CN113629230B - Lithium ion battery cathode material and preparation method thereof - Google Patents
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Abstract
The invention discloses a lithium ion battery cathode material and a preparation method thereof, wherein the preparation method of the material comprises the following steps: firstly, synthesizing polydopamine nano-microspheres by a nano-emulsion assembling method, and then uniformly coating molybdenum disulfide nano-sheets on the surfaces of the polydopamine nano-microspheres through a hydrothermal reaction; preparation of molybdenum disulfide/polydopamine-derived carbon microspheres (MoS) through high-temperature calcination process 2 a/C composite); finally MoS 2 the/C composite material and the nano-silicon are mixed and ground according to a certain proportion to prepare a final product. The preparation method is simple and environment-friendly, and the prepared cathode material has high capacity, long circulation and excellent conductive property; in addition, the scheme can accurately regulate and control MoS by controlling the addition of the nano-silicon 2 The mixing ratio of the/C composite material and the nano silicon is adjusted, so that a slave product with the optimal performance is obtained.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a lithium ion battery cathode material and a preparation method thereof.
Background
Lithium Ion Batteries (LIBs) are well known to be one of the important energy storage systems for portable electronic devices and electric vehicles. In the past decades, lithium ion batteries have received much attention due to the ever increasing energy consumption and energy storage requirements. The graphite has the advantages of environmental friendliness, low cost, good cycling stability and the like, is a standard commercial negative electrode material of a lithium ion battery, but has relatively low theoretical capacity (372 mAh & g) -1 ) But prevents the use of LIBs in high energy systems. Therefore, the development of high performance electrode materials with high energy density and high cycling stability is a urgent task for portable electronic and electric vehicles.
Molybdenum disulfide (MoS) 2 ) The graphene-like two-dimensional material is a representative two-dimensional material with a graphene-like structure, weak van der Waals force between layers is beneficial to the diffusion of lithium ions and electrons, and the high theoretical lithium storage capacity (670 mAh.g) is caused by the double-layer charge storage capacity -1 ) Is considered to be a promising lithium ion battery cathode material. However, in the circulation process, due to poor intrinsic conductivity and large mechanical strain, the capacity attenuation is serious, and the application of molybdenum disulfide in the field of lithium ion battery cathode materials is greatly limited. To address the above limitations, researchers have sought to improve the overall conductivity and structural stability of molybdenum disulfide materials. One of the most effective strategies is to combine molybdenum disulfide with a high-conductivity carbon-based carrier, so as to better cope with the huge volume change caused by lithiation/delithiation in the circulation process, and simultaneously inhibit the agglomeration of molybdenum disulfide nanosheets, thereby improving the mechanical strength and conductivity of the whole material. The application number is ' 201910158874.2 ' and the name is ' hollow sandwich type SiO for lithium ion battery cathode material 2 /C/MoS 2 The hybrid microsphere' patent discloses that one inner layer is SiO 2 The middle layer is a carbon layer, and the outer layer is MoS 2 The hollow sandwich-type structure hybrid microspheres of (1) are deficient in that, on the one hand, it is silica obtained by hydrolysis of tetraethoxysilane, resulting in silica with carbon, moS 2 The ratio of the components is not adjustable, and the performance of the final product is difficult to adjust in time according to the requirement; on the other hand, there is a report of SiO in the battery reaction 2 Can generate Li 2 SiO 3 Or Li 4 SiO 4 But irreversible, its presence mainly serves as a buffer, and the effect of improving the battery performance is not significant.
The theoretical specific capacity of silicon is 4200mAh/g, and the silicon material is rich in storage capacity in the earth crust, low in cost and environment-friendly, so that the silicon material is one of the most potential novel negative electrode materials, but the huge volume expansion (300%) of the silicon material in the charging and discharging process can cause the pulverization of particles and the breakage of SEI film, thereby seriously affecting the cycling stability performance of the battery. Therefore, how to inhibit the volume expansion of silicon to develop a high-capacity and high-cycle stability cathode material is a technical problem in the field of lithium ion batteries.
