CN112551594B - Lamellar nano cobalt oxyhydroxide and preparation method and application thereof - Google Patents
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Abstract
The invention relates to a lamellar nanometer cobalt oxyhydroxide and a preparation method and application thereof, under the condition of oil bath, hexamethylenetetramine and cobalt chloride hexahydrate are reacted by a coprecipitation method to generate cobalt hydroxide precipitate, and the precipitate is washed and dried; then oxidizing cobalt hydroxide by utilizing ammonium persulfate in a sodium hydroxide solution, and washing and drying the precipitate; grinding and sieving to obtain the product. The prepared nano cobalt oxyhydroxide is prepared into a lithium ion battery cathode, the first coulombic efficiency of the lithium ion battery cathode is up to 88%, the lithium ion battery cathode still has the specific discharge capacity of 942mAh/g after being subjected to charge-discharge circulation for 60 times under different currents and then being subjected to charge-discharge circulation for 300 times under the current density of 0.5C (1C= 890 mA/g), and the cobalt oxyhydroxide has a better application prospect in the aspect of lithium ion battery cathode materials.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to lamellar nano cobalt oxyhydroxide, and a preparation method and application thereof.
Background
The graphite-based lithium ion battery cathode material applied commercially at present has low specific capacity, and dendritic lithium is easily generated in the heavy-current charging and discharging process to cause a safety problem.
The cobalt oxide has higher theoretical mass specific capacity and small voltage hysteresis effect, and is expected to become a novel negative electrode material of the lithium ion battery. However, the electronic conductivity and lithium ion diffusion rate of the cobalt oxide are low, and the volume change is large in the charging and discharging process, so that the electrode material is pulverized, the capacity is rapidly attenuated, and the cycle performance and the rate capability are poor, so that the application of the cobalt oxide in the field of lithium ion battery cathode materials is restricted.
Therefore, how to improve the performance of the metal oxide negative electrode material in the lithium ion battery is a problem to be solved urgently.
Disclosure of Invention
The invention provides a lamellar nano cobalt oxyhydroxide, a preparation method and application thereof, and aims to solve the technical problems of low initial coulombic efficiency, poor rate capability, poor cycle stability and the like of a metal oxide negative electrode material in a lithium ion battery in the prior art to a certain extent.
The technical scheme for solving the technical problems is as follows: a preparation method of lamellar nano cobalt oxyhydroxide comprises the following steps:
mixing the alkaline solution with a cobalt source solution, and reacting at a preset temperature to obtain cobalt hydroxide;
oxidizing the cobalt hydroxide by ammonia persulfate or hydrogen peroxide under an alkaline condition to obtain the lamellar nano cobalt oxyhydroxide.
The lamellar nano cobalt oxyhydroxide prepared by the in-situ growth method under the alkaline condition is mutually adhered, so that the interface resistance between the lamellar layers is reduced, the transmission of electrons in the energy storage material is facilitated, the migration path of lithium ions is shortened, and the rate capability of the nano cobalt oxyhydroxide is improved.
Optionally, in the preparation method of the lamellar nano cobalt oxyhydroxide, the alkaline substance in the alkaline solution is any one of hexamethylenetetramine, sodium hydroxide, potassium hydroxide and ammonia water.
Optionally, the method for preparing lamellar nano cobalt oxyhydroxide comprises a step of dissolving cobalt source in cobalt source solution, wherein the cobalt source is any one of cobalt chloride hexahydrate, cobalt sulfate hexahydrate and cobalt nitrate.
Optionally, in the preparation method of the lamellar nano cobalt oxyhydroxide, the predetermined temperature is 85 to 140 ℃.
Optionally, the method for preparing the lamellar nano cobalt oxyhydroxide, wherein the step of oxidizing the cobalt hydroxide with ammonia persulfate or hydrogen peroxide under an alkaline condition to obtain the lamellar nano cobalt oxyhydroxide, specifically comprises:
adding ammonium persulfate or hydrogen peroxide and the cobalt hydroxide into a sodium hydroxide solution to obtain a mixed solution;
and adjusting the pH value of the mixed solution to make the mixed solution alkaline, and reacting for 10-20 hours under the alkaline condition to obtain the lamellar nano cobalt oxyhydroxide.
Optionally, the lamellar nano cobalt oxyhydroxide preparation method, wherein the concentration of the alkaline solution is 0.01-1.0mol/L; the concentration of the cobalt source solution is 0.01-1.0mol/L.
Optionally, the preparation method of the lamellar nano cobalt oxyhydroxide comprises the step of preparing a solution of the cobalt oxyhydroxide, wherein the concentration ratio of the alkaline solution to the source solution is 3-8:1.
