CN114914418B - Silicon-based nano composite anode material and preparation method thereof - Google Patents
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Abstract
The invention discloses a silicon-based nano composite anode material and a preparation method thereof, which relate to the technical field of lithium ion batteries, and the preparation method comprises the following steps: mixing graphene oxide, a binder, a dispersing agent and silicon nano particles under a protective atmosphere, ball-milling, and then adding deionized water into the mixed materials to obtain slurry; carrying out spray granulation on the slurry through a spray granulation tower to obtain powder; calcining the powder in a reducing atmosphere to obtain a silicon nanocomposite material coated by the redox graphene with a core-shell structure; and (3) taking Mg-doped ZnO as a target material, and coating the surface of the silicon nanocomposite coated by the redox graphene by adopting a powder magnetron sputtering coating technology to obtain the graphene oxide-coated silicon nanocomposite. The silicon-based nano composite anode material prepared by the invention not only can improve the multiplying power performance and the electrical performance, but also can inhibit the expansion of the nano silicon material, slow down the crushing of the nano silicon material and improve the cycle performance.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a silicon-based nano composite anode material and a preparation method thereof.
Background
At present, a plurality of automobile companies research electric automobiles, and the time required for full charge is long in terms of the situation of the electric automobiles designed at present, so that the requirements of people at present cannot be met. Most of the existing lithium ion battery cathode materials use traditional graphite materials, the theoretical capacity of the existing lithium ion battery cathode materials is 372mAh/g, and the existing lithium ion battery cathode materials cannot meet the future development requirements of electric automobiles. Therefore, the development of the cathode material for the high-performance lithium ion battery with quick charge, high energy density and long service time is a key for the development of the electric automobile, and is also a key for realizing green and environment protection and relieving environmental pollution.
Currently, the cathode material of the commercial battery is mainly graphite, the capacity improvement of the graphite almost reaches the limit, and the development of a novel battery cathode material with higher and better performance is the only way to meet the market demand. Silicon is one of the best choices currently used as a battery cathode, the theoretical specific capacity of a silicon material is high and reaches 4200mAh/g, the reaction activity with electrolyte is low, and a discharge platform is also low. However, silicon has a very fatal disadvantage in that silicon materials undergo a volume change (up to 300%) during charge and discharge processes, resulting in pulverization of active materials, resulting in the active materials falling off from a current collector, and eventually resulting in a sharp decrease in capacity, thereby preventing the development of silicon cathodes. The inhibition of the volume expansion and pulverization of the silicon material by coating it is a very effective method. The conductivity of the silicon material itself is several orders of magnitude lower than that of the graphite material, and when the silicon material is coated, some materials with better conductivity are required to be selected for coating the silicon material.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides a silicon-based nano composite anode material and a preparation method thereof.
The invention provides a preparation method of a silicon-based nanocomposite anode material, which comprises the following steps:
s1, mixing graphene oxide, a binder, a dispersing agent and silicon nano particles under a protective atmosphere, ball-milling, and then adding deionized water into the mixed materials to obtain slurry;
s2, carrying out spray granulation on the slurry through a spray granulation tower to obtain powder;
s3, calcining the powder in a reducing atmosphere to obtain a silicon nanocomposite coated by the redox graphene with a core-shell structure;
and S4, coating the surface of the silicon nanocomposite coated by the redox graphene by taking Mg-doped ZnO as a target material and adopting a powder magnetron sputtering coating technology to obtain the silicon nanocomposite anode material jointly coated by the Mg-doped ZnO and the redox graphene.
Preferably, in S1, the mass ratio of graphene oxide, binder, dispersant, silicon nanoparticles is 2:2-3:2-3:18; wherein the graphene oxide is prepared by a Hummers method; the binder is styrene butadiene rubber or polyacrylic acid; the dispersing agent is sodium carboxymethyl cellulose.
