CN110156092B - Dried persimmon-shaped cobaltosic oxide lithium battery negative electrode material and preparation method thereof - Google Patents
Dried persimmon-shaped cobaltosic oxide lithium battery negative electrode material and preparation method thereof Download PDFInfo
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- CN110156092B CN110156092B CN201910509415.4A CN201910509415A CN110156092B CN 110156092 B CN110156092 B CN 110156092B CN 201910509415 A CN201910509415 A CN 201910509415A CN 110156092 B CN110156092 B CN 110156092B
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Abstract
The application discloses a dried persimmon-shaped cobaltosic oxide lithium battery negative electrode material and a preparation method thereof, wherein the preparation method comprises the following steps: dissolving cobalt salt in water to prepare a cobalt salt solution; adding 1, 2, 4 triazole into the cobalt salt solution, and then adding 3, 5-dimethylpyrazole to form a light purple red solution; adding hydrazine hydrate into the solution until a mauve pasty precipitate is obtained, heating in a water bath at 90 ℃ for 30 minutes, centrifugally separating, washing the precipitate with deionized water for three times, washing with absolute ethyl alcohol for three times, and drying to obtain a mauve cobalt precursor; and (3) calcining the obtained cobalt precursor at high temperature by using a temperature-controlled muffle furnace, and naturally cooling to obtain the persimmon cake-shaped cobaltosic oxide. The dried persimmon-shaped cobaltosic oxide cathode material consists of dried persimmon-shaped cobaltosic oxide with a hierarchical structure assembled by small particles. The cobaltosic oxide negative electrode material has better charge and discharge capacity and good cycle performance.
Description
Technical Field
The invention relates to a dried persimmon-shaped cobaltosic oxide lithium battery negative electrode material and a preparation method thereof.
Background
At present, the power lithium ion battery is a bottleneck restricting the development of new energy automobiles, and the development of a novel lithium ion battery with high specific capacity, good stability, long service life and strong environmental adaptability is urgent. The specific capacity of the current industrially applied negative electrode materials such as graphite, soft carbon, hard carbon and the like is relatively low (the theoretical specific capacity of the graphite is only 372mAh.-1) The lithium ion battery anode material is not easy to charge and discharge rapidly, has poor overcharge and overdischarge resistance, is difficult to meet the requirement, and needs to be developed urgently. Cobaltosic oxide (Co)3O4) The theoretical specific capacity of (A) is 890372mAh.-1The volume of the lithium ion battery is greatly reduced, the chemical property is stable, and the lithium ion battery is one of ideal negative electrode materials of the power lithium battery.
Cobaltosic oxide (Co)3O4) Is gray black or black powder, and has density of 6.0-6.2g/cm3Molecular weight 240.80. Co3O4Belonging to the cubic system, having a lattice parameter a =0.811 nm and AB2O4The spinel structure has a framework of a three-dimensional network structure with tetrahedrons and octahedrons coplanar, and the structure is favorable for ion diffusion. With magnetic iron oxide Fe3O4Is heterogeneous and isomorphous.
The invention patent with publication number CN108483513A discloses a preparation method of three-dimensional flower-like cobaltosic oxide, which comprises the following steps: weighing cobalt acetate tetrahydrate solid and SDS (sodium dodecyl sulfate) in a beaker, adding ethylene glycol and deionized water, and stirring until solid particles are completely dissolved to obtain a solution A; weighing a second component of metal nitrate and TBAB in another beaker, adding ethylene glycol, and stirring until solid particles are completely dissolved to obtain a solution B; pouring the solution B into the solution A, continuously stirring for 30min, adding urea, continuously stirring for 60min, transferring the solution into a hydrothermal kettle, and heating in a drying oven at 180 ℃ for 8 h; and cooling, taking out the reaction liquid, pouring the reaction liquid into a centrifugal tube, centrifuging for 5min at the speed of 4000rad/s, washing the precipitate with deionized water, washing the precipitate with absolute ethyl alcohol for multiple times, drying the precipitate, and roasting in a muffle furnace at 300 ℃ for 180 min.