Optionally, in the step of adding ammonium persulfate or hydrogen peroxide and the cobalt hydroxide to a sodium hydroxide solution to obtain a mixed solution, the temperature of the sodium hydroxide solution is 25 to 100 ℃.
Based on the same inventive concept, the invention also provides a lamellar nano cobalt oxyhydroxide, which is prepared by the preparation method.
Based on the same inventive concept, the invention also provides application of the lamellar nano cobalt oxyhydroxide serving as a lithium ion battery cathode material.
The lamellar nano cobalt oxyhydroxide serving as an energy storage material has the advantages of low production cost, simple and convenient method and much higher capacity than that of the graphite carbon material which is commercially applied at present, the average discharge capacities are 1145, 1092, 998, 798 and 619mAh/g respectively under the current densities of 0.2C, 0.5C, 1C, 3C and 5C, the material prepared by the method has the specific discharge capacity of 942mAh/g after 300 cycles under the current density of 0.5C, and the first coulombic efficiency reaches 88%. In addition, the lithium ion battery anode material has the specific discharge capacity of 950mAh/g after being subjected to charge-discharge cycling for 70 times under different multiplying powers and then being subjected to charge-discharge cycling for 300 times under the current density of 0.5C, and has a good application prospect in the aspect of lithium ion battery anode materials.
Drawings
FIG. 1 is a flow chart of a preparation method of lamellar nano cobalt oxyhydroxide according to an embodiment of the present invention;
FIG. 2 is an X-ray powder diffraction pattern of the energy storage material obtained in example 1;
FIG. 3 is a scanning electron microscope image of the energy storage material obtained in example 1;
FIG. 4 is a TEM image of the energy storage material obtained in example 1;
FIG. 5 is a graph of specific capacity versus efficiency at different currents tested for use as a negative electrode material for a lithium battery of the energy storage material obtained in example 1;
FIG. 6 is a graph showing the change of specific discharge capacity with cycle number of the energy storage materials obtained in examples 1 to 5 and comparative example 1.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. 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.
The negative electrode material of the graphite-based lithium ion battery which is commercially applied at present has low mass-to-capacity ratio, and dendritic lithium is easily generated in the large-current charging and discharging process to cause a safety problem, so that the negative electrode material of the lithium ion battery which can replace the graphite base and has good safety performance, high mass-to-capacity ratio and low price is urgently needed to be researched and developed. The cobalt oxide has higher theoretical mass specific capacity and small voltage hysteresis effect, and is expected to become a novel negative electrode material of the lithium ion battery. However, the application of cobalt oxide in the field of lithium ion battery cathode materials is limited by the defects of low electronic conductivity, low lithium ion diffusion rate, large volume change in the charging and discharging process, pulverization of electrode materials, rapid capacity attenuation, poor cycle performance and rate capability.
In view of the above disadvantages of cobalt oxide, in some cases, graphene and cobalt monoxide are compounded to alleviate the volume effect of cobalt monoxide in the charging and discharging processes, but in the preparation process, ultrasound, stirring and high-temperature calcination are used, so that the preparation process is complicated, and batch preparation is difficult to achieve.
The first discharge specific capacity of the cobalt oxyhydroxide cathode reported in the prior art can reach 1000-1600mAh/g, but the cobalt oxyhydroxide cathode has poor cycle stability and is attenuated to 400mAh/g after being charged and discharged for 40 times under the current density of 100 mA/g.
Based on this, the present invention provides a solution to the above technical problem, and the details thereof will be explained in the following embodiments.
Referring to fig. 1, as shown in fig. 1, an embodiment of the present invention provides a method for preparing a lamellar nano cobalt oxyhydroxide, including the following steps:
s10, mixing the alkaline solution with a cobalt source solution, and reacting at a preset temperature to obtain cobalt hydroxide;
specifically, under the condition of oil bath at 85-140 ℃, the alkaline solution and the cobalt source solution are mixed by adopting a coprecipitation method and then react to generate the cobalt hydroxide. Wherein, the alkaline solution can be one of hexamethylenetetramine, sodium hydroxide, potassium hydroxide or ammonia water; the cobalt source solution may be one of cobalt chloride hexahydrate, cobalt sulfate hexahydrate, or cobalt nitrate. It is understood that the heating conditions can be other heating methods besides oil bath, and the synthesis temperature can be 85 ℃ to 90 ℃,90 ℃ to 95 ℃,95 ℃ to 100 ℃,100 ℃ to 105 ℃,105 ℃ to 110 ℃,110 ℃ to 115 ℃,115 ℃ to 120 ℃,120 ℃ to 125 ℃,125 ℃ to 130 ℃,130 ℃ to 135 ℃, and 135 ℃ to 140 ℃.
