CN112038618A - Nano silicon powder polymeric sphere composite negative electrode material with hollow structure and preparation method and application thereof - Google Patents
Nano silicon powder polymeric sphere composite negative electrode material with hollow structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of electrochemical power supplies, in particular to a nano silicon powder polymeric sphere composite negative electrode material with a hollow structure and a preparation method and application thereof. The composite negative electrode material disclosed by the invention is mainly prepared from the following components in percentage by mass: 1-2% of carbon nano tube or graphene, 4-5% of bonding carbon, 10-12% of asphalt carbon and 85-81% of spherical nano silicon powder; the preparation method comprises the steps of adding sodium carboxymethylcellulose and calcium carbonate into a suspension obtained by ultrasonic dispersion of polyvinylpyrrolidone, spherical nano silicon powder and carbon nano tube/graphene, stirring at a high speed, adding deionized water to adjust the solid content of the suspension, and performing spray drying, asphalt coating, high-temperature carbonization and dilute hydrochloric acid treatment to obtain the nano silicon powder. The invention discloses a nano silicon powder polymeric sphere composite negative electrode material with a hollow structure, which is used for relieving volume expansion in a lithium embedding process so as to prolong the cycle life of a battery; and the preparation process is simple and is suitable for popularization and application.
Description
Technical Field
The invention relates to the technical field of electrochemical power supplies, in particular to a nano silicon powder polymeric sphere composite negative electrode material with a hollow structure, a preparation method thereof and application of the nano silicon powder polymeric sphere composite negative electrode material in a lithium ion battery.
Background
The existing commercial lithium ion battery graphite cathode material is close to the theoretical lithium storage capacity (372mAh/g) of graphite, and in order to further improve the energy density of the existing lithium ion battery, a high-capacity silicon-based cathode material is urgently needed to be developed.
Although the theoretical lithium storage capacity of silicon reaches 4200mAh/g, which is 10 times more than that of graphite, the silicon is the first choice for the negative electrode material of the new generation of lithium ion batteries. However, after lithium storage by silicon, the volume expansion exceeds 300%, electrical contact with a current collector is easily lost due to huge volume change in the charging and discharging processes, and meanwhile, the repeated volume change in the lithium releasing and inserting process easily causes instability of an SEI film formed on the surface of a silicon material, so that capacity is rapidly attenuated.
In summary, the technical problem to be solved by the skilled person is how to provide a composite negative electrode material with a special structure to effectively alleviate the volume expansion of a silicon-based lithium storage negative electrode material in the lithium intercalation process, thereby improving the cycle life of the battery.
Disclosure of Invention
In view of the above, the present invention provides a nano silicon powder polymeric sphere composite anode material with a hollow structure and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a nano silicon powder polymeric sphere composite negative electrode material with a hollow structure is mainly prepared from the following components in percentage by mass:
1-2% of carbon nano tube or graphene, 4-5% of bonding carbon, 10-12% of asphalt carbon and 85-81% of spherical nano silicon powder.
Further, the bonding carbon is obtained by carbonizing sodium carboxymethylcellulose and polyvinylpyrrolidone at high temperature; the pitch carbon is obtained by carbonizing pitch at high temperature.
Specifically, under the vacuum high-temperature condition, the sodium carboxymethylcellulose and the polyvinylpyrrolidone are decomposed at high temperature to generate a carbon material, and the carbon material can play a role in bonding and pinning the spherical nano silicon powder.
The invention also aims to provide a preparation method of the nano silicon powder polymeric sphere composite anode material with the hollow structure, which comprises the following steps:
1) respectively weighing polyvinylpyrrolidone, spherical nano silicon powder and carbon nano tube or graphene, and then carrying out ultrasonic dispersion to obtain a suspension;
2) adding sodium carboxymethylcellulose and calcium carbonate into the suspension obtained in the step 1), stirring at a high speed, then adding deionized water to control the solid content of the suspension, and performing spray drying to obtain powder;
3) adding asphalt into tetrahydrofuran, stirring and dissolving to obtain a dissolved solution, then adding the powder prepared in the step 2) into the dissolved solution, and drying to obtain a precursor with a layer of asphalt coated on the surface;
4) carbonizing the precursor prepared in the step 3) at high temperature to obtain particles, and treating the particles with dilute hydrochloric acid to finally obtain the nano silicon powder polymeric sphere composite negative electrode material with the hollow structure.
