CN110668505B - Cobalt-containing two-dimensional accordion-shaped nanosheet material and preparation method and application thereof - Google Patents

Cobalt-containing two-dimensional accordion-shaped nanosheet material and preparation method and application thereof Download PDF

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CN110668505B
CN110668505B CN201910908985.0A CN201910908985A CN110668505B CN 110668505 B CN110668505 B CN 110668505B CN 201910908985 A CN201910908985 A CN 201910908985A CN 110668505 B CN110668505 B CN 110668505B
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张潇予
余志鹏
姜付义
杜伟
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Abstract

The invention discloses a cobalt-containing two-dimensional accordion-shaped nanosheet material as well as a preparation method and application thereof. The cobalt-containing two-dimensional accordion-like nanosheet material is characterized by Mn1‑xCoxV2O6Wherein x is more than or equal to 0.1 and less than or equal to 0.5, the shape is an accordion-shaped nano sheet, the thickness is between 10 and 100nm, and the length/width is between 1 and 100 mu m. According to the method, the nano material is prepared by a one-step hydrothermal method, and the material with the accordion-shaped nanosheet shape is obtained by changing conditions such as cobalt-manganese ratio, reaction time and the like. The method has the characteristics of simple reaction process, easy operation of steps, regular shape of the prepared nanosheet, high efficiency and stability as a lithium ion battery cathode material, high specific capacity, good cycling stability and the like.

Description

Cobalt-containing two-dimensional accordion-shaped nanosheet material and preparation method and application thereof
Technical Field
The invention belongs to the field of electrochemical energy, and particularly relates to a method for synthesizing Mn with better performance by doping cobalt into manganese vanadate nanosheets1-xCoxV2O6And (3) a negative electrode material.
Background
The manganese vanadate is a lithium ion battery cathode material with good performance, and has considerable application prospect due to abundant reserves, cheap price of constituent elements. Although the manganese vanadate has a special layered structure and should have high theoretical specific capacity, the manganese vanadate negative electrode material can form a partial amorphous state in the lithiation and delithiation processes, so that the layered structure collapses, the lithium storage capacity and the specific capacity of the manganese vanadate negative electrode material are greatly reduced, and the long-term cycle performance is influenced. In addition, most of manganese vanadate materials reported in documents and patents are irregular particles, microtubes, microrods and the like, which are not beneficial to ion migration and maintenance of morphological structures in the charging and discharging processes, so that active materials are stripped from current collectors, and development and application of the manganese vanadate materials as negative electrode materials are limited.
CN 105280917A discloses a preparation method of manganese metavanadate serving as a negative electrode material of a lithium ion battery, which comprises the following steps of mixing deionized water and dimethyl sulfoxide according to a volume ratio VWater (W):VDimethyl sulfoxideMixing the materials in a ratio of 1: 1-2, placing the mixture in a water bath kettle at the temperature of 60-90 ℃, ultrasonically stirring the mixture for 0.5-2 h (2), adding a vanadium source and a manganese source into the mixed solution according to the molar ratio of the vanadium element to the manganese element of 2:1, and controlling the concentration of vanadium ions in the mixed solution to be 0.1-0.5 mol/L; adjusting the pH value to 4-7 by ammonia water or acetic acid, and carrying out ultrasonic stirring reaction for 2-6 h to obtain a reactant; filtering the reactant, and cleaning with deionized water and alcohol; and drying for 4-6 h at 50-80 ℃ under the vacuum degree of 5-100 Pa to obtain manganese metavanadate tetrahydrate. The negative electrode material has low temperature required by reaction, simple reaction process and convenient industrial control, but the synthesized product has micron rod-shaped and granular appearance, and is difficult to maintain the initial appearance after repeated circulation, so that the stability and the cyclicity of the product are poor, and the maximum specific capacity is only about 430 mAh/g.