The adhesive is styrene-butadiene rubber or polyacrylic acid, wherein the styrene-butadiene rubber is an aqueous adhesive, and is a substance with both hydrophilicity and lipophilicity, the aqueous group and the surface group of the foil are combined to form adhesive force, so that the dispersibility and the slurry stability are facilitated, and the oily chain segment and the negative graphite are combined to form adhesive force, so that the adhesive effect is achieved; polyacrylic acid is a water-soluble chain polymer, can form polyacrylate with a plurality of metal ions, can form hydrogen bond action with the surface of a silicon-carbon active material, endows stronger bonding force between active particles and a current collector, and can relieve the volume expansion effect of a silicon-based material, and is mainly used as a binder to improve the stability of slurry.
The dispersing agent is sodium carboxymethyl cellulose (CMC), which is an ionic linear polymer substance, is easily dissolved in cold and hot water and polar solvent to form transparent viscous liquid, and can be added when the electrode slurry is prepared, so that the viscosity of the slurry can be improved and the slurry precipitation can be prevented.
Preferably, in S1, ball milling is carried out for 4-10 hours, and the ball milling rotating speed is 200-500r/min.
Preferably, in S1, deionized water is added to adjust the viscosity of the slurry to 3000-5000 Pa.S.
Preferably, in S2, the process parameters of spray granulation are: the feeding speed of the slurry is 50-100kg/h, the air inlet temperature is 230-245 ℃, the air outlet temperature is 110-115 ℃, the rotating speed of an atomizing disk is 12000-14000r/min, and the negative pressure in the tower is 0.2-0.5Mpa; obtaining solid powder with particle size D50 of 10-13 μm and tap density of 1.3-1.4cm 3 /g。
Preferably, in S3, the powder is calcined for 15-30min in a microwave sintering furnace at 400-500 ℃ in a reducing atmosphere of a mixed gas of nitrogen and hydrogen; wherein, the volume ratio of nitrogen to hydrogen in the mixed gas is 100:5-10.
Preferably, the specific operation of the microwave calcination is as follows: heating to 300 ℃ at a heating rate of 2 ℃/min, and preserving heat for 5min; then heating to 400-450 ℃ at a heating rate of 1.5 ℃/min, calcining for 15-30min, and finally cooling to room temperature at a cooling rate of 1.5 ℃/min.
Preferably, in S4, the process parameters of the powder magnetron sputtering coating are as follows: the sputtering power is 1-5w/cm 2 The cathode power supply adopts a constant current mode, the current is 30-45A, the deposition voltage is 350-450V, and the time is 2-10min.
Preferably, in S4, the thickness of the film layer of the coating film is controlled to be 100-180nm.
The invention also provides the silicon-based nano composite anode material prepared by the method.
The beneficial effects are that: according to the invention, the nano silicon material is coated by redox graphene, so that the volume expansion of the nano silicon material serving as the negative electrode material of the lithium ion battery in the circulating process is inhibited, the crushing of the nano silicon material is slowed down, and the circulating performance is improved; then coating the silicon anode material by adopting Mg-doped ZnO, so as to further increase the coating uniformity and conductivity, improve the electronic conductivity of the silicon anode material and increase the multiplying power performance of the silicon anode material.