The concentration of the hexamethylenetetramine solution is 0.01-1mol/L, the concentration of the cobalt chloride hexahydrate solution is 0.01-1mol/L, the stirring speed is 100-600 r/min during reaction, the oil bath heating time is 10-20h, the precipitate is subjected to suction filtration separation after being cooled, washed by deionized water for 3-6 times and dried at the temperature of 60-100 ℃.
And S20, oxidizing the cobalt hydroxide by using ammonium persulfate or hydrogen peroxide under an alkaline condition to obtain the lamellar nano cobalt oxyhydroxide.
Specifically, in a sodium hydroxide solution at 25-100 ℃, cobalt hydroxide is oxidized by ammonium persulfate or hydrogen peroxide, the pH is adjusted to make the mixed solution alkaline, and the oxidation time is 10-20h. Washing the precipitate with deionized water for 3-6 times, drying at 60-100 deg.C, and grinding. And after cooling, grinding and sieving to obtain the lamellar nano cobalt oxyhydroxide energy storage material.
Based on the same inventive concept, the invention also provides a lamellar nano cobalt oxyhydroxide, which is prepared by the preparation method, and the specific preparation process is as described above and is not described herein again.
Based on the same inventive concept, the invention also provides application of the laminar nano cobalt oxyhydroxide, which is used as a negative electrode material of a lithium ion battery, through tests, the first coulombic efficiency reaches 88%, and the specific discharge capacity of 942mAh/g is still obtained after 60 times of charge-discharge cycles under different current densities and then 300 times of charge-discharge cycles under the current density of 0.5C (1C =890mA/g).
The lamellar nano cobalt oxyhydroxide provided by the invention, and the preparation method and application thereof are further explained by specific preparation examples and comparative examples.
Example 1
Under the condition of an oil bath at 95 ℃, mixing an alkaline hexamine solution and a cobalt chloride hexahydrate solution by adopting a coprecipitation method to generate a cobalt hydroxide precipitate, wherein the concentration of the hexamine solution is 0.10mol/L, the concentration of the cobalt chloride hexahydrate solution is 0.02mol/L, the stirring speed is 500 r/min during reaction, the oil bath is heated for 10h, the precipitate is subjected to suction filtration separation after cooling, washed for 5 times by deionized water and dried at 80 ℃. Cobalt hydroxide was oxidized with ammonium persulfate or hydrogen peroxide in sodium hydroxide solution at room temperature, adjusted pH =14, oxidation time 10h. The precipitate was washed 3 times with deionized water, dried at 80 ℃ and ground. And after cooling, grinding and sieving to obtain the lamellar nano cobalt oxyhydroxide energy storage material. Thus obtaining the nano-sheet layered cobalt oxyhydroxide energy storage material.
Example 2
Under the condition of an oil bath at 95 ℃, mixing an alkaline hexamine solution and a cobalt chloride hexahydrate solution by adopting a coprecipitation method to generate a cobalt hydroxide precipitate, wherein the concentration of the hexamine solution is 0.12mol/L, the concentration of the cobalt chloride hexahydrate solution is 0.02mol/L, the stirring speed is 500 r/min during reaction, the oil bath is heated for 12h, the precipitate is subjected to suction filtration separation after cooling, washed for 5 times by deionized water and dried at 80 ℃. Cobalt hydroxide was oxidized with ammonium persulfate or hydrogen peroxide in sodium hydroxide solution at room temperature, adjusted pH =14, oxidation time 12h. The precipitate was washed 3 times with deionized water, dried at 80 ℃ and ground. And after cooling, grinding and sieving to obtain the lamellar nano cobalt oxyhydroxide energy storage material. Thus obtaining the nano-sheet layered cobalt oxyhydroxide energy storage material.
Example 3
Under the condition of an oil bath at 95 ℃, mixing an alkaline hexamine solution and a cobalt chloride hexahydrate solution by adopting a coprecipitation method to generate a cobalt hydroxide precipitate, wherein the concentration of the hexamine solution is 0.12mol/L, the concentration of the cobalt chloride hexahydrate solution is 0.02mol/L, the stirring speed is 500 r/min during reaction, the oil bath is heated for 14h, the precipitate is subjected to suction filtration separation after cooling, washed by deionized water for 5 times, and dried at 80 ℃. Cobalt hydroxide was oxidized with ammonium persulfate or hydrogen peroxide in sodium hydroxide solution at room temperature, adjusted pH =14, oxidation time 14h. The precipitate was washed 3 times with deionized water, dried at 80 ℃ and ground. And after cooling, grinding and sieving to obtain the lamellar nano cobalt oxyhydroxide energy storage material. Thus obtaining the nano-sheet layered cobalt oxyhydroxide energy storage material.