Disclosure of Invention
The invention aims to provide a dried persimmon-shaped cobaltosic oxide lithium battery negative electrode material and a preparation method thereof.
In order to achieve the purpose, the technical scheme provided by the invention is as follows: a preparation method of a dried persimmon-shaped cobaltosic oxide lithium battery negative electrode material comprises the following steps:
the first step is as follows: dissolving cobalt salt in water to prepare a cobalt salt solution;
the second step is that: under the condition of stirring, diluting the cobalt salt solution by 10 times, then adding 1, 2, 4 triazole, and then adding 3, 5-dimethylpyrazole to form a first solution;
the third step: adding hydrazine hydrate to the first solution under stirring until a paste is obtained;
the fourth step: heating the paste in a water bath at 70-90 ℃ to generate a precipitate, then carrying out centrifugal separation, washing the obtained precipitate with deionized water, then washing with absolute ethyl alcohol, and then drying to obtain a cobalt precursor;
the fifth step: and (3) placing the cobalt precursor in a crucible, then covering the crucible with a cover, then performing high-temperature calcination by using a temperature-controlled muffle furnace, and naturally cooling to obtain the persimmon cake-shaped cobaltosic oxide.
The preferable technical scheme is as follows: in the first step, the concentration of the cobalt salt solution is 0.1-0.5 mol/L.
The preferable technical scheme is as follows: the cobalt salt is cobalt nitrate, cobalt acetate or cobalt chloride.
The preferable technical scheme is as follows: in the second step, the molar ratio of the cobalt salt to the 1, 2, 4 triazole is 1:2-1: 5; the molar ratio of the cobalt salt to the 3, 5-dimethylpyrazole is 1:1.5-1: 3.
The preferable technical scheme is as follows: in the second step, the molar ratio of cobalt salt to hydrazine hydrate is 1:20 to 1: 25.
The preferable technical scheme is as follows: in the second step and the third step, the stirring speed is 180-220 r/min, and the reaction temperature is 20-25 ℃.
The preferable technical scheme is as follows: the temperature condition during drying is 50-70 ℃.
The preferable technical scheme is as follows: in the fifth step, the calcination temperature is 450-600 ℃, the calcination time is 1-3 hours, and the heating rate is 1-5 ℃/min.
In order to achieve the purpose, the technical scheme provided by the invention is as follows: a dried persimmon-shaped cobaltosic oxide lithium battery negative electrode material is prepared according to the preparation method.
Drawings
FIG. 1 is a scanning electron micrograph of a dried persimmon cobaltosic oxide battery negative electrode material according to the present application.
Fig. 2 is an XRD spectrum of the persimmon cake-shaped cobaltosic oxide battery negative electrode material of the present application.
Fig. 3 shows the cycle performance of the negative electrode material of the persimmon cake-shaped cobaltosic oxide battery.
Due to the application of the technical scheme, compared with the prior art, the invention has the advantages that:
the dried persimmon-shaped cobaltosic oxide cathode material prepared by the invention is composed of dried persimmon-shaped cobaltosic oxide with a hierarchical structure assembled by small particles, and has excellent charge and discharge capacity and good cycle performance.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
The first embodiment is as follows: dried persimmon-shaped cobaltosic oxide lithium battery negative electrode material and preparation method thereof
A preparation method of a dried persimmon-shaped cobaltosic oxide lithium battery negative electrode material comprises the following steps:
Step 3, adding hydrazine hydrate into the solution forming the mauve complex under the stirring condition until mauve paste is obtained; the stirring speed is 200r/min, and the reaction temperature is 22.5 ℃.
And 4, heating the mauve paste in a water bath at 90 ℃ for 30 minutes to obtain mauve precipitates. Performing centrifugal separation, washing the precipitate with deionized water for three times, washing with absolute ethyl alcohol for three times, and drying to obtain a purple red cobalt precursor;
and 5, placing the obtained mauve cobalt precursor into a crucible (covered), calcining at high temperature by using a temperature-controlled muffle furnace, and naturally cooling to obtain the persimmon cake-shaped cobaltosic oxide.