Drawings
Fig. 1 is an SEM image of a silicon-based nanocomposite anode material prepared in example 3 of the present invention.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
A preparation method of a silicon-based nanocomposite anode material comprises the following steps:
s1, graphene oxide, styrene-butadiene rubber, sodium carboxymethyl cellulose and silicon nano particles with the particle size of 80nm prepared by a Hummers method are mixed according to a mass ratio of 2:2:3:18 adding the mixture into a ball mill, introducing argon/nitrogen (the ratio is 1:1) inert atmosphere, ball milling for 5 hours under the protection of the argon/nitrogen inert atmosphere, wherein the ball milling rotating speed is 300r/min, adding the mixture into a vacuum stirrer after ball milling is finished, injecting deionized water into the stirrer, stirring for 2 hours, wherein the stirring rotating speed is 500r/min, and adjusting the viscosity to 3800 Pa.S, so that uniformly-dispersed and good slurry is obtained;
s2, filtering the slurry by using a 200-mesh sun screen, adding the obtained uniformly dispersed slurry into a feed barrel, feeding the slurry into a spray granulation tower through a peristaltic pump, wherein the feeding speed is controlled to be 60kg/h of the slurry, the air inlet temperature is controlled to be 238 ℃, the air outlet temperature is controlled to be 113 ℃, the rotating speed of an atomization plate is controlled to be 13500r/min, the negative pressure in the tower is 0.1MPa, and the solid powder particle size D50 is 11 mu m, and the tap density is 1.35cm 3 /g；
S3, sieving the obtained powder particles with a 200-mesh sieve, putting the sieve into a graphite crucible, putting the crucible into a microwave sintering furnace protected by nitrogen/hydrogen reducing atmosphere (the volume ratio is 100:5), heating to 300 ℃ at a heating rate of 2 ℃/min, preserving heat for 5min, heating to 450 ℃ at a heating rate of 1.5 ℃/min, calcining for 15min, and cooling to room temperature at a cooling rate of 1.5 ℃/min to obtain the redox graphene-coated silicon nanocomposite with the core-shell structure;
s4, taking Mg-doped ZnO as a target material, wherein the purity of the target material is more than 3N, placing the silicon nanocomposite material coated by the redox graphene into a process cavity of a coating device, vacuumizing the process cavity, and ensuring that the background vacuum degree requirement is superior to that of 5 multiplied by 10 - 4 Pa; re-introducing process gas (nitrogen) into the process cavity to maintain the air pressure in the process cavity at 0.3Pa, ensuring that the air cleanliness of the coating environment reaches ten thousand levels, the humidity is below 50%, the temperature is 20 ℃, starting a cathode power supply of the coating equipment, and coating the powder, wherein the coating power is 1W/cm 2 And the cathode power supply adopts a constant current mode, the current is 40A, the deposition voltage is 300V, the Mg-doped ZnO target material is uniformly coated on the surface of the composite material through a powder surface coating technology, and the thickness of the Mg-doped ZnO film layer is controlled to be 130nm, so that the silicon-based nano composite anode material jointly coated by the redox graphene and the Mg-doped ZnO is obtained.
Example 2
A preparation method of a silicon-based nanocomposite anode material comprises the following steps:
s1, graphene oxide, polyacrylic acid, sodium carboxymethyl cellulose and silicon nano particles with the particle size of 60nm prepared by a Hummers method are mixed according to a mass ratio of 2:3:2:18, adding the mixture into a ball mill, introducing argon/nitrogen (the ratio is 1:1) inert atmosphere, ball milling for 6 hours under the protection of the argon/nitrogen inert atmosphere, adding the ball mill into a vacuum stirrer after ball milling is completed at the speed of 400r/min, injecting deionized water into the stirrer, stirring for 2 hours at the speed of 500r/min, and adjusting the viscosity to 4000 Pa.S, thereby obtaining uniformly-dispersed and good slurry;
s2, filtering the slurry by using a 200-mesh sun screen, adding the obtained uniformly dispersed slurry into a feed barrel, feeding the slurry into a spray granulation tower through a peristaltic pump, wherein the feeding speed is controlled to be 50kg/h of the slurry, the air inlet temperature is controlled to be 230 ℃, the air outlet temperature is controlled to be 115 ℃, the rotating speed of an atomizing disk is controlled to be 12000r/min, the negative pressure in the tower is 0.2MPa, and the solid powder particle size D50 is 13 mu m, and the tap density is 1.3cm 3 /g；
S3, sieving the obtained powder particles with a 200-mesh sieve, putting the sieve into a graphite crucible, putting the crucible into a microwave sintering furnace protected by nitrogen/hydrogen reducing atmosphere (the volume ratio is 100:10), heating to 300 ℃ at a heating rate of 2 ℃/min, preserving heat for 5min, heating to 400 ℃ at a heating rate of 1.5 ℃/min, calcining for 15min, and cooling to room temperature at a cooling rate of 1.5 ℃/min to obtain the redox graphene-coated silicon nanocomposite with the core-