It is worth to say that the nano-crystallization of silicon can reduce the cracking of the SEI film on the surface of the silicon material, and simultaneously shorten the diffusion distance of lithium ions in the silicon material, which is more beneficial to the exertion of the lithium storage capacity. The spherical nano silicon powder has the most industrialized prospect in all silicon-based nano materials, and the invention designs the multi-particle nano silicon powder polymerization sphere structure with the hollow structure, so that the volume of the nano silicon powder is increased in the lithium embedding process, and the expansion of the material is converted to the inner hollow structure to relieve the volume expansion of the material due to the hollow structure in the interior, thereby finally prolonging the cycle life of the material.
Further, the preparation method of the hollow-structure nano silicon powder polymeric sphere composite negative electrode material comprises the steps of preparing the hollow-structure nano silicon powder polymeric sphere, carrying out asphalt carbon coating and high-temperature carbonization on the surface, and treating with dilute hydrochloric acid; the method comprises the following specific steps:
dissolving polyvinylpyrrolidone by using deionized water, adding spherical nano silicon powder and carbon nano tubes or graphene for ultrasonic dispersion, adding sodium carboxymethylcellulose as a thickening agent and a binder for high-speed dispersion and uniform stirring, then adding calcium carbonate for high-speed stirring, simultaneously adding deionized water for adjusting solid content, spraying by using a spray dryer to obtain dried powder, transferring the obtained powder into a tetrahydrofuran solution containing asphalt for continuous stirring and drying to obtain a precursor with a layer of asphalt coated on the surface, then carbonizing at high temperature under a vacuum condition, removing a calcium template in particles by using dilute hydrochloric acid, and finally obtaining the nano silicon powder polymerized ball composite cathode material with a hollow structure.
Furthermore, compared with the prior art, the technical scheme disclosed and protected by the invention has the advantages that the nano silicon powder polymeric sphere composite negative electrode material with the hollow structure is designed in a public manner, so that the volume expansion in the lithium embedding process is relieved, and the cycle life of the battery is prolonged; and the preparation process is simple and is suitable for popularization and application.
Preferably, in the step 1), the mass ratio of the polyvinylpyrrolidone to the spherical nano silicon powder to the carbon nanotube/graphene is 2: (81-85): (1-2).
Preferably, in the step 2), the mass ratio of the sodium carboxymethylcellulose to the calcium carbonate to the polyvinylpyrrolidone is (6-12): 20: and 2, adding deionized water to ensure that the solid content of the suspension is 10-15%.
Further preferably, in the step 2), the inlet temperature of spray drying is 200-250 ℃, and the feeding amount is 500-1500 mL/min.
Preferably, in the step 3), the mass concentration of the dissolving solution is 5-10%.
Preferably, in the step (4), the high-temperature carbonization temperature is 1000-1100 ℃, and the molar concentration of the dilute hydrochloric acid is 1-5 mol/L.
The invention also provides application of the nano silicon powder polymeric sphere composite negative electrode material prepared by the method in a lithium ion battery.
According to the invention, through the structure of the hollow structure, the volume change of the material in the lithium releasing and embedding process can be obviously improved, the capacity loss caused by the loss of electric contact between active substance particles and a current collector is avoided, the stability of the pole piece structure is maintained, the cycle life of the battery can be prolonged, and finally the nano silicon powder polymeric sphere composite negative electrode material shows excellent performance in the lithium ion battery, and is suitable for popularization and application in the market.