CN 104528830B discloses a preparation method of manganese metavanadate serving as a negative electrode material of a lithium ion battery, which comprises the following steps: preparing sodium orthovanadate and manganese salt into a mixed solution according to a molar ratio of V to Mn of 1-3 to 1; adjusting the pH value of the mixed solution to 7-8, stirring for 10min, transferring into a reaction kettle, and reacting at the temperature of 160 ℃ and 260 ℃ for 124h to obtain a solution of a crude product; cooling the solution of the obtained crude product to room temperature, washing and drying to obtain manganese vanadate Mn6.87(OH)3(VO4)3.6(V2O7)0.2Nano-micron material. The method realizes the low-temperature controllable preparation of the manganese vanadate, and has the advantages of low energy consumption, environmental friendliness and pure product. However, from which manganese Mn vanadate6.87(OH)3(VO4)3.6(V2O7)0.2The scanning electron microscope analysis chart of the nano particles shows that although the material is uniform in shape and size, the product is granular in shape, and the stable and long-term use of the negative electrode material is not facilitated. In addition, manganese Mn vanadate6.87(OH)3(VO4)3.6(V2O7)0.2The scanning electron microscope analysis chart of the microtube shows that the performance of the cathode material cannot be obviously improved when the width of the microtube is 5 micrometers.
Namely, the stability and the cyclicity of the lithium ion battery cathode material manganese vanadate disclosed by the prior art as a cathode material are poor, and the long-term cycle performance is influenced.
Disclosure of Invention
The invention aims to solve the technical problem of providing a cobalt-containing two-dimensional accordion-shaped nanosheet material, and a preparation method and application thereof, and particularly Mn1-xCoxV2O6(x is more than or equal to 0.1 and less than or equal to 0.5) two-dimensional accordion-shaped nanosheet material, and a preparation method and application thereof. The invention has the characteristics of simple reaction process, easy operation of steps, special two-dimensional accordion-shaped prepared nanosheet shape, high efficiency and stability as a lithium ion battery cathode material, high specific capacity, good cycling stability and the like.
The preparation method of the invention is used for realizing one of the purposes of the invention.
The method comprises the following steps:
(1) weighing and mixing salts containing a cobalt source and a manganese source according to the molar ratio of cobalt to manganese of 1: 1-9, placing the mixture into a beaker A, adding deionized water, and stirring and dissolving. Wherein the salt containing a cobalt source is any one of cobalt chloride, cobalt nitrate and cobalt sulfate, and the manganese source is any one of manganese nitrate, manganese chloride and manganese sulfate;
(2) weighing ammonium metavanadate according to the molar ratio of the salts to the ammonium metavanadate of 1: 1-3, weighing polyvinylpyrrolidone (PVP) according to 1-50% of the total mass of the salts, placing the PVP in a beaker B, pouring deionized water, and stirring and dissolving at 70-80 ℃;
(3) adding the solution in the beaker B into the beaker A, adding ammonia water to adjust the pH of the mixed solution to be between 8 and 10, and stirring for 2 to 5 minutes at room temperature;
(4) sealing the obtained crude product solution into a reaction kettle, putting the reaction kettle into an oven, setting the temperature to be 120-200 ℃, and reacting for 6-24 hours;
(5) and (3) completing the heating reaction, completely centrifuging the solution, removing supernatant, and drying the precipitate in an oven at the temperature of 60-80 ℃ for 2-24 hours to obtain the prepared sample.
According to the scheme, the nano material is prepared by a one-step hydrothermal method, and the material with the accordion-shaped nanosheet shape is obtained by changing conditions such as cobalt-manganese ratio, reaction time and the like.
In order to realize the second purpose of the invention, the nano material prepared by the invention.
The two-dimensional accordion-shaped nanosheet material prepared by the method is characterized in that the nanometer negative material manganese vanadate nanosheet is doped with cobalt and Mn1-xCoxV2O6Wherein x is more than or equal to 0.1 and less than or equal to 0.5, the shape is an accordion-shaped nano sheet, the thickness is between 10 and 100nm, and the length/width is between 1 and 100 mu m.
