CN114975907A - Vanadium boride coated nickel cobalt lithium manganate positive electrode material and preparation method thereof - Google Patents

Vanadium boride coated nickel cobalt lithium manganate positive electrode material and preparation method thereof Download PDF

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CN114975907A
CN114975907A CN202210297537.3A CN202210297537A CN114975907A CN 114975907 A CN114975907 A CN 114975907A CN 202210297537 A CN202210297537 A CN 202210297537A CN 114975907 A CN114975907 A CN 114975907A
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positive electrode
electrode material
nickel cobalt
lithium manganate
vanadium boride
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庄严
赵宇辉
鲍迎庆
关明云
贾海浪
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Jiangsu University of Technology
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    • 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 belongs to the technical field of lithium ion batteries, and particularly relates to a vanadium boride-coated nickel cobalt lithium manganate positive electrode material and a preparation method thereof, wherein the preparation method comprises the following steps: 1) will VCl 3 Stirring and mixing the aqueous solution and the ethanol solution of the nickel cobalt lithium manganate positive electrode material, and then dripping NaBH 4 Continuously stirring the solution for reaction for 2 hours; 2) carrying out vacuum filtration, washing and drying on the solution obtained after the reaction in the step 1) to obtain a vanadium boride coated nickel cobalt lithium manganate positive electrode material, and marking the positive electrode material as an NCM @ V-B material. The method for generating the vanadium boride coating in situ is beneficial to improving the stability and the electrochemical performance of the vanadium boride coating, and has better corrosion resistance and wear resistance.

Description

Vanadium boride coated nickel cobalt lithium manganate positive electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a vanadium boride-coated nickel cobalt lithium manganate positive electrode material and a preparation method thereof.
Background
With the rapid development of Lithium Ion Batteries (LIBs) in emerging fields such as electric vehicles and power grid energy storage, LIBs with more excellent performance are required to meet more application requirements. The influence of the selection of the anode material on the performance of the LIBs is very important, and the method has important research significance for improving the high specific capacity and the long cycle life of the anode material. High nickel layered positive electrode oxide LiNi 0.8 Co 0.1 Mn 0.1 O 2 The (NCM811) has the advantages of high energy density and high specific capacity and is expected to become a preferred material in the energy storage market. However, there are some problems with NCM811 that prevent its large scale application. The phase transformation in the positive electrode material and on the surface of the positive electrode material can cause secondary particles to generate intergranular cracks along Grain Boundaries (GBs), and the material structure is damaged. The interfacial film (CEI) formation and growth of the positive electrode and the electrolyte continuously consumes the electrolyte and lithium ions, which not only generates gas but also causes the dissolution of Transition Metal (TM), resulting in the degradation of the electrochemical performance of NCM 811. In addition, oxygen on the surface of the high nickel positive electrode becomes unstable at high pressure and easily escapes from the surface, and the escape of oxygen not only oxidizes the organic electrolyte but also causes cation reduction or aggravates structural phase change. Generally, the above-mentioned adverse reactions are not generated singly, and chain reactions may occur, thereby continuously deteriorating the electrochemical performance of the high nickel cathode material. In response to these problems, much effort is expended to explore the improvement in the electrochemical properties of the positive electrode material. For example, introducing a doping material into the interior or the surface of the material, and designing and synthesizing a single crystal structure with a micron or nanometer level, etc., have a good effect of improving the performance of the cathode material. In addition, surface modification is also considered as an effective method for improving these problems. For example, carbon materials (graphene), conductive polymers (polyaniline), metal oxides (titanium oxide), metal phosphates (aluminum phosphate), and the like have been widely reported to have significant effects in stabilizing the interface of NCM811 and suppressing side reactions, and the like. However, the method is not limited to the specific methodMany coating materials are difficult to conform during electrochemical cycling and even have some impact on rate performance.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
In order to improve the electrochemical performance and stability of a nickel cobalt lithium manganate (NCM) cathode material in the prior art, the invention aims to provide a preparation method of a vanadium boride-coated nickel cobalt lithium manganate (NCM) cathode material.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a vanadium boride-coated nickel cobalt lithium manganate positive electrode material specifically comprises the following steps:
1) will VCl 3 Stirring and mixing the aqueous solution and the ethanol solution of the nickel cobalt lithium manganate positive electrode material, and then dripping NaBH 4 Continuously stirring the solution for reaction for 2 hours;
2) and (2) carrying out vacuum filtration, washing and drying on the solution obtained after the reaction in the step 1) to obtain a vanadium boride coated nickel cobalt lithium manganate positive electrode material, which is recorded as an NCM @ V-B material.