Compared with the prior art, the invention discloses a nano silicon powder polymeric sphere composite anode material with a hollow structure and a preparation method and application thereof, and the nano silicon powder polymeric sphere composite anode material has the following beneficial effects:
1) the existence of the hollow structure in the prepared nano silicon powder polymeric sphere can buffer the volume change of nano silicon powder in the process of lithium intercalation and deintercalation, thereby not only maintaining the stability of the pole piece structure, but also prolonging the cycle life of the battery;
2) the carbon nano tube/graphene provides a conductive network in the polymeric sphere composite negative electrode material, so that the phenomenon that the volume change of nano silicon particles causes the loss of electric contact of active substances and the influence on capacity exertion is avoided;
3) the bonding carbon can effectively bond the nano silicon powder particles together, and the contact effect among the nano particles is improved;
4) the asphalt carbon can improve the surface performance of polymer spheres, improve the integrity of particles, improve the charging and discharging efficiency, further relieve the volume change and prolong the cycle life.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an SEM image of a nano silicon powder polymeric sphere composite negative electrode material with a hollow structure prepared by the invention;
fig. 2 is a comparative graph of capacity retention rate obtained by testing after negative electrode sheets made of the silicon-carbon composite materials prepared in example 1 and comparative example 1 of the present invention are assembled into a 2032 button cell.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the specification, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention discloses a nano silicon powder polymeric sphere composite negative electrode material with a hollow structure, which is mainly prepared from the following components in percentage by mass:
1-2% of carbon nano tube or graphene, 4-5% of bonding carbon, 10-12% of asphalt carbon and 85-81% of spherical nano silicon powder.
In addition, the embodiment of the invention discloses a preparation method of the nano silicon powder polymeric sphere composite anode material with the hollow structure, which comprises the following steps:
1) respectively weighing polyvinylpyrrolidone (used as a surfactant to improve the dispersibility of nano materials such as nano silicon powder, carbon nano tubes and the like) and nano silicon powder, carbon nano tubes or graphene according to a formula, and performing ultrasonic dispersion to obtain a suspension with uniformly dispersed components;
2) stirring the suspension obtained in the step 1) at a high speed, adding sodium carboxymethylcellulose (serving as a thickening agent and a binder) according to a formula proportion, dispersing at a high speed, stirring uniformly, adding calcium carbonate (serving as a template with a hollow structure), stirring uniformly at a high speed, and adding deionized water to control the solid content of the suspension to be within a range of 10-15 wt.%;
3) carrying out spray drying on the suspension obtained in the step 2) by using a spray dryer, controlling the temperature of a spray inlet to be 200-250 ℃ and the feeding amount to be 500-1500 mL/min, and obtaining dry powder;
4) weighing asphalt powder according to a formula ratio, adding the asphalt powder into tetrahydrofuran, stirring and dissolving, and adding the dry powder obtained in the step 3) into the tetrahydrofuran solution after the asphalt is dissolved, continuously stirring, and simultaneously heating and drying to obtain a precursor with a layer of asphalt coated on the surface;
5) and (3) transferring the precursor in the step 4) into a vacuum furnace, carbonizing at the high temperature of 1000-1100 ℃, decomposing calcium carbonate, and removing a calcium template in particles by using 1-5 mol/L of dilute hydrochloric acid to finally obtain the nano silicon powder polymeric sphere composite negative electrode material with a hollow structure.
Wherein, the attached figure 1 is an SEM image of the nano silicon powder polymeric sphere composite cathode material with the hollow structure, and the center of the prepared nano silicon powder polymeric sphere has an obvious hollow structure, and the structure can provide a buffer space for the volume expansion of the nano silicon powder lithium-embedded removal, reduce the expansion of a pole piece and prolong the cycle life.
The technical solution of the present invention is further described below with reference to specific examples, but the content of the present invention is not limited to the following examples.