The preferred embodiment is: the concentration of the cobalt salt solution in the step 1 is 0.3 mol/L.
The cobalt salt solution in step 1 is a cobalt nitrate aqueous solution.
The molar ratio of the cobalt salt to the 1, 2, 4 triazole in the step 2 is 1: 3.5; the molar ratio of the cobalt salt to the 3, 5-dimethylpyrazole was 1: 2.25.
The molar ratio of the cobalt salt to the hydrazine hydrate in the step 3 is 1: 22.5.
The drying temperature in step 4 was 60 ℃.
And (3) during calcination in the step 5, covering the crucible, wherein the temperature is 525 ℃, the time is 2 hours, and the heating rate is 3 ℃/min.
The scanning electron micrograph of the dried persimmon-shaped cobaltosic oxide battery negative electrode material prepared in the embodiment is shown in fig. 1; the XRD spectrogram of the persimmon cake-shaped cobaltosic oxide battery negative electrode material is shown in figure 2; the cycle performance of the cake-shaped cobaltosic oxide battery negative electrode material is shown in fig. 3.
Example two: dried persimmon-shaped cobaltosic oxide lithium battery negative electrode material and preparation method thereof
A preparation method of a dried persimmon-shaped cobaltosic oxide lithium battery negative electrode material comprises the following steps:
the first step is as follows: dissolving cobalt salt in water to prepare a cobalt salt solution;
the second step is that: under the condition of stirring, diluting the cobalt salt solution by 10 times, then adding 1, 2, 4 triazole, and then adding 3, 5-dimethylpyrazole to form a first solution;
the third step: adding hydrazine hydrate to the first solution under stirring until a paste is obtained;
the fourth step: heating the paste in a water bath at 80 ℃ to generate a precipitate, then carrying out centrifugal separation, washing the obtained precipitate with deionized water, then washing with absolute ethyl alcohol, and then drying to obtain a cobalt precursor;
the fifth step: and (3) placing the cobalt precursor in a crucible, then covering the crucible with a cover, then performing high-temperature calcination by using a temperature-controlled muffle furnace, and naturally cooling to obtain the persimmon cake-shaped cobaltosic oxide.
The preferred embodiment is: in the first step, the concentration of the cobalt salt solution is 0.1 mol/L.
The preferred embodiment is: the cobalt salt is cobalt acetate.
The preferred embodiment is: in the second step, the molar ratio of the cobalt salt to the 1, 2, 4 triazole is 1: 2; the molar ratio of the cobalt salt to the 3, 5-dimethylpyrazole was 1: 1.5.
The preferred embodiment is: in the second step, the molar ratio of cobalt salt to hydrazine hydrate was 1: 20.
The preferred embodiment is: in the second and third steps, the stirring speed was 180r/min and the reaction temperature was 25 ℃.
The preferred embodiment is: the temperature condition during drying was 50 ℃.
The preferred embodiment is: in the fifth step, the calcination temperature is 450 ℃, the calcination time is 3 hours, and the temperature rise rate is 1 ℃/min.
A dried persimmon-shaped cobaltosic oxide lithium battery negative electrode material is prepared according to the preparation method.
Example three: dried persimmon-shaped cobaltosic oxide lithium battery negative electrode material and preparation method thereof
A preparation method of a dried persimmon-shaped cobaltosic oxide lithium battery negative electrode material comprises the following steps:
the first step is as follows: dissolving cobalt salt in water to prepare a cobalt salt solution;
the second step is that: under the condition of stirring, diluting the cobalt salt solution by 10 times, then adding 1, 2, 4 triazole, and then adding 3, 5-dimethylpyrazole to form a first solution;
the third step: adding hydrazine hydrate to the first solution under stirring until a paste is obtained;
the fourth step: heating the paste in a water bath at 70 ℃ to generate a precipitate, then carrying out centrifugal separation, washing the obtained precipitate with deionized water, then washing with absolute ethyl alcohol, and then drying to obtain a cobalt precursor;
the fifth step: and (3) placing the cobalt precursor in a crucible, then covering the crucible with a cover, then performing high-temperature calcination by using a temperature-controlled muffle furnace, and naturally cooling to obtain the persimmon cake-shaped cobaltosic oxide.
