CN110071273B - Doped nickel cobalt lithium manganate and preparation method and application thereof - Google Patents

Doped nickel cobalt lithium manganate and preparation method and application thereof Download PDF

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CN110071273B
CN110071273B CN201910300130.XA CN201910300130A CN110071273B CN 110071273 B CN110071273 B CN 110071273B CN 201910300130 A CN201910300130 A CN 201910300130A CN 110071273 B CN110071273 B CN 110071273B
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刘坤
李道聪
夏昕
杨茂萍
汪杰
伊克巴尔·阿扎尔
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Hefei Gotion High Tech Power Energy Co Ltd
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    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract

The invention discloses doped nickel cobalt lithium manganate and a preparation method and application thereof, wherein the doped nickel cobalt lithium manganate comprises the following steps: adding boric acid and vanadyl acetylacetonate into the nickel-cobalt-manganese precursor to obtain a mixture A; adding ethanol into the mixture A, uniformly dispersing to obtain a dispersion liquid, heating and stirring the dispersion liquid until the ethanol is evaporated to dryness to obtain a doped precursor; adding a lithium source into the doped precursor, and fully mixing to obtain a mixture B; and carrying out two-stage annealing treatment on the mixture B to obtain the doped ternary nickel cobalt lithium manganate. The preparation method has the advantages that the co-doping preparation process of the ternary cathode material is simple, the uniform doping of the cathode material can be realized, and the large-scale production is easy.

Description

Doped nickel cobalt lithium manganate and preparation method and application thereof
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to doped nickel cobalt lithium manganate and a preparation method and application thereof.
Background
Liquid Lithium Ion Batteries (LIBs) are widely used in mobile electronic devices due to their high energy density. Recently, their applications have diversified to larger systems such as electric vehicles and energy storage systems. The rapid growth of the LIB industry has created a continuing need for improved performance. In particular, increased energy storage capacity is a primary task to achieve longer battery usage, and the development of high capacity cathode materials is a critical requirement. Thermal and structural stability, lifetime, and suppression of side reactions with the electrolyte are also essential for the development of improved cathode materials.
By surface modification or coating during charging and dischargingSuppression and control of high oxidation of the positive electrode material is one of the commonly used means. Many of the prior attempts have focused on the use of inorganic oxides such as Al2O3，MnO2，MgO，ZnO，TiO2，V2O5，Sm2O3And AlPO4To improve and enhance the stability of the surface of the positive electrode, mainly because they have excellent oxidation resistance. However, with the conventional MexOy compound, due to poor electronic and ionic conductivity involved, in LIB applications, although previous studies have reported that the electrochemical performance of the positive electrode is enhanced, the MexOy compound as a coating material causes the insulating coating to easily passivate the electron and ion transport rates, affecting the effective progress of chemical reactions.
Other methods use lithium-containing inorganic oxides (e.g., Li)eMnePO4，LieNiePO4，Li4SiO4，LiNbO3And Li3PO4) To obtain lithium ions on the surface of the positive electrode and form a protective layer. However, pure lithium-containing inorganic compounds tend to have lower electron conductivity and higher surface resistance, and excessive coating, for example, can form an interfacial layer that prevents the transfer of ions and electrons, thereby causing a loss of material capacity. The lithium-containing inorganic oxide often has a stable structure under high voltage, prevents the electrolyte from being oxidized, and stabilizes an interface structure, thereby effectively avoiding the problem of high impedance of the traditional inorganic oxide-coated interface. Among the various materials, B2O3、V2O5Can be used as a positive electrode coating material at the same time, the coating material is easy to fall off, and the coated active material is exposed under the electrolyte again to cause the electrical property to be reduced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of doped nickel cobalt lithium manganate, the preparation method provides a simple co-doping preparation process of a ternary cathode material, solves the problems that the existing MexOy compound is used as a coating material to cause an insulating coating and is easy to passivate the transmission rate of electrons and ions, and simultaneously solves the problem that the traditional B compound is easy to carry out2O3、V2O5When the material is used as a positive electrode coating material, the coating material is easy to fall off, and the preparation method can realize uniform doping of the positive electrode material and is easy for large-scale production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of doped lithium nickel cobalt manganese oxide comprises the following steps:
a. adding boric acid and vanadyl acetylacetonate into the nickel-cobalt-manganese precursor to obtain a mixture A;
b. adding ethanol into the mixture A, uniformly dispersing to obtain a dispersion liquid, heating and stirring the dispersion liquid until the ethanol is evaporated to dryness to obtain a doped precursor;
c. adding a lithium source into the doped precursor, and fully mixing to obtain a mixture B;
d. and carrying out two-stage annealing treatment on the mixture B to obtain the doped ternary nickel cobalt lithium manganate.