Disclosure of Invention
In view of the problems in the background art, an object of the present invention is to provide a negative electrode material for a lithium ion battery, which has high capacity, long cycle, and excellent conductive characteristics, and a method for preparing the same, which is simple and environmentally friendly.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a lithium ion battery negative electrode material comprises the following steps:
(1) Dissolving dopamine hydrochloride and a template agent in a mixed solution of water and ethanol, continuously stirring, adding 1,3, 5-trimethylbenzene, adding alkali liquor to adjust the pH value of the mixed solution to 7-9, preferably 7.5-8, reacting at room temperature for 2-5h, separating to obtain a precipitate, washing the precipitate for multiple times by using a mixed solution of water and ethanol to remove the template agent in the precipitate, and performing vacuum drying at the temperature of 60-70 ℃ for 6-12h to obtain the polydopamine nanospheres. Further preferably, the template is a block copolymer F127; the volume ratio of water to ethanol in the mixed solution of water and ethanol is 1; the alkali liquor is ammonia water solution.
(2) Ultrasonically dispersing the polydopamine nano-microspheres in a dispersion liquid, adding a molybdenum source and a sulfur source, and uniformly mixing to obtain a mixed liquid; transferring the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal reaction for 20-48h at 160-220 ℃, and sequentially carrying out centrifugal separation, washing and drying on the reaction product to obtain a black product; calcining the black product in protective gas to obtain molybdenum disulfide/polydopamine derived carbon microspheres (MoS) 2 a/C composite); preferably, the dispersion liquid is a mixed solution of water and ethanol; the molybdenum source is sodium molybdate, and the sulfur source is thiourea; the mass ratio of the molybdenum source to the sulfur source is 1; the temperature of the calcination treatment600-800 deg.C for 2-4h; the protective gas is inert gas.
(3) And mixing and grinding the molybdenum disulfide/polydopamine derived carbon microspheres and nano silicon to obtain a target product. Preferably, the mass ratio of the molybdenum disulfide/polydopamine-derived carbon microspheres to the nano silicon is 5-20; the average grain diameter of the nano silicon is 50nm; the grinding time is 0.5-2h.
The invention also provides a lithium ion battery cathode material which is prepared by the preparation method.
The invention has the following beneficial effects:
(1) The dopamine-hydrochloride nano-microsphere is synthesized by taking dopamine hydrochloride as a monomer and adopting a nano-emulsion assembly method under the support of a template agent, and the method is simple and does not need complex polymerization steps; then carbonizing the polydopamine nano-microspheres through calcination to obtain polydopamine-derived carbon microspheres, wherein the polydopamine contains nitrogen, so that the obtained carbon microspheres are nitrogen-doped carbon, and the improvement of the conductivity and the electrochemical performance of the cathode material is facilitated;
(2) According to the invention, the molybdenum disulfide is directly grown on the surface of the polydopamine nano-microsphere, so that the aggregation of molybdenum disulfide nano-sheets can be effectively prevented, the specific surface area of the material is increased, and the contact area of the active material and the electrolyte is increased;
(3) The scheme firstly prepares MoS 2 the/C composite material is blended with the nano-silicon, and the MoS can be accurately regulated and controlled by controlling the addition of the nano-silicon 2 The mixing proportion of the/C composite material and the nano silicon is adjusted, so that the optimal performance is obtained; meanwhile, the nano silicon has a great contribution to the capacity and is suitable for mass production; in addition, the spherical polydopamine-derived carbon microspheres can play a role in buffering to inhibit the expansion of silicon volume in the circulation process.
Drawings
Fig. 1 is an SEM image of the polydopamine nanospheres prepared in example 1.
Figure 2 is a TEM image of the molybdenum disulfide/polydopamine derivatized carbon microspheres from example 1.