The invention adopts sodium borohydride (NaBH) with reducibility 4 ) And VCl 3 Vanadium boride is generated through reaction and is combined with surface oxygen of the layered oxide NCM, and an NCM @ V-B thin layer is coated on the surface of the NCM in situ in a covalent bond mode. The boron element (2s22p1) has special electron deficiency and strong bond binding capacity, can easily react with the metal element vanadium to generate vanadium boride (V-B) which is coated on the surface of the NCM, and the coating layer is uniform, so that the electrochemical performance of the NCM cathode material is improved.
Preferably, said VCl 3 The mass concentration of the aqueous solution is 3-10 mg/mL; the mass concentration of the nickel cobalt lithium manganate positive electrode material in the ethanol solution of the nickel cobalt lithium manganate positive electrode material is 40 mg/mL; the NaBH 4 NaBH in solution 4 The mass concentration of (b) is 3-15 mg/mL.
Preferably, the VCl 3 And NaBH 4 The molar ratio of the used amount is 1: 3.
Preferably, the mass fraction of vanadium boride (V-B) in the vanadium boride-coated nickel cobalt lithium manganate positive electrode material is 0.5-1.5 wt%.
Preferably, the washing in step 2) is washing with deionized hydrous ethanol for several times respectively, and the drying is drying at 80 ℃.
Preferably, the nickel cobalt lithium manganate positive electrode material is an NCM811 positive electrode material.
The invention also aims to provide the vanadium boride-coated nickel cobalt lithium manganate positive electrode material prepared by the method.
Has the advantages that:
(1) according to the invention, a simple wet coating synthesis method is adopted, sodium borohydride is used as a boron source and can also be used as a reducing agent, a covalent bond is formed by utilizing the strong affinity of oxygen on the surface of a nickel cobalt lithium manganate (NCM) material under a reduction condition, a firm vanadium boride thin layer is further generated in situ, and the vanadium boride coated nickel cobalt lithium manganate positive electrode material (NCM @ V-B) is formed, and the coating layer is uniform and firm and has good stability. Compared with the defect that the stability is poor easily when the coating is coated on the surface of the anode material through post-treatment in the prior art, the method for generating the vanadium boride coating in situ is beneficial to improving the stability and the electrochemical performance of the vanadium boride coating.
(2) Compared with other metal boride coating layers, the prepared vanadium boride coating layer has better corrosion resistance and wear resistance, and can resist the attack of HF; in addition, the vanadium boride also has low resistivity (approximately equal to 41 mu omega cm), so that the vanadium boride-coated nickel cobalt lithium manganate positive electrode material has excellent conductivity.
(3) The method is simple and convenient, has low cost, realizes the development idea of low cobalt in the field of lithium ion batteries, and is beneficial to large-scale production and social acceptance.
Drawings
The technical solutions of the present invention are further described below with reference to the drawings, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
FIG. 1 is an XPS spectrum of an NCM @ 1% V-B cathode material prepared in example 2 of the present invention;
wherein a is a total spectrum; b is an enlarged view of the Ni 2p peak in the total spectrum; c is an enlarged view of the V2 p peak in the total spectrum; d is an enlarged view of the B1s peak in the total spectrum.
FIG. 2 is a projection electron microscope (TEM) photograph of the NCM prepared in comparative example 1 and the NCM @ 1% V-B positive electrode material prepared in example 2 according to the present invention; where a, B are the NCM prepared in comparative example 1 and c, d are the NCM @ 1% V-B prepared in example 1.
FIG. 3 is a plot of charge/discharge capacity versus voltage for the first cycle for the NCM prepared in comparative example 1, the NCM @ 0.5% V-B prepared in example 1, the NCM @ 1% V-B prepared in example 2, and the NCM @ 1.5% V-B prepared in example 3.
FIG. 4 is a graph of the cycling performance at 1C for the NCM prepared in comparative example 1, the NCM @ 0.5% V-B prepared in example 1, the NCM @ 1% V-B prepared in example 2, and the NCM @ 1.5% V-B prepared in example 3.
FIG. 5a is a graph of capacity versus voltage for the NCM prepared in comparative example 1 at different cycle periods; FIG. 5B is a graph of the capacity versus voltage for different cycle periods for NCM @ 1% V-B prepared in example 2.
FIG. 6 is a graph of the rate capability of the NCM prepared in comparative example 1, the NCM @ 0.5% V-B prepared in example 1, the NCM @ 1% V-B prepared in example 2, and the NCM @ 1.5% V-B prepared in example 3 at different rates.
FIG. 7 shows the average discharge capacity retention at different rates for the NCM prepared in comparative example 1, the NCM @ 0.5% V-B prepared in example 1, the NCM @ 1% V-B prepared in example 2, and the NCM @ 1.5% V-B prepared in example 3.
