[0040] When doping amounts of Mg, Al, Ti, and F are 0.05, 0.05, 0.05 and 0.05 respectively, a sample including the nickel source material, the magnesium source material, the cobalt source material, the aluminum source material, the manganese source material and the titanium source material is weighed the sample at a molar ratio of Ni:Mg:Co:Al:Mn:Ti=(0.6-x):x:(0.2-y):y:(0.2-z):z, and divided into two parts. And then, the two parts are respectively dissolved at molar ratios of (Ni+Mg):(Co+Al):(Mn+Ti)=5:2:3 and 7:2:1 in an appropriate amount of deionized water to prepare 1 mol/L of the mixed sulfate solutions a and b. Sodium hydroxide solution and ammonia are mixed into a mixed solution referred to as a solution c, wherein the solution c is composed of the sodium hydroxide at a concentration of 2.0 mol/L and ammonia at a concentration of 0.5 mol/L. The prepared solutions a and b are slowly dropped into a reaction vessel with the solution c and stirring continuously. The pH is adjusted to be around 11 by adding the ammonia. The reaction temperature is 50 C., and the co-precipitation is conducted for 5 hours, and then aging is conducted for 12 hours at 70 C. The product is then filtered and washed several times until no sulfate ion is detected using BaCl.sub.2 solution, and then the product is dried and grinded to obtain spherical precursor powder. 0.105 mol of LiOH H.sub.2O, 9.0093 g of the precursor powder and 0.128 g of LiF are weighed and mixed together with absolute ethanol which acts as a dispersant, and fully grinded evenly, and then placed in a blast oven to be dried and finely grinded, and finally placed in a tube furnace. Temperature is raised to 500 C. at a rate of 5 C./min in an oxygen-enriched air atmosphere (flow rate 500 ml/min), so that pre-sintering is conducted for 5 hours under 500 C., and then temperature is raised to 725 C. at a rate of 2 C./min and sintering is conducted for 15 hours. Finally, natural cooling is conducted in the oxygen-enriched atmosphere, and the product is taken out and grinded finely, to obtain the target product LiNi.sub.0.55Mg.sub.0.05Co.sub.0.15Al.sub.0.05Mn.sub.0.15Ti.sub.0.05O.sub.1.95F.sub.0.05 of the positive electrode material.

[0041] A constant current charge and discharge test is conducted on the prepared positive electrode material LiNi.sub.0.55Mg.sub.0.05Co.sub.0.15Al.sub.0.05Mn.sub.0.15Ti.sub.0.05O.sub.1.95F.sub.0.05 of lithium-ion batteries. According to the test results, it shows that the discharge specific capacity of the positive electrode material is reduced, but the cycling performance is significantly improved. At room temperature, when the charge and discharge voltage range is 2.7-4.5V and the constant current charge and discharge ratio is 0.5 C, the initial discharge specific capacity of the positive electrode material for lithium-ion batteries can reach 223.3 mAh.Math.g.sup.1. Further, the discharge specific capacity is still 189.8 mAh.Math.g.sup.1 after 50 times of charging and discharging cycles, and the capacity retention rate is 85%.

[0042] Above descriptions are merely preferred embodiments of the present invention, and is not intended to limit the scope of the present invention. Any modifications, equivalent substitutions, improvements etc. within the spirit and principles of the present invention should fall within the scope of the present invention.