Further, in the step a, the concentration of the nickel-cobalt-manganese precursor in the dispersion liquid is 0.67g/mL, the concentration of the boric acid is 6.67 mmol/L-33.33 mmol/L, and the concentration of the vanadyl acetylacetonate is 6.67 mmol/L-33.33 mmol/L.
Further, in step b, the dispersion is uniform by means known to those skilled in the art, such as ultrasonic dispersion, stirring dispersion, and the like, and the heating and stirring steps are as follows: heating and stirring at 60-80 ℃.
Further, the lithium source is added according to the molar ratio of Li to Me of 1.01-1.07, wherein Me is the molar sum of Ni, Co and Mn in the doped precursor.
Preferably, in step c, the lithium source is one of lithium carbonate, lithium hydroxide, lithium acetate and lithium nitrate.
Further, in step c, the specific steps of fully mixing are as follows: ball milling is carried out for 1-3 h at 200-400 rpm.
Further, in step d, the two-stage annealing treatment specifically comprises the following steps: firstly, heating the mixture B at 250-500 ℃ for 5h in an oxygen atmosphere, then heating, and annealing at 700-770 ℃ for 8-16 h.
The invention also aims to provide doped nickel cobalt lithium manganate prepared by adopting the preparation method.
Further, the chemical formula of the doped nickel cobalt lithium manganate is (LiNi)0.8Co0.1Mn0.1)(BO3)x(BO4)y(V2O5)zO2-3x-4y-5zWherein x + y is 0.001-0.005, and z is 0.001-0.005.
The third purpose of the invention is to provide the application of the doped nickel cobalt lithium manganate in the preparation of lithium ion batteries.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method provided by the invention can realize uniform doping coating modification of the positive electrode material, the boron and vanadium co-doped coating layer is not easy to fall off, the positive electrode material can be effectively prevented from being in direct contact with electrolyte, and the material structure transformation and the side reaction of the material and the electrolyte are inhibited.
Drawings
FIG. 1 shows the cycle data under the conditions of 1C in comparative examples 1 to 3 and example 3.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Lithium Source, H used in the following examples3BO3Vanadyl acetylacetonate and ethanol were both analytical grade, and the nickel-cobalt-manganese precursor was battery grade, and both were commercially available products.
Example 1
a. Adding 0.001moL H into 100g of nickel-cobalt-manganese precursor3BO3And 0.001moL of vanadyl acetylacetonate to obtain a mixture A;
b. adding 150mL of ethanol into the mixture A, performing ultrasonic dispersion for 10min, stirring and heating at 80 ℃ until the solvent is evaporated to dryness to obtain a doping precursor, wherein the addition of the solvent for dissolution can ensure more uniform dispersion of the doping substance, so that the aim of uniform doping is fulfilled;
c. adding LiOH & H into the doped precursor according to the molar ratio of Li to Me of 1.01(Me is the molar sum of Ni, Co and Mn in the doped precursor)2Ball-milling the O in a planetary ball mill for 2 hours at the rotating speed of 200rpm to obtain a mixture B;
d. and heating the mixture B at 250 ℃ for 5h in an oxygen atmosphere, then heating to 700 ℃ for annealing for 8h to prepare doped nickel cobalt lithium manganate, and performing pre-sintering at a lower temperature and then performing high-temperature sintering by adopting two-stage annealing treatment to obtain the doped nickel cobalt lithium manganate with the best performance.
Example 2
a. Adding 0.005moL of H into 100g of nickel-cobalt-manganese precursor3BO3And 0.005moL of vanadyl acetylacetonate to give a mixture A;
b. adding 150mL of ethanol into the mixture A, performing ultrasonic dispersion for 10min, stirring and heating at 80 ℃ until the solvent is evaporated to dryness, and thus obtaining a doped precursor;
c. adding LiOH & H into the doped precursor according to the molar ratio of Li to Me of 1.07(Me is the molar sum of Ni, Co and Mn in the doped precursor)2Ball-milling the O in a planetary ball mill for 2 hours at the rotating speed of 400rpm to obtain a mixture B;
d. and heating the mixture B at 500 ℃ for 5h in an oxygen atmosphere, and then heating to 770 ℃ for annealing for 16h to obtain the doped nickel cobalt lithium manganate.