Figure 3 is a graph of the cycling performance of nano-silicon @ molybdenum disulfide/polydopamine derived carbon microspheres prepared in example 5 of the present invention and molybdenum disulfide prepared in comparative example 1.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the technical solutions in the embodiments of the present invention are described below in conjunction with the embodiments, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments, and therefore other embodiments obtained by a person of ordinary skill in the art without creative efforts belong to the protection scope of the present invention. The specific conditions not specified in the examples were conducted according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated as conventional commercial products which are commercially available from manufacturers.
Example 1
A preparation method of a lithium ion battery negative electrode material comprises the following steps:
(1) Dissolving 1g of block copolymer F127 and 1.5g of dopamine hydrochloride in a mixed solution of 50mL of deionized water and 50mL of ethanol, continuously stirring for 0.5h at room temperature to obtain a colorless clear solution, adding 2mL1,3, 5-trimethylbenzene into the solution, adding ammonia water to adjust the pH value to 8, continuously reacting for 4h, centrifuging to collect a black product, centrifuging and washing with water and ethanol for 5 times, and finally drying in a vacuum oven at 60 ℃ for 12h to obtain the polydopamine nanospheres.
(2) Dispersing 50mg of the polydopamine nano-microspheres obtained in the previous step into a dispersion liquid of 30mL of deionized water and 30mL of ethanol, then adding 200mg of sodium molybdate and 200mg of thiourea, uniformly mixing to obtain a mixed solution, then transferring the mixed solution into a 100mL stainless steel autoclave with a tetrafluoroethylene lining, carrying out hydrothermal treatment at 200 ℃ for 24h, carrying out centrifugation to collect a black product, carrying out multiple centrifugal washing with the deionized water and the ethanol, and drying in a vacuum oven at 60 ℃ for 12h. And finally, calcining at 800 ℃ for 2 hours under the protection of argon atmosphere at the heating rate of 5 ℃/min to obtain the molybdenum disulfide/polydopamine derived carbon microspheres.
(3) And mixing and grinding the molybdenum disulfide/polydopamine derived carbon microspheres and nano silicon for 1h according to a mass ratio of 19.
Fig. 1 is an SEM image of the polydopamine nanosphere prepared in this embodiment, and it can be observed from fig. 1 that the prepared polydopamine nanosphere has an obvious spherical morphology and good dispersibility, the particle size distribution is between 150nm and 250nm, and the polydopamine-derived carbon microspheres formed after carbonization are nitrogen-doped carbon, which can improve the conductivity and electrochemical properties of the material.
Fig. 2 is a TEM image of the molybdenum disulfide/polydopamine-derived carbon microsphere prepared in this embodiment, and it can be seen from fig. 2 that molybdenum disulfide nanosheets uniformly grow on the surface of the polydopamine-derived carbon microsphere, so that the problem of agglomeration of the molybdenum disulfide nanosheets in the synthesis process is solved, the specific surface area of the material is increased, the contact area between the active material and the electrolyte is increased, and the active sites are increased, thereby facilitating the transmission of lithium ions and electrons. In addition, the spherical morphology is perfectly preserved, indicating excellent structural stability.
Example 2
(1) Dissolving 1g of block copolymer F127 and 1.5g of dopamine hydrochloride in a mixed solution of 50mL of deionized water and 50mL of ethanol, continuously stirring at room temperature for 0.5h to obtain a colorless clear solution, adding 2mL1,3, 5-trimethylbenzene into the solution, adding ammonia water to adjust the pH value to 8, continuously reacting for 4h, centrifuging to collect a black product, centrifuging and washing with water and ethanol for 3-5 times, and finally drying in a vacuum oven at 60 ℃ for 12h to obtain the polydopamine nanospheres.
(2) Dispersing 50mg of the polydopamine nano-microspheres obtained in the previous step into a dispersion liquid of 30mL of deionized water and 30mL of ethanol, then adding 200mg of sodium molybdate and 200mg of thiourea, uniformly mixing to obtain a mixed solution, then transferring the mixed solution into a 100mL stainless steel autoclave with a tetrafluoroethylene lining, carrying out hydrothermal treatment at 200 ℃ for 24h, carrying out centrifugation to collect a black product, carrying out multiple centrifugal washing with the deionized water and the ethanol, and drying in a vacuum oven at 60 ℃ for 12h. And finally, calcining at 800 ℃ for 2 hours under the protection of argon atmosphere at the heating rate of 5 ℃/min to obtain the molybdenum disulfide/polydopamine derived carbon microspheres.