Detailed Description
Example 1
1) 10mg of VCl are weighed out 3 Dissolved in 3mL of deionized water to give VCl 3 Aqueous solution (3.33mg/mL), followed by VCl 3 The aqueous solution was stirred with 50mL of an ethanol solution (40mg/mL) containing 2g of NCM811 as a positive electrode materialMixing, and then dropwise adding 2mL of a solution containing 7.5mg of NaBH 4 The solution (3.75mg/mL) is continuously stirred and reacted for 2 hours;
2) and (2) carrying out vacuum filtration on the solution obtained after the reaction in the step 1), washing the obtained sample with deionized hydrous ethanol for several times, and then putting the washed sample into a forced air drying oven for drying at 80 ℃ to obtain the vanadium boride-coated nickel cobalt lithium manganate positive electrode material, which is recorded as NCM @ 0.5% V-B material.
Example 2
1) 20mg of VCl are weighed out 3 Dissolved in 3mL of deionized water to give VCl 3 Aqueous solution (6.66mg/mL), followed by VCl 3 The aqueous solution was mixed with 50mL of an ethanol solution (40mg/mL) containing 2g of NCM811 as a positive electrode material under stirring, and then 2mL of a solution containing 15mg of NaBH was added dropwise 4 The solution (7.5mg/mL) is continuously stirred and reacted for 2 hours;
2) and (2) carrying out vacuum filtration on the solution obtained after the reaction in the step 1), washing the obtained sample with deionized hydrous ethanol for several times, and then putting the washed sample into a forced air drying oven for drying at 80 ℃ to obtain the vanadium boride-coated nickel cobalt lithium manganate positive electrode material, which is recorded as NCM @ 1% V-B material.
Example 3
1) 30mg of VCl are weighed out 3 Dissolved in 3mL of deionized water to give VCl 3 Aqueous solution (10.0mg/mL), followed by VCl 3 The aqueous solution was mixed with 50mL of an ethanol solution (40mg/mL) containing 2g of NCM811 as a positive electrode material under stirring, and then 2mL of a solution containing 22.5mg of NaBH was added dropwise 4 The solution (11.25mg/mL) is stirred continuously for reaction for 2 h;
2) and (2) carrying out vacuum filtration on the solution obtained after the reaction in the step 1), washing the obtained sample with deionized hydrous ethanol for several times, and then putting the washed sample into a forced air drying oven for drying at 80 ℃ to obtain the vanadium boride-coated nickel cobalt lithium manganate positive electrode material, which is recorded as NCM @ 1.5% V-B material.
Comparative example 1
Original NCM811 without addition of VCl 3 And NaBH 4 The sample obtained by the above treatment under the conditions of (1) was an NCM material.
Application example:
the NCM @ 0.5% V-B material, the NCM @ 1% V-B material, the NCM @ 1.5% V-B material, and the NCM material obtained in examples 1-3 and comparative example 1 were mixed with conductive carbon black (Super-P, Taiyuan lithium technology Co., Ltd.) and polyvinylidene fluoride (PVDF, national drug group chemical Co., Ltd.) in a mass ratio of 8:1:1, and then N-methylpyrrolidone (NMP) was added and stirred for 6 hours. The obtained mixed slurry is uniformly coated on an aluminum foil, dried in an oven at 110 ℃ for 12h and then cut into 12mm circular pole pieces for performance test, and the test results are as follows.
As shown in fig. 1, an XPS spectrum of the NCM @ 1% V-B cathode material prepared in example 2 is shown. The peaks at 873.0eV and 855.1eV in FIG. 1b correspond to Ni 2p 1/2 And Ni 2p 3/2 Track of Ni 2p 3/2 Split into two peaks, corresponding to Ni respectively 2+ And Ni 3+ It is shown that the thin V-B layer coating NCM811 has no effect on the chemical valence of Ni element. FIG. 1c is a V2 p spectrum with 3 peaks V 0 、V 2p 1/2 And V2 p 3/2 。V 2p 3/2 Can be split into three peaks, and is positioned at V of 515.9eV 3+ 516.7eV V 4+ And V of 517.5eV 5+ This indicates that in the V-B compound, vanadium exists in a plurality of oxidation states. The peak at 188.7eV in the spectrum of FIG. 1d B1s is assigned to B 0 The peak at 191.5eV is ascribed to B 3+ Corresponding to the V-B compound and B, respectively 2 O 3 And the peak at 193.7eV corresponds to BO x This suggests that B in the V-B thin layer may form covalent bonds with surface oxygen in the NCM, thereby allowing the V-B compound to be successfully coated on the surface of the positive material. According to an XPS spectrogram, vanadium boride is successfully synthesized and coated on the surface of NCM811 to form the vanadium boride-coated nickel cobalt lithium manganate positive electrode material.