Example 4
Under the condition of an oil bath at 85 ℃, mixing an alkaline hexamine solution and a cobalt chloride hexahydrate solution by adopting a coprecipitation method to generate a cobalt hydroxide precipitate, wherein the concentration of the hexamine solution is 0.10mol/L, the concentration of the cobalt chloride hexahydrate solution is 0.02mol/L, the stirring speed is 400 r/min during reaction, the heating time of the oil bath is 16h, the precipitate is washed by deionized water for 5 times after cooling, and the precipitate is dried at 80 ℃. Cobalt hydroxide was oxidized with ammonium persulfate or hydrogen peroxide in sodium hydroxide solution at room temperature, adjusted pH =14, oxidation time 16h. The precipitate was washed 3 times with deionized water, dried at 80 ℃ and ground. And after cooling, grinding and sieving to obtain the lamellar nano cobalt oxyhydroxide energy storage material. Thus obtaining the nano-sheet layered cobalt oxyhydroxide energy storage material.
Example 5
Under the condition of 105 ℃ oil bath, mixing an alkaline hexamine solution and a cobalt chloride hexahydrate solution by adopting a coprecipitation method to generate a cobalt hydroxide precipitate, wherein the concentration of the hexamine solution is 0.14mol/L, the concentration of the cobalt chloride hexahydrate solution is 0.02mol/L, the stirring speed in the reaction is 300 r/min, the heating time of the oil bath is 18h, the precipitate is washed by deionized water for 5 times after cooling, and the precipitate is dried at 80 ℃. Cobalt hydroxide was oxidized at room temperature in sodium hydroxide solution with ammonium persulfate or hydrogen peroxide, adjusted to pH =14, for 18h. The precipitate was washed 3 times with deionized water, dried at 80 ℃ and ground. And after cooling, grinding and sieving to obtain the lamellar nano cobalt oxyhydroxide energy storage material. Thus obtaining the nano-sheet layered cobalt oxyhydroxide energy storage material.
Comparative example 1
Under the condition of an oil bath at 95 ℃, mixing an alkaline hexamine solution and a cobalt chloride hexahydrate solution by adopting a coprecipitation method to generate a cobalt hydroxide precipitate, wherein the concentration of the hexamine solution is 0.10mol/L, the concentration of the cobalt chloride hexahydrate solution is 0.02mol/L, the stirring speed is 500 r/min during reaction, the oil bath is heated for 10h, the precipitate is cooled, then subjected to suction filtration and separation, washed for 5 times by deionized water, dried at 80 ℃ and ground. After cooling, grinding and sieving to prepare the hexagonal nano cobalt hydroxide material. Thus obtaining the nano cobalt hydroxide material with hexagonal shape.
Comparative example 2
Under the condition of oil bath at 95 ℃, an alkaline hexamethylenetetramine solution and a cobalt chloride hexahydrate solution are mixed and precipitated by adopting a coprecipitation method to generate cobalt hydroxide, and the obtained cobalt hydroxide is calcined in a muffle furnace at 400 ℃ for 3 hours to obtain a cobaltosic oxide nano material serving as a comparison material. The concentration of the hexamethylene tetramine solution is 0.10mol/L, the concentration of the cobalt chloride hexahydrate solution is 0.02mol/L, the stirring speed is 500 r/min during reaction, and the heating time of the oil bath is 10h.
In order to test that the energy storage material provided by the invention has energy storage characteristics and can be used as a lithium battery cathode material, the energy storage materials obtained in the examples and the comparative examples are tested in terms of X-ray powder diffraction, a scanning electron microscope, a transmission electron microscope, a charge-discharge curve and the like, and the test results are shown in FIGS. 2 to 6.