(3) And mixing and grinding the molybdenum disulfide/polydopamine derived carbon microspheres and nano silicon for 1h according to a mass ratio of 9.
Example 3
(1) Dissolving 1g of block copolymer F127 and 1.5g of dopamine hydrochloride in a mixed solution of 50mL of deionized water and 50mL of ethanol, continuously stirring for 0.5h at room temperature to obtain a colorless clear solution, adding 2mL1,3, 5-trimethylbenzene into the solution, adding ammonia water to adjust the pH value to 8, continuously reacting for 4h, centrifuging to collect a black product, centrifuging and washing for 3-5 times with water and ethanol for multiple times, and finally drying in a vacuum oven at 60 ℃ for 12h to obtain the polydopamine nanospheres.
(2) Dispersing 50mg of the polydopamine nano-microspheres obtained in the previous step into a dispersion liquid of 30mL of deionized water and 30mL of ethanol, then adding 200mg of sodium molybdate and 200mg of thiourea, uniformly mixing to obtain a mixed solution, then transferring the mixed solution into a 100mL stainless steel autoclave with a tetrafluoroethylene lining, carrying out hydrothermal treatment at 200 ℃ for 24h, carrying out centrifugation to collect a black product, carrying out multiple centrifugal washing with the deionized water and the ethanol, and drying in a vacuum oven at 60 ℃ for 12h. And finally, calcining at 800 ℃ for 2 hours under the protection of argon atmosphere at the heating rate of 5 ℃/min to obtain the molybdenum disulfide/polydopamine derived carbon microspheres.
(3) And mixing and grinding the molybdenum disulfide/polydopamine derived carbon microspheres and nano silicon for 1 hour according to the mass ratio of 5.67.
Example 4
(1) Dissolving 1g of block copolymer F127 and 1.5g of dopamine hydrochloride in a mixed solution of 50mL of deionized water and 50mL of ethanol, continuously stirring for 0.5h at room temperature to obtain a colorless clear solution, adding 2mL1,3, 5-trimethylbenzene into the solution, adding ammonia water to adjust the pH value to 8, continuously reacting for 4h, centrifuging to collect a black product, centrifuging and washing for 3-5 times with water and ethanol for multiple times, and finally drying in a vacuum oven at 60 ℃ for 12h to obtain the polydopamine nanospheres.
(2) Dispersing 50mg of the obtained polydopamine nano-microspheres in a dispersion liquid of 30mL of deionized water and 30mL of ethanol, then adding 200mg of sodium molybdate and 200mg of thiourea, uniformly mixing to obtain a mixed solution, then transferring the mixed solution into a 100mL stainless steel autoclave with a tetrafluoroethylene lining, carrying out hydrothermal reaction at 200 ℃ for 24 hours, carrying out centrifugation to collect a black product, carrying out multiple centrifugal washing with deionized water and ethanol, and drying in a vacuum oven at 60 ℃ for 12 hours. And finally, calcining at 800 ℃ for 2 hours under the protection of argon atmosphere at the heating rate of 5 ℃/min to obtain the molybdenum disulfide/polydopamine derived carbon microspheres.
(3) And mixing and grinding the molybdenum disulfide/polydopamine derived carbon microspheres and nano silicon for 0.5h according to a mass ratio of 9.
Example 5
(1) Dissolving 1g of block copolymer F127 and 1.5g of dopamine hydrochloride in a mixed solution of 50mL of deionized water and 50mL of ethanol, continuously stirring for 0.5h at room temperature to obtain a colorless clear solution, adding 2mL1,3, 5-trimethylbenzene into the solution, adding ammonia water to adjust the pH value to 8, continuously reacting for 4h, centrifuging to collect a black product, centrifuging and washing for 3-5 times with water and ethanol for multiple times, and finally drying in a vacuum oven at 60 ℃ for 12h to obtain the polydopamine nanospheres.