Furthermore, the XRD spectrum of the product shows the intensity and position of diffraction peak of the product and manganese vanadate standard card (MnV)2O6No.72-1837) and no hetero-phase diffraction peak.
In order to achieve the third purpose of the invention, the application of the nano material prepared by the invention is realized.
The two-dimensional accordion-shaped nanosheet material prepared by the method is applied as a lithium ion battery cathode material.
The two-dimensional accordion-shaped nanosheets prepared by the method are used as a negative electrode material, multiple tests such as XRD, SEM and TEM are carried out, the two-dimensional accordion-shaped nanosheets are used as active materials to coat a pole piece to assemble a button battery, electrochemical performance tests such as impedance analysis and multiplying power cycle analysis are carried out, and test results show that the product of the invention has higher specific capacity, higher stability and higher cyclicity when being used as the negative electrode material of the lithium ion battery compared with the common negative electrode material manganese metavanadate of the lithium ion battery.
The outstanding substantive characteristic of the invention is that the prepared manganese vanadate material doped with the cobalt element, namely Mn1-xCoxV2O6(x is more than or equal to 0.1 and less than or equal to 0.5) two-dimensional accordion-shaped nanosheet material, and the two-dimensional accordion-shaped nanosheet material has the remarkable beneficial effects of high multiplying power, high energy storage and long service life when being applied as a lithium electronic negative electrode material. The analysis reason is that the cobalt atom completes atomic replacement with partial manganese atom in the manganese vanadate, and the existence of + 3-valent cobalt in the crystal structure causesThe formation of an electric field in the electrode is realized, the migration path of lithium ions in the embedding/separating process during charging and discharging is shortened, the transportation of the lithium ions and electrons is promoted, and excellent lithium storage performance is obtained, including high capacity and high rate, and meanwhile, due to the catalytic action of cobalt, the crystal structure grows to be regularly arranged two-dimensional organ-shaped nanosheet morphology (the organ-shaped layered structure is stable when being used as a lithium battery cathode material, and the structure is not easy to collapse during charging and discharging), so that the lithium battery electrode material has better structural stability and specific capacity (improved by 100-160%) compared with a manganese vanadate cathode material; further from the analysis of a crystal atom structure, the doping of cobalt element in the crystal structure of the two-dimensional accordion-shaped nano sheet enhances the interface bonding force, stronger Li-Co ionic bond can reduce the accumulation of charges at the interface during charging and discharging, offset the weakening effect of partial lithiation on the interface strength, improve the interface bonding strength and reduce the fracture and peeling of the active material, compared with other manganese vanadate materials in the forms of irregular particles, micron tubes, micron rods and the like, the method overcomes the peeling and loss of the active material caused by ion migration during charging and discharging, further has the cycle stability of the far-exceeding manganese vanadate material, and is 0.1A g-1Can still maintain more than 1000mAh g after circulating for 300 circles under the current density-1The specific capacity of (A).
Compared with the prior art, the invention has the beneficial effects that:
the Mn of the invention1-xCoxV2O6(x is more than or equal to 0.1 and less than or equal to 0.5) cobalt is doped in the molecular structure of the nano sheet material, the nano sheet material is in a two-dimensional accordion-shaped shape, wherein the thickness of the nano material is between 10 and 100nm, and the length/width is between 1 and 100 mu m.
According to the preparation method, the cobalt element is added by adopting hydrothermal synthesis, and the appropriate content ratio of the cobalt element to the manganese element is adjusted, so that the doping effect of the cobalt is optimal, and the battery cathode material with high multiplying power, high energy storage and long service life is prepared. In addition, the preparation method of the invention uses PVP as a dispersant, and improves the material performance, because PVP is a very characteristic synthetic compound, which is soluble in water and most of organic solvents, and has very low toxicity and good physiological intermiscibility, and moreover, the price of the raw material butyrolactone is lower.
The product is subjected to multiple tests such as XRD, SEM, TEM and the like, and is used as an active material to coat a pole piece to assemble a button battery, and electrochemical performance tests such as impedance analysis, multiplying power cycle analysis and the like are performed, and test results show that the product serving as a negative electrode material (more than 900 mAh/g) is improved by more than 100-160% in specific capacity compared with a manganese vanadate material (about 400 mAh/g), and has stronger structural stability and charge-discharge cyclicity.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 shows Mn as a product of example 10.9Co0.1V2O6XRD diffraction pattern of
FIG. 2 shows Mn as a product of example 10.9Co0.1V2O6SEM image of
FIG. 3 shows Mn as a product of example 20.8Co0.2V2O6SEM image of
FIG. 4 shows Mn as a product of example 20.8Co0.2V2O6The weight ratio of the elements
FIG. 5 shows Mn as a product of example 30.7Co0.3V2O6Raman spectrum of
FIG. 6 shows Mn as a product of example 30.7Co0.3V2O6Comparison graph of cycle performance of lithium ion battery cathode material with manganese vanadate
FIG. 7 is a drawing showingExample 4 product Mn0.6Co0.4V2O6TEM image of
FIG. 8 shows Mn as a product of example 40.6Co0.4V2O6Comparison graph of cycle performance of lithium ion battery cathode material with manganese vanadate
FIG. 9 shows Mn as a product of example 50.5Co0.5V2O6EDS element distribution mapping chart
FIG. 10 shows Mn as a product of example 50.5Co0.5V2O6Charge-discharge performance diagram as lithium ion battery cathode material
FIG. 11 shows Mn as a product of example 50.5Co0.5V2O6Graph for comparing rate performance of lithium ion battery cathode material with manganese vanadate
Detailed Description
The present invention will now be described in more detail with reference to the accompanying drawings, in which preferred embodiments of the invention are shown, it being understood that one skilled in the art may modify the invention herein described while still achieving the beneficial results of the present invention. Accordingly, the following description should be construed as broadly as possible to those skilled in the art and not as limiting the invention.
Example 1
At room temperature, 2.28mmol of manganese chloride and 0.25mmol of cobalt chloride (namely the molar ratio of Mn: Co ═ 9:1) are weighed and poured into a beaker A, 10ml of deionized water is added for dissolution, 0.5g of PVP and 4.8mmol of ammonium metavanadate are weighed and poured into a beaker B, 37ml of deionized water is added for dissolution at 70-80 ℃, the solution in the beaker B is dropwise poured into the beaker A, ammonia water is added for adjusting the pH value of the solution to 8, and the solution is stirred at room temperature for 4 min. The obtained reaction solution is put into a reaction kettle and put into an oven, the temperature is set to be 180 ℃, and the reaction time is 18 hours. And putting the reacted crude solution into a centrifuge tube, centrifuging the solution for three times by using deionized water, washing the solution once by using absolute ethyl alcohol, finishing centrifugation, pouring out supernate, drying the supernate in an oven at 60 ℃, slightly and uniformly grinding the supernate, filling the powder into a bottle, and waiting for detection.
The product Mn is0.9Co0.1V2O6By X-ray diffraction (XRD) analysis and scanning electron microscope analysis, as shown in figures 1 and 2, XRD spectrogram result shows intensity and position of diffraction peak of product and manganese vanadate standard card (MnV)2O6No.72-1837) and no hetero-phase diffraction peak, indicating that Mn with higher purity is obtained0.9Co0.1V2O6(x is more than or equal to 0.1 and less than or equal to 0.5) sample, and the doping of Co does not change MnV2O6The basic crystal structure of (a); scanning electron microscope analysis shows that the product consists of a large number of accordion-shaped nano sheets, and the thickness of the nano sheets is 30-35 mu m.
The resulting product Mn0.9Co0.1V2O6And MnV2O6The lithium ion battery anode material is tested as a lithium ion battery anode material, and specific capacity comparison data of the lithium ion battery anode material under different current densities are shown in table 1.
TABLE 1
Figure BDA0002212125240000051
Figure BDA0002212125240000061
As can be seen from Table 1, Mn was obtained as a product after doping with cobalt0.9Co0.1V2O6At 0.1Ag-1The specific capacity is improved by 27.4 percent under the current density of (2) and is 0.2Ag-1The specific capacity is improved by 75.3 percent and 0.5Ag is added under the current density of-1、1Ag-1、2Ag-1、5Ag-1、10Ag-1The specific capacity is improved by more than 100% under the current density.
Example 2
At room temperature, 2.16mmol of manganese chloride and 0.54mmol of cobalt nitrate (namely Mn: Co ═ 4:1) are weighed and poured into a beaker A, 10ml of deionized water is added for dissolution, then 0.5g of PVP and 4.8mmol of ammonium metavanadate are weighed and poured into a beaker B, 37ml of deionized water is added for dissolution at 70-80 ℃, the solution in the beaker B is poured into the beaker A, ammonia water is added, the pH value is adjusted to 8, and the mixture is stirred at room temperature for 4 min. The obtained reaction solution is put into a reaction kettle and put into an oven, the temperature is set to be 180 ℃, and the reaction time is 18 hours. And putting the reacted crude solution into a centrifuge tube, centrifuging the solution for three times by using deionized water, washing the solution once by using absolute ethyl alcohol, putting the solution into a 60-DEG C oven for drying, slightly grinding the solution, filling the solution into a bottle, and detecting the solution in the bottle.
The SEM image of the product is shown in figure 3, the sample has an accordion-shaped nano structure, is regular and ordered, has a stable accordion-shaped laminated structure, is not easy to collapse in charging and discharging processes, and improves the stability of the product; figure 4 reflects the mass ratio of the elements in the product.
The resulting product Mn0.8Co0.2V2O6The manganese vanadate and the manganese vanadate are respectively used as the negative electrode materials of the lithium ion battery to be tested, and the specific capacity comparison data of the sample and the manganese vanadate is shown in table 2, so that Mn obtained after cobalt is doped in a manganese vanadate nanosheet0.8Co0.2V2O6The cycle performance of the battery is improved.
TABLE 2
Figure BDA0002212125240000062
Figure BDA0002212125240000071
From Table 2, Mn0.8Co0.2V2O6The specific capacity of the material is greatly improved compared with that of the manganese vanadate material not doped with cobalt, and the current density is 1Ag-1Mn (m) of0.8Co0.2V2O6The specific capacity is improved by more than 2 times, and the result proves that the manganese vanadate can obtain a lithium battery cathode material with better performance after being doped with cobalt.
Example 3
Weighing 1.92mmol of manganese sulfate and 0.82mmol of cobalt chloride (namely Mn: Co ═ 7:3) at room temperature, pouring into a beaker A, adding 10ml of deionized water for dissolving, weighing 0.5g of PVP and 4.8mmol of ammonium metavanadate, pouring into a beaker B, adding 37ml of deionized water for dissolving at 70-80 ℃, dropwise pouring the solution in the beaker B into the beaker A, adding ammonia water, adjusting the pH value to 9, and stirring at room temperature for 4 min. The obtained reaction solution is put into a reaction kettle and put into an oven, the temperature is set to be 180 ℃, and the reaction time is 18 hours. And putting the reacted crude solution into a centrifuge tube, centrifuging the solution for three times by using deionized water, washing the solution once by using absolute ethyl alcohol, finishing centrifugation, pouring out supernate, drying the supernate in an oven at 60 ℃, slightly and uniformly grinding the supernate, filling the powder into a bottle, and waiting for detection.
The sample is subjected to electrochemical analysis, a product Raman diagram is shown in figure 5, the product and the sample in the image are similar in shape, and the performance of the manganese vanadate is hardly damaged.
Using manganese vanadate and Mn0.7Co0.3V2O6The cycle comparison diagram of the lithium ion batteries respectively used as the cathode materials is shown in FIG. 6, and it can be seen that Mn obtained after cobalt is doped in the manganese vanadate nanosheets0.7Co0.3V2O6The cycle performance of the battery is improved, and the coulomb efficiency is almost still 100%.
The resulting product Mn0.7Co0.3V2O6The specific capacities of the lithium ion batteries using manganese vanadate as the negative electrode material, respectively, are shown in table 3.
TABLE 3
Figure BDA0002212125240000072
Figure BDA0002212125240000081
Analysis Table 3 shows that Mn0.7Co0.3V2O6The specific capacity of the alloy is compared with that of common MnV2O6The cathode material is greatly improved, and has higher specific capacity than manganese vanadate under various current densities, especially the current density of 1Ag-1And 2Ag-1Mn (m) of0.8Co0.2V2O6The specific capacity is improved by more than 2.6 times.
Example 4
Weighing 1.08mmol of manganese nitrate and 0.72mmol of cobalt chloride (namely Mn: Co ═ 3:2) at room temperature, pouring into a beaker A, adding 10ml of deionized water for dissolving, weighing 0.5g of PVP and 4.8mmol of ammonium metavanadate, pouring into a beaker B, adding 37ml of deionized water for dissolving in an environment at 70-80 ℃, dropwise pouring the solution in the beaker B into the beaker A, adding ammonia water, adjusting the pH value to 9, and stirring at room temperature for 4 min. The obtained reaction solution is put into a reaction kettle and put into an oven, the temperature is set to be 180 ℃, and the reaction time is 18 hours. And putting the reacted crude solution into a centrifuge tube, centrifuging the solution for three times by using deionized water, washing the solution once by using absolute ethyl alcohol, finishing centrifugation, pouring out supernate, drying the supernate in an oven at 60 ℃, slightly and uniformly grinding the supernate, filling the powder into a bottle, and waiting for detection.
Wherein the TEM image of the product, as shown in FIG. 7, shows the product Mn0.6Co0.4V2O6The appearance is in a nanometer sheet shape.
Using manganese vanadate and Mn0.6Co0.4V2O6The cycle comparison graph of the lithium ion batteries respectively used as the cathode materials is shown in fig. 8, and it can be seen that Mn obtained after cobalt is doped in the manganese vanadate nanosheets0.6Co0.4V2O6The cycle performance of the battery is improved, and the coulomb efficiency is almost still 100%. The rate performance of the sample versus manganese vanadate is shown in table 4.
TABLE 4 Mn of the product obtained0.6Co0.4V2O6Specific capacity comparison with manganese vanadate
Figure BDA0002212125240000082
As can be seen from Table 4, the specific capacity of manganese vanadate at each current density is much lower than that of Mn0.6Co0.4V2O6The specific capacity of the sample obtained in this example was up to 156.47% at the different current densities mentioned above.
Example 5
Weighing 1.2mmol of manganese nitrate and 1.2mmol of cobalt chloride (namely Mn: Co ═ 1:1) at room temperature, pouring into a beaker A, adding 10ml of deionized water for dissolving, weighing 0.5g of PVP and 4.8mmol of ammonium metavanadate, pouring into a beaker B, adding 37ml of deionized water for dissolving in an environment at 70-80 ℃, dropwise pouring the solution in the beaker B into the beaker A, adding ammonia water, adjusting the pH value to 10, and stirring at room temperature for 4 min. The obtained reaction solution is put into a reaction kettle and put into an oven, the temperature is set to be 180 ℃, and the reaction time is 18 hours. And putting the reacted crude solution into a centrifuge tube, centrifuging the solution for three times by using deionized water, washing the solution once by using absolute ethyl alcohol, finishing centrifugation, pouring out supernate, drying the supernate in an oven at 60 ℃, slightly and uniformly grinding the supernate, filling the powder into a bottle, and waiting for detection.
Mn of the above product0.5Co0.5V2O6The EDS image of (a) is shown in fig. 9.
The charge-discharge curve chart of the assembled battery coated with the electrode plate is shown in FIG. 10, and the rate performance chart is shown in FIG. 11. Sample Mn0.5Co0.5V2O6The ratio of the ratio to the ratio of manganese vanadate is shown in Table 5.
Table 5: the resulting product Mn0.5Co0.5V2O6Specific capacity comparison data with manganese vanadate
Figure BDA0002212125240000091
From the analysis in Table 5, Mn0.5Co0.5V2O6The material is a benign material with specific capacity greatly exceeding that of manganese vanadate and is 0.1Ag-1、0.2Ag-1The specific capacity can reach 28.067%, 83.82% and 0.5A g% under the current density-1、1Ag-1、2A g-1、5Ag-1、10A g-1The current density of the lithium battery anode material can reach 123.9%, 113.44%, 137.76%, 116.37% and 103.34%, and the lithium battery anode material with better performance is obtained after the manganese vanadate is doped with cobalt.
The experiments of examples 1-5 demonstrate that Mn is successfully obtained by the present invention1-xCoxV2O6(x is more than or equal to 0.1 and less than or equal to 0.5) two-dimensional accordion-shaped nanosheet material, and the two-dimensional accordion-shaped nanosheet material has high multiplying power, high energy storage and long service life when being used as a lithium electronic negative electrode materialThe method has the remarkable beneficial effects. Compared with the manganese vanadate material, the essential change of the embodiment is that cobalt is doped, the addition of cobalt salt promotes the growth of crystal morphology to generate accordion-shaped nanosheets, and the lithium battery electrode test also proves that the specific capacity of the lithium battery cathode material battery is multiplied. The reason for remarkably improving the analysis technical effect is that the crystal structure is changed by doping and replacing part of manganese element with cobalt, the catalytic action of the cobalt enables the crystal structure to grow into the regularly arranged two-dimensional organ-shaped nanosheet shape, the specific capacity of the battery is remarkably improved when the battery is used as a lithium battery cathode material, the migration path of lithium ions in the embedding/separating process during charging and discharging is shortened due to the existence of the cobalt element in the crystal structure, meanwhile, the interface binding force is enhanced due to the existence of the cobalt element in the crystal structure of the two-dimensional organ-shaped nanosheet, the stripping and loss of an active material caused by ion migration during charging and discharging are overcome, and the battery has the cycle stability of a far-exceeding manganese vanadate material.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (2)

1. The preparation method of the cobalt-containing two-dimensional accordion-shaped nanosheet material is characterized by comprising the following steps of:
(1) weighing and mixing salts containing a cobalt source and a manganese source according to the molar ratio of cobalt to manganese of 1: 1-9, placing the mixture in a container A, adding deionized water, stirring and dissolving,
the cobalt source-containing salts are any one of cobalt chloride, cobalt nitrate and cobalt sulfate, and the manganese source-containing salts are any one of manganese nitrate, manganese chloride and manganese sulfate;
(2) weighing ammonium metavanadate according to the molar ratio of the salts to the ammonium metavanadate of 1: 1-3, weighing polyvinylpyrrolidone (PVP) according to 1-50% of the total mass of the salts, placing the two into a container B, pouring deionized water into the container B, and stirring and dissolving at 70-80 ℃;
(3) adding the solution in the container B into the container A to obtain a mixed solution, adding ammonia water, adjusting the pH of the mixed solution to be between 8 and 10, and stirring at room temperature for 2 to 5 minutes;
(4) then sealing the mixed liquid into a reaction kettle, putting the reaction kettle into an oven, setting the temperature to be 120-200 ℃, and reacting for 6-24 hours;
(5) after the heating reaction is finished, centrifuging the obtained solution, removing supernatant, and drying the precipitate in an oven at the temperature of 60-80 ℃ for 2-24 hours to obtain a cobalt-containing two-dimensional accordion-shaped nanosheet material;
wherein the cobalt-containing two-dimensional accordion-shaped nanosheet material is Mn1-xCoxV2O6Wherein x is more than or equal to 0.1 and less than or equal to 0.5, the shape is an accordion-shaped nano sheet, the thickness is between 10 and 100nm, and the length/width is between 1 and 100 mu m.
2. The use of the cobalt-containing two-dimensional accordion-like nanoplatelets prepared by the method of claim 1 as a lithium battery negative electrode material.
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