As shown in fig. 2, are projection electron microscope (TEM) photographs of the NCM prepared in comparative example 1 and the NCM @ 1% V-B cathode material prepared in example 2; where a, B are the NCMs prepared in comparative example 1, c, d are the NCMs @ 1% V-B prepared in example 1, the NCM images in FIGS. 2a, B are smooth surfaced with lattice fringes having a spacing of about 0.475nm corresponding to the (003) plane of NCM811, and the NCM @ 1% V-B material in FIGS. 2c, d has an amorphous thin layer having a thickness of about 2.5nm on the surface, with the (003) plane of NCM811 being clearly visible below the thin layer. The vanadium boride (V-B) is successfully coated on the surface of the NCM811 material.
As shown in FIG. 3, the first-turn charge-discharge capacity vs. voltage curves for the NCM prepared in comparative example 1, the NCM @ 0.5% V-B prepared in example 1, the NCM @ 1% V-B prepared in example 2, and the NCM @ 1.5% V-B prepared in example 3 are shown.
As shown in FIG. 4, there is a graph of the cycling performance at 1C for the NCM prepared in comparative example 1, the NCM @ 0.5% V-B prepared in example 1, the NCM @ 1% V-B prepared in example 2, and the NCM @ 1.5% V-B prepared in example 3. It can be seen that the vanadium boride-coated nickel cobalt lithium manganate positive electrode material prepared by the method has good circulation stability, and the stability after 500 cycles of circulation is obviously improved.
As shown in fig. 5, fig. 5a is a graph of capacity versus voltage for the NCM prepared in comparative example 1 at different cycle periods; FIG. 5B is a graph of the capacity versus voltage for different cycle periods for NCM @ 1% V-B prepared in example 2.
As shown in FIG. 6, the discharge specific capacity of the vanadium boride-coated nickel cobalt lithium manganate positive electrode material prepared in the application is higher than that of the non-coated NCM material, as compared with the NCM prepared in comparative example 1, the NCM prepared in example 1 @ 0.5% V-B, the NCM prepared in example 2 @ 1% V-B and the NCM prepared in example 3 @ 1.5% V-B are shown in a ratio performance graph under different ratios.
As shown in FIG. 7, the average discharge capacity retention rates of the NCM prepared in comparative example 1, the NCM @ 0.5% V-B prepared in example 1, the NCM @ 1% V-B prepared in example 2 and the NCM @ 1.5% V-B prepared in example 3 under different multiplying factors are shown, and the vanadium boride-coated nickel cobalt lithium manganate positive electrode material prepared in the application has higher average discharge capacity retention rate than that of the uncoated NCM material.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. A preparation method of a vanadium boride-coated nickel cobalt lithium manganate positive electrode material is characterized by comprising the following steps:
1) will VCl 3 Stirring and mixing the aqueous solution and the ethanol solution of the nickel cobalt lithium manganate positive electrode material, and then dripping NaBH 4 Continuously stirring the solution for reaction for 2 hours;
2) and (2) carrying out vacuum filtration, washing and drying on the solution obtained after the reaction in the step 1) to obtain a vanadium boride coated nickel cobalt lithium manganate positive electrode material, which is recorded as an NCM @ V-B material.
2. The method for preparing the vanadium boride-coated nickel cobalt lithium manganate positive electrode material of claim 1, wherein the VCl is VCl 3 The mass concentration of the aqueous solution is 3-10 mg/mL; the mass concentration of the nickel cobalt lithium manganate positive electrode material in the ethanol solution of the nickel cobalt lithium manganate positive electrode material is 40 mg/mL; the NaBH 4 NaBH in solution 4 The mass concentration of (b) is 3-15 mg/mL.
3. The method for preparing the vanadium boride-coated nickel cobalt lithium manganate positive electrode material of claim 1, wherein the VCl is VCl 3 And NaBH 4 The molar ratio of the used amount is 1: 3.
4. The method for preparing the vanadium boride-coated nickel cobalt lithium manganate positive electrode material of claim 1, wherein the mass fraction of vanadium boride (V-B) in the vanadium boride-coated nickel cobalt lithium manganate positive electrode material is 0.5-1.5 wt%.
5. The method for preparing the vanadium boride-coated nickel cobalt lithium manganate positive electrode material of claim 1, wherein the washing in step 2) is washing with deionized hydrous ethanol for several times, and the drying is drying at 80 ℃.
6. The method for preparing the vanadium boride-coated lithium nickel cobalt manganese oxide positive electrode material according to claim 1, wherein the lithium nickel cobalt manganese oxide positive electrode material is an NCM811 positive electrode material.
7. A vanadium boride-coated nickel cobalt lithium manganate positive electrode material prepared by the method of any one of claims 1 to 6.
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CN115465901A (en) * 2022-11-01 2022-12-13 贺州学院 Method for completely coating surface of lithium ion battery anode material

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