Example 1:
a preparation method of a nano silicon powder polymeric sphere composite anode material with a hollow structure specifically comprises the following steps:
1) weighing 2g of polyvinylpyrrolidone, 85g of nano silicon powder and 1g of carbon nano tube, adding into 800g of deionized water, and performing ultrasonic dispersion to obtain a suspension with uniformly dispersed components;
2) stirring the suspension obtained in the step 1) at a high speed, adding 6g of sodium carboxymethylcellulose, fully stirring to dissolve the sodium carboxymethylcellulose, adding 20g of calcium carbonate template and about 210g of deionized water, and uniformly mixing to obtain uniform slurry with the solid content of about 10 wt.%;
3) carrying out ultrasonic stirring and spray drying on the uniform slurry obtained in the step 2), controlling the inlet temperature of a sprayer to be 250 ℃ and the feeding amount to be 500ml/min, and obtaining dry powder;
4) weighing 15g of asphalt powder, adding the asphalt powder into a tetrahydrofuran solution, stirring and dissolving, then adding the dry powder obtained in the step 3), stirring and mixing uniformly, and heating and drying to obtain a precursor of which the surface layer is coated with a layer of asphalt;
5) and (3) transferring the precursor in the step 4) into a vacuum furnace, carbonizing at high temperature under the vacuum condition of 1100 ℃, decomposing calcium carbonate, and removing the calcium template in the particles by using 1mol/L dilute hydrochloric acid to obtain the nano silicon powder polymeric sphere composite negative electrode material with the hollow structure.
Example 2:
a preparation method of a nano silicon powder polymeric sphere composite anode material with a hollow structure specifically comprises the following steps:
1) weighing 2g of polyvinylpyrrolidone, 81g of nano silicon powder and 2g of carbon nano tube, adding into 500g of deionized water, and performing ultrasonic dispersion to obtain a suspension with uniformly dispersed components;
2) stirring the suspension obtained in the step 1) at a high speed, adding 12g of sodium carboxymethylcellulose, fully stirring to dissolve the sodium carboxymethylcellulose, adding 20g of calcium carbonate template and about 160g of deionized water, and uniformly mixing to obtain uniform slurry with the solid content of about 15 wt.%;
3) carrying out ultrasonic stirring and spray drying on the uniform slurry obtained in the step 2), controlling the inlet temperature of a spraying machine at 200 ℃ and the feeding amount at 1500ml/min, and obtaining dry powder;
4) weighing 20g of asphalt powder, adding the asphalt powder into a tetrahydrofuran solution, stirring and dissolving, then adding the dry powder obtained in the step 3), stirring and mixing uniformly, and heating and drying to obtain a precursor with a layer of asphalt coated on the surface layer;
5) and (3) transferring the precursor in the step 4) into a vacuum furnace, carbonizing at high temperature under the vacuum condition of 1000 ℃, decomposing calcium carbonate, and removing a calcium template in particles by using 5mol/L dilute hydrochloric acid to obtain the nano silicon powder polymeric sphere composite negative electrode material with a hollow structure.
Example 3:
a preparation method of a nano silicon powder polymeric sphere composite anode material with a hollow structure specifically comprises the following steps:
1) weighing 2g of polyvinylpyrrolidone, 83g of nano silicon powder and 2g of graphene, adding the mixture into 800g of deionized water, and performing ultrasonic dispersion to obtain a suspension with uniformly dispersed components;
2) stirring the suspension obtained in the step 1) at a high speed, adding 10g of sodium carboxymethylcellulose, fully stirring to dissolve the sodium carboxymethylcellulose, adding 20g of calcium carbonate template and about 100g of deionized water, and uniformly mixing to obtain uniform slurry with the solid content of about 11.5 wt.%;
3) carrying out ultrasonic stirring and spray drying on the uniform slurry obtained in the step 2), controlling the inlet temperature of a spraying machine at 220 ℃ and the feeding amount at 1000ml/min, and obtaining dry powder;
4) weighing 17g of asphalt powder, adding the asphalt powder into a tetrahydrofuran solution, stirring and dissolving, then adding the dry powder obtained in the step 3), stirring and mixing uniformly, and heating and drying to obtain a precursor of which the surface layer is coated with a layer of asphalt;
5) and (3) transferring the precursor in the step 4) into a vacuum furnace, carbonizing at high temperature under the vacuum condition of 1100 ℃, decomposing calcium carbonate, and removing a calcium template in particles by using 3mol/L dilute hydrochloric acid to obtain the nano silicon powder polymeric sphere composite negative electrode material with a hollow structure.
In order to further verify the excellent effects of the present invention, the inventors also performed the following comparative and measurement experiments:
the silicon-carbon composite material prepared in the embodiment 1 is prepared into a negative plate, and is assembled into a 2032 button cell for testing the cycle life, the material performance data is shown in table 1, and the capacity retention rate curve is shown in fig. 2.
The graph shows that the cycle life of the silicon-carbon composite material with the hollow structure is obviously prolonged compared with that of the nano silicon powder in the comparative example, the hollow structure provides a buffer space for the expansion of the nano silicon powder in the lithium releasing and embedding process, the volume change of a pole piece is reduced, the structural integrity of the pole piece is maintained, and the cycle life is prolonged.
The method for testing the cycle performance of the battery comprises the following steps:
discharging to 0.01V at a current density of 100mA/g, discharging to 0.005V at a current of 10mA/g, standing for 3min, and charging to 1.5V at a current density of 100mA/g, thereby testing the cycle performance in one cycle.
TABLE 1
Comparative experiment 1:
the nano silicon powder in the step 1 of the embodiment 1 is taken as a negative electrode material to be assembled into a 2032 button cell to test the cycle life, the material performance data is shown in table 1, and the curve of the capacity retention rate is shown in fig. 2.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. The nano silicon powder polymeric sphere composite negative electrode material with the hollow structure is characterized by being mainly prepared from the following components in percentage by mass:
1-2% of carbon nano tube or graphene, 4-5% of bonding carbon, 10-12% of asphalt carbon and 85-81% of spherical nano silicon powder.
2. The nano silicon powder polymeric sphere composite anode material with the hollow structure as claimed in claim 1, wherein the binder carbon is obtained by high temperature carbonization of sodium carboxymethyl cellulose and polyvinylpyrrolidone.
3. The preparation method of the nano silicon powder polymeric sphere composite anode material with the hollow structure as claimed in any one of claims 1 to 2, characterized by comprising the following steps:
1) respectively weighing polyvinylpyrrolidone, spherical nano silicon powder and carbon nano tube/graphene, and then carrying out ultrasonic dispersion to obtain a suspension;
2) adding sodium carboxymethylcellulose and calcium carbonate into the suspension obtained in the step 1), stirring at a high speed, then adding deionized water to control the solid content of the suspension, and performing spray drying to obtain powder;
3) adding asphalt into tetrahydrofuran, stirring and dissolving to obtain a dissolved solution, then adding the powder prepared in the step 2) into the dissolved solution, and drying to obtain a precursor with a layer of asphalt coated on the surface;
4) carbonizing the precursor prepared in the step 3) at high temperature to obtain particles, and treating the particles with dilute hydrochloric acid to finally obtain the nano silicon powder polymeric sphere composite negative electrode material with the hollow structure.
4. The method for preparing the nano silicon powder polymeric sphere composite anode material with the hollow structure as claimed in claim 3, wherein in the step 1), the mass ratio of polyvinylpyrrolidone, spherical nano silicon powder and carbon nanotube/graphene is 2: (81-85): (1-2).
5. The method for preparing the nano silicon powder polymeric sphere composite anode material with the hollow structure according to claim 3, wherein in the step 2), the mass ratio of sodium carboxymethyl cellulose, calcium carbonate and polyvinylpyrrolidone is (6-12): 20: and 2, adding deionized water to ensure that the solid content of the suspension is 10-15%.
6. The method for preparing the nano silicon powder polymeric sphere composite anode material with the hollow structure as claimed in claim 3 or 5, wherein in the step 2), the inlet temperature of spray drying is 200-250 ℃, and the feeding amount is 500-1500 mL/min.
7. The method for preparing the hollow-structured nano silicon powder polymeric sphere composite anode material as claimed in claim 3, wherein in the step (3), the mass concentration of the dissolving solution is 5-10%.
8. The method for preparing the hollow-structured nano silicon powder polymeric sphere composite anode material as claimed in claim 3, wherein in the step (4), the high-temperature carbonization temperature is 1000-1100 ℃, and the molar concentration of the dilute hydrochloric acid is 1-5 mol/L.
9. Application of the nano silicon powder polymeric sphere composite negative electrode material prepared by the method of any one of claims 3 to 8 or the nano silicon powder polymeric sphere composite negative electrode material of any one of claims 1 to 2 in a lithium ion battery.
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