Example 3
a. Adding 0.002moL of H into 100g of nickel-cobalt-manganese precursor3BO3And 0.003moL of vanadyl acetylacetonate to give a mixture A;
b. adding 150mL of ethanol into the mixture A, performing ultrasonic dispersion for 10min, stirring and heating at 80 ℃ until the solvent is evaporated to dryness, and thus obtaining a doped precursor;
c. adding LiOH & H into the doped precursor according to the molar ratio of Li to Me of 1.03(Me is the molar sum of Ni, Co and Mn in the doped precursor)2Ball-milling for 2 hours in a planetary ball mill at the rotating speed of 230rpm to obtain a mixture B;
d. and heating the mixture B at 450 ℃ for 5h in an oxygen atmosphere, and then heating to 730 ℃ for annealing for 12h to obtain the doped nickel cobalt lithium manganate.
Example 4
a. Adding 0.003moL L H into 100g of nickel-cobalt-manganese precursor3BO3And 0.002moL of vanadyl acetylacetonate to obtain a mixture A;
b. adding 150mL of ethanol into the mixture A, performing ultrasonic dispersion for 10min, stirring and heating at 80 ℃ until the solvent is evaporated to dryness, and thus obtaining a doped precursor;
c. adding LiOH & H into the doped precursor according to the molar ratio of Li to Me of 1.05(Me is the molar sum of Ni, Co and Mn in the doped precursor)2Ball-milling the O in a planetary ball mill for 2 hours at the rotating speed of 350rpm to obtain a mixture B;
d. and heating the mixture B at 300 ℃ for 5h in an oxygen atmosphere, and then heating to 750 ℃ for annealing for 10h to obtain the doped nickel cobalt lithium manganate.
Example 5
a. Adding 0.003moL L H into 45g of nickel-cobalt-manganese precursor3BO3And 0.002moL of vanadyl acetylacetonate to obtain a mixture A;
b. adding 150mL of ethanol into the mixture A, performing ultrasonic dispersion for 10min, stirring and heating at 60 ℃ until the solvent is evaporated to dryness, and thus obtaining a doped precursor;
c. adding lithium carbonate into the doping precursor according to the molar ratio of Li to Me of 1.05(Me is the molar sum of Ni, Co and Mn in the doping precursor), and performing ball milling for 1h in a planetary ball mill at the rotating speed of 350rpm to obtain a mixture B;
d. and heating the mixture B at 300 ℃ for 5h in an oxygen atmosphere, and then heating to 750 ℃ for annealing for 10h to obtain the doped nickel cobalt lithium manganate.
Example 6
a. Adding 0.002moL of H into 120g of nickel-cobalt-manganese precursor3BO3And 0.003moL of vanadyl acetylacetonate to give a mixture A;
b. adding 150mL of ethanol into the mixture A, performing ultrasonic dispersion for 10min, stirring and heating at 70 ℃ until the solvent is evaporated to dryness, and thus obtaining a doped precursor;
c. adding lithium nitrate into the doping precursor according to the molar ratio of Li to Me of 1.04(Me is the molar sum of Ni, Co and Mn in the doping precursor) and carrying out ball milling for 3 hours in a planetary ball mill at the rotating speed of 230rpm to obtain a mixture B;
d. and heating the mixture B at 450 ℃ for 5h in an oxygen atmosphere, and then heating to 730 ℃ for annealing for 12h to obtain the doped nickel cobalt lithium manganate.
Comparative example 1
a. Adding 0.002moL of H into 100g of nickel-cobalt-manganese precursor3BO3Obtaining a mixture A;
b. adding 150mL of ethanol into the mixture A, performing ultrasonic dispersion for 10min, stirring and heating at 80 ℃ until the solvent is evaporated to dryness, and thus obtaining a doped precursor;
c. adding LiOH & H into the doped precursor according to the molar ratio of Li to Me of 1.03(Me is the molar sum of Ni, Co and Mn in the doped precursor)2Ball-milling for 2 hours in a planetary ball mill at the rotating speed of 230rpm to obtain a mixture B;
d. and heating the mixture B at 450 ℃ for 5h in an oxygen atmosphere, and then heating to 730 ℃ for annealing for 12h to obtain the doped nickel cobalt lithium manganate.
Comparative example 2
a. Adding 0.003moL of vanadyl acetylacetonate into 100g of nickel-cobalt-manganese precursor to obtain a mixture A;
b. adding 150mL of ethanol into the mixture A, performing ultrasonic dispersion for 10min, stirring and heating at 80 ℃ until the solvent is evaporated to dryness to obtain a doped precursor;
c. adding LiOH & H into the doped precursor according to the molar ratio of Li to Me of 1.03(Me is the molar sum of Ni, Co and Mn in the doped precursor)2Ball-milling for 2 hours in a planetary ball mill at the rotating speed of 230rpm to obtain a mixture B;
d. and heating the mixture B at 450 ℃ for 5h in an oxygen atmosphere, and then heating to 730 ℃ for annealing for 12h to obtain the doped nickel cobalt lithium manganate.