Specifically, fig. 2 is an X-ray powder diffraction pattern of the energy storage material obtained in example 1, and it can be seen from the figure that the energy storage material contains a cobalt oxyhydroxide phase, and the crystal planes of cobalt oxyhydroxide (003), (012), (015), and (110) are distinct. Fig. 3 is a scanning electron microscope image of the energy storage material obtained in example 1, it can be seen from (a) of fig. 3 that the prepared energy storage material is composed of irregularly shaped nano-scale particles, and from (b) of fig. 3 that the energy storage material has a nano-scale lamellar structure. Fig. 4 is a transmission electron microscope image of the energy storage material obtained in example 1, and it can be seen from the image that the prepared energy storage material has a nano-sheet structure. Fig. 5 is a specific capacity and efficiency diagram obtained by testing when the energy storage material obtained in example 1 is used as a lithium battery negative electrode material, average discharge capacities of the energy storage material are 1145, 1092, 998, 798 and 619mAh/g under current densities of 0.2C, 0.5C, 1C, 3C and 5C, respectively, the material prepared by the invention has a specific discharge capacity of 942mAh/g after 300 cycles at a current density of 0.5C, and the first coulombic efficiency reaches 88%. The first discharge specific capacity is 1134.6mAh/g, the first charge specific capacity is 1008.0mAh/g, and the first coulombic efficiency is 88.84%. Fig. 6 is a graph of specific capacity versus cycle number of the energy storage materials obtained in examples 1 to 5 and comparative examples 1 to 2 under different currents when used as negative electrode materials of lithium batteries, and it can be seen from the graph that the specific capacity of the energy storage material of example 1 is the largest, the specific discharge capacities of the energy storage materials obtained in examples 1 to 5 and comparative examples 1 to 2 after 300 cycles at a current density of 0.5C are 953, 844, 392, 347, 140, 88 and 411mAh/g, respectively, and 1, 2, 3, 4, 5, 6 and 7 in fig. 6 represent the specific capacities of the energy storage materials obtained in examples 1 to 5 and comparative examples 1 to 2 as a function of the cycle number, respectively.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. A preparation method of lamellar nano cobalt oxyhydroxide is characterized by comprising the following steps:
mixing the alkaline solution with a cobalt source solution, and reacting at a preset temperature to obtain cobalt hydroxide;
oxidizing the cobalt hydroxide by using ammonium persulfate or hydrogen peroxide under an alkaline condition to obtain lamellar nano cobalt oxyhydroxide; the step of oxidizing the cobalt hydroxide by ammonia persulfate or hydrogen peroxide under an alkaline condition to obtain the lamellar nano cobalt oxyhydroxide specifically comprises the following steps:
adding ammonia persulfate or hydrogen peroxide and the cobalt hydroxide into a sodium hydroxide solution to obtain a mixed solution;
adjusting the pH value of the mixed solution to make the mixed solution alkaline, and reacting for 10-20 hours under the alkaline condition to obtain lamellar nano cobalt oxyhydroxide;
in the step of adding ammonia persulfate or hydrogen peroxide and the cobalt hydroxide into the sodium hydroxide solution to obtain a mixed solution, the temperature of the sodium hydroxide solution is 25-100 ℃;
the concentration of the alkaline solution is 0.01-1.0mol/L;
the concentration of the cobalt source solution is 0.01-1.0mol/L;
the concentration ratio of the alkaline solution to the cobalt source solution is 3-8:1.
2. The method for preparing the lamellar nano cobalt oxyhydroxide according to claim 1, wherein the alkaline substance in the alkaline solution is any one of hexamethylenetetramine, sodium hydroxide, potassium hydroxide and ammonia water.
3. The method for preparing the lamellar nano cobalt oxyhydroxide according to claim 1, wherein the cobalt source in the cobalt source solution is any one of cobalt chloride hexahydrate, cobalt sulfate hexahydrate, and cobalt nitrate.
4. The method for preparing the lamellar nano cobalt oxyhydroxide according to claim 1, wherein the predetermined temperature is 85 to 140 ℃.
5. A lamellar nano cobalt oxyhydroxide, characterized by being prepared by the preparation method according to any one of claims 1 to 4.
6. Use of the lamellar nano cobalt oxyhydroxide according to claim 5 as a negative electrode material for lithium ion batteries.
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| CN102820466A (en) * | 2012-08-17 | 2012-12-12 | 浙江大学 | Cathode material of lithium ion battery based on hydroxyl cobalt oxide and preparation method of cathode material |
| WO2014205186A2 (en) * | 2013-06-20 | 2014-12-24 | The Regents Of The University Of Michigan | Electrochemical device electrode including cobalt oxyhydroxide |
| CN110364365A (en) * | 2018-04-11 | 2019-10-22 | 中国科学院青岛生物能源与过程研究所 | A kind of method that electrochemical oxidation process prepares single layered porous hydroxy cobalt oxide nanometer sheet |
| CN108598470A (en) * | 2018-04-23 | 2018-09-28 | 湖南工学院 | Lithium ion battery negative material and the method for preparing lithium ion battery negative electrode |
| CN110479277A (en) * | 2019-08-30 | 2019-11-22 | 济南大学 | A method of promoting the catalysis fixed nitrogen reaction of nano-hydroxy cobalt oxide |
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