(2) Dispersing 50mg of the polydopamine nano-microspheres obtained in the previous step into a dispersion liquid of 30mL of deionized water and 30mL of ethanol, then adding 200mg of sodium molybdate and 200mg of thiourea, uniformly mixing to obtain a mixed solution, then transferring the mixed solution into a 100mL stainless steel autoclave with a tetrafluoroethylene lining, carrying out hydrothermal treatment at 200 ℃ for 24h, carrying out centrifugation to collect a black product, carrying out multiple centrifugal washing with the deionized water and the ethanol, and drying in a vacuum oven at 60 ℃ for 12h. And finally, calcining for 2 hours at 800 ℃ under the protection of argon atmosphere at the heating rate of 5 ℃/min to obtain the molybdenum disulfide/polydopamine derived carbon microspheres.
(3) And mixing and grinding the molybdenum disulfide/polydopamine derived carbon microspheres and nano silicon for 2 hours according to the mass ratio of 9.
Comparative example 1
200mg of sodium molybdate and 200mg of thiourea were dissolved in a dispersion of 30mL of deionized water and 30mL of ethanol, and then the solution was transferred to a 100mL tetrafluoroethylene-lined stainless steel autoclave, hydrothermal at 200 ℃ for 24h, centrifuged to collect the black product, centrifuged several times with deionized water and ethanol, washed, and dried in a vacuum oven at 60 ℃ for 12h. And finally, calcining at 800 ℃ for 2h under the protection of argon atmosphere at the heating rate of 5 ℃/min to obtain the molybdenum disulfide nanosheet.
Comparative example 2
(1) Dissolving 1g of block copolymer F127 and 1.5g of dopamine hydrochloride in a mixed solution of 50mL of deionized water and 50mL of ethanol, continuously stirring at room temperature for 0.5h to obtain a colorless clear solution, adding 2mL1,3, 5-trimethylbenzene into the solution, adding ammonia water to adjust the pH value to 8, continuously reacting for 4h, centrifuging to collect a black product, centrifuging and washing for 5 times with water and ethanol for multiple times, and finally drying in a vacuum oven at 60 ℃ for 12h to obtain the polydopamine nanospheres.
(2) Dispersing 50mg of the polydopamine nano-microsphere obtained in the previous step into a dispersion liquid of 30mL of deionized water and 30mL of ethanol, then adding a mixed solution in which 200mg of sodium molybdate and 200mg of thiourea are dissolved, then transferring the solution into a 100mL stainless steel autoclave with a tetrafluoroethylene lining, carrying out hydrothermal treatment at 200 ℃ for 24h, carrying out centrifugation to collect a black product, carrying out centrifugal washing with deionized water and ethanol for multiple times, and drying in a vacuum oven at 60 ℃ for 12h. And finally, calcining for 2 hours at 800 ℃ under the protection of argon atmosphere at the heating rate of 5 ℃/min to obtain the molybdenum disulfide/polydopamine derived carbon microspheres.
Comparative example 3
Dissolving 1g of block copolymer F127 and 1.5g of dopamine hydrochloride in a mixed solution of 50mL of deionized water and 50mL of ethanol, continuously stirring at room temperature for 0.5h to obtain a colorless clear solution, adding 2mL1,3, 5-trimethylbenzene into the solution, adding ammonia water to adjust the pH value to 8, continuously reacting for 4h, centrifuging to collect a black product, centrifuging and washing for 5 times with water and ethanol, and drying in a vacuum oven at 60 ℃ for 12h. And finally, calcining at 800 ℃ for 2h under the protection of argon atmosphere at the heating rate of 5 ℃/min to obtain the polydopamine-derived carbon microspheres.