Comparative example 3
a. Adding 150mL of ethanol into 100g of nickel-cobalt-manganese precursor, performing ultrasonic dispersion for 10min, stirring and heating at 80 ℃ until the solvent is evaporated to dryness to obtain a doped precursor;
b. adding LiOH & H into the doped precursor according to the molar ratio of Li to Me of 1.03(Me is the molar sum of Ni, Co and Mn in the doped precursor)2Ball-milling for 2 hours in a planetary ball mill at the rotating speed of 230rpm to obtain a mixture B;
c. and heating the mixture B at 450 ℃ for 5h in an oxygen atmosphere, and then heating to 730 ℃ for annealing for 12h to obtain the doped nickel cobalt lithium manganate.
The doped lithium nickel cobalt manganese oxide prepared in the examples and the comparative examples is used as a positive electrode, a sheet making process of a power buckling manufacturing process is carried out in a drying room, a CR2016 button cell is assembled in an argon-filled glove box, and then electrochemical performance test is carried out at room temperature. Wherein, the charging and discharging interval is 3.0-4.3V, and one-time charging and discharging test is carried out in sequence, and the test result is shown in table 1, so as to evaluate the electrochemical performance of the material.
TABLE 1 comparative examples 1-3 and example 3 Charge and discharge tests
Figure BDA0002027956650000071
Note: in the table, 0.2C (mAh/g), 0.33C (mAh/g) and 0.5C (mAh/g) respectively represent the specific discharge capacity of the battery at 0.2C, 0.33C and 0.5C, 1C (1st) and 1C (50th) respectively represent the specific discharge capacity of the battery at the first cycle and the 50th cycle, and 50th @1C represents the capacity retention rate of the battery after 50 cycles.
Meanwhile, the button cell is subjected to 1C cycle performance test, the test result is shown in figure 1, and the test result can be seen from figure 1 and table 1, compared with comparative examples 1-3, the first effect and different multiplying power are improved, the cycle is good, and the excellent performance of the boron and vanadium co-doped nickel cobalt lithium manganate is fully illustrated.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (8)

1. A preparation method of doped lithium nickel cobalt manganese oxide is characterized by comprising the following steps:
a. adding boric acid and vanadyl acetylacetonate into the nickel-cobalt-manganese precursor to obtain a mixture A;
b. adding ethanol into the mixture A, uniformly dispersing to obtain a dispersion liquid, heating and stirring the dispersion liquid until the ethanol is evaporated to dryness to obtain a doped precursor;
c. adding a lithium source into the doped precursor, and fully mixing to obtain a mixture B;
d. heating the mixture B at 250-500 ℃ for 5h in an oxygen atmosphereThen heating, annealing at 700-770 ℃ for 8-16 h for two-stage annealing treatment to obtain doped ternary nickel cobalt lithium manganate (LiNi)0.8Co0.1Mn0.1)(BO3)x(BO4)y(V2O5)zO2-3x-4y-5zWherein x + y = 0.001-0.005, and z = 0.001-0.005.
2. The method of claim 1, wherein in the step b, the concentration of the nickel-cobalt-manganese precursor in the dispersion is 0.3-0.8 g/mL, the concentration of the boric acid is 6.67-33.33 mmol/L, and the concentration of the vanadyl acetylacetonate is 6.67-33.33 mmol/L.
3. The preparation method according to claim 1, wherein in the step b, the heating and stirring are specifically performed by: heating and stirring at 60-80 deg.C.
4. The method according to claim 1, wherein in the step c, the lithium source is added according to a molar ratio of Li to Me of 1.01-1.07, wherein the molar amount of Me is the molar sum of Ni, Co and Mn in the doping precursor.
5. The method of claim 1, wherein in step c, the lithium source is one of lithium carbonate, lithium hydroxide, lithium acetate, and lithium nitrate.
6. The method according to claim 1, wherein in step c, the specific steps of thoroughly mixing are as follows: ball milling is carried out for 1-3 h at 200-400 rpm.
7. The doped nickel cobalt lithium manganate is characterized by being prepared by the preparation method of any one of claims 1 to 6.
8. Use of the doped lithium nickel cobalt manganese oxide according to claim 7 for the preparation of lithium ion batteries.
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DE19935091A1 (en) * 1999-07-27 2001-02-08 Emtec Magnetics Gmbh Lithium intercalation compounds containing lithium manganese oxide
CN103413931A (en) * 2013-08-08 2013-11-27 北京大学 Boron-doped lithium-rich anode material for lithium ion batteries and preparation method of material
CN105375010A (en) * 2015-11-26 2016-03-02 长沙矿冶研究院有限责任公司 Preparation method of high compaction density lithium ion cathode material
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