The preferred embodiment is: in the first step, the concentration of the cobalt salt solution is 0.5 mol/L.
The preferred embodiment is: the cobalt salt is cobalt chloride.
The preferred embodiment is: in the second step, the molar ratio of the cobalt salt to the 1, 2, 4 triazole is 1: 5; the molar ratio of the cobalt salt to the 3, 5-dimethylpyrazole was 1:3.
The preferred embodiment is: in the second step, the molar ratio of cobalt salt to hydrazine hydrate was 1: 25.
The preferred embodiment is: in the second and third steps, the stirring speed was 220 r/min and the reaction temperature was 20 ℃.
The preferred embodiment is: the temperature condition during drying was 70 ℃.
The preferred embodiment is: in the fifth step, the calcination temperature is 600 ℃, the calcination time is 1 hour, and the temperature rise rate is 5 ℃/min.
A dried persimmon-shaped cobaltosic oxide lithium battery negative electrode material is prepared according to the preparation method.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (7)
1. A preparation method of a dried persimmon-shaped cobaltosic oxide lithium battery negative electrode material is characterized by comprising the following steps of: comprises the following steps:
the first step is as follows: dissolving cobalt salt in water to prepare a cobalt salt solution;
the second step is that: under the condition of stirring, diluting the cobalt salt solution by 10 times, then adding 1, 2, 4 triazole, and then adding 3, 5-dimethylpyrazole to form a first solution;
the third step: adding hydrazine hydrate to the first solution under stirring until a paste is obtained;
the fourth step: heating the paste in a water bath at 70-90 ℃ to generate a precipitate, then carrying out centrifugal separation, washing the obtained precipitate with deionized water, then washing with absolute ethyl alcohol, and then drying to obtain a cobalt precursor;
the fifth step: placing the cobalt precursor in a crucible, then covering the crucible with a cover, then performing high-temperature calcination by using a temperature-controlled muffle furnace, and naturally cooling to obtain persimmon cake-shaped cobaltosic oxide;
in the second step, the molar ratio of the cobalt salt to the 1, 2, 4 triazole is 1:2-1: 5; the molar ratio of the cobalt salt to the 3, 5-dimethylpyrazole is 1:1.5-1: 3.
2. The method for producing a negative electrode material for a dried-persimmon-like cobaltosic oxide lithium battery as defined in claim 1, wherein: in the first step, the concentration of the cobalt salt solution is 0.1-0.5 mol/L.
3. The method for producing a negative electrode material for a dried-persimmon-like cobaltosic oxide lithium battery as defined in claim 1, wherein: the cobalt salt is cobalt nitrate, cobalt acetate or cobalt chloride.
4. The method for producing a negative electrode material for a dried-persimmon-like cobaltosic oxide lithium battery as defined in claim 1, wherein: in the second step, the molar ratio of cobalt salt to hydrazine hydrate is 1:20 to 1: 25.
5. The method for producing a negative electrode material for a dried-persimmon-like cobaltosic oxide lithium battery as defined in claim 1, wherein: in the second step and the third step, the stirring speed is 180-220 r/min, and the reaction temperature is 20-25 ℃.
6. The method for producing a negative electrode material for a dried-persimmon-like cobaltosic oxide lithium battery as defined in claim 1, wherein: the temperature condition during drying is 50-70 ℃.
7. The method for producing a negative electrode material for a dried-persimmon-like cobaltosic oxide lithium battery as defined in claim 1, wherein: in the fifth step, the calcination temperature is 450-600 ℃, the calcination time is 1-3 hours, and the heating rate is 1-5 ℃/min.
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