The cathode materials prepared in examples 1-5 and comparative examples 1-3 were made into 2032 button cells for electrochemical performance test, and the test results are shown in the following table:
TABLE 1 Performance test results
As can be seen from comparative example 1 and comparative example 2 in Table 1, the discharge capacity of the molybdenum disulfide is low, the cycle performance is poor, and the capacity and the cycle are obviously improved after the molybdenum disulfide is compounded with a carbon material; therefore, the defect that the intrinsic conductivity of the molybdenum disulfide material is poor can be obviously improved by the constructed molybdenum disulfide/polydopamine derived carbon microsphere structure.
It can be seen from example 1 and comparative example 2 that the addition of nano-silicon can effectively improve the discharge capacity of the composite material, indicating that nano-silicon has an obvious contribution to the capacity; it can be seen from examples 2, 4 and 5 that when the amount of silicon added is the same, the cycle stability of the material can be effectively improved as the polishing time increases.
Figure 3 is a graph of the cycling performance at a current density of 0.2A/g for the nanosilicon @ molybdenum disulfide/polydopamine derived carbon microspheres prepared in example 5 and for the molybdenum disulfide prepared in comparative example 1. From the figure, it can be observed that after 100 cycles, the capacity of the pure molybdenum disulfide nanosheet is only 128.7mAh/g, and in contrast, the capacity of the composite anode material prepared in example 5 can still be maintained at 680.2mAh/g after 100 cycles, which indicates excellent cycle stability.
The above description is only for the preferred embodiment of the present invention, and should not be taken as limiting the invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications, equivalents, and improvements may be made without departing from the principles of the invention, and such improvements and modifications should be considered within the scope of the invention.
Claims (8)
1. A preparation method of a lithium ion battery cathode material is characterized by comprising the following steps: the method comprises the following steps:
(1) Dissolving dopamine hydrochloride and a template agent in a mixed solution of water and ethanol, adding 1,3, 5-trimethylbenzene, adding alkali liquor to adjust the pH value of the mixed solution to 7-9, reacting at room temperature for 2-5 hours, separating to obtain a precipitate, removing the template agent in the precipitate, and drying to obtain polydopamine nano microspheres; the particle size distribution of the polydopamine nano-microspheres is between 150nm and 250 nm;
(2) Dispersing the polydopamine nano-microspheres in a dispersion liquid, adding a molybdenum source and a sulfur source, and uniformly mixing to obtain a mixed liquid; transferring the mixed solution into a high-pressure reaction kettle for hydrothermal reaction to obtain a black product; calcining the black product in a protective gas to obtain molybdenum disulfide/polydopamine derived carbon microspheres; the dispersion liquid is a mixed solution of water and ethanol;
(3) Mixing and grinding molybdenum disulfide/polydopamine derived carbon microspheres and nano silicon to obtain a target product; the mass ratio of the molybdenum disulfide/polydopamine derived carbon microspheres to the nano silicon is (5-20).
2. The preparation method of the lithium ion battery anode material according to claim 1, characterized in that: in the step (1), the template is a block copolymer F127; the volume ratio of water to ethanol in the mixed solution of water and ethanol is 1.
3. The preparation method of the lithium ion battery anode material according to claim 1, characterized in that: in the step (1), the alkali liquor is an ammonia water solution; the pH value of the mixed solution is 7.5-8.
4. The preparation method of the lithium ion battery anode material according to claim 1, characterized in that: in the step (1), the method for removing the template agent in the precipitate is to wash the precipitate for multiple times by using a mixed solution of water and ethanol.
5. The preparation method of the lithium ion battery anode material according to claim 1, characterized in that: in the step (2), the molybdenum source is sodium molybdate, and the sulfur source is thiourea; the mass ratio of the molybdenum source to the sulfur source is 1.
6. The preparation method of the lithium ion battery negative electrode material according to claim 1, characterized in that: in the step (2), the temperature of the hydrothermal reaction is 160-220 ℃ and the time is 20-48h.
7. The preparation method of the lithium ion battery anode material according to claim 1, characterized in that: in the step (2), the calcining treatment temperature is 600-800 ℃, and the time is 2-4h.
8. A lithium ion battery negative electrode material is characterized in that: which is prepared by the preparation method according to any one of claims 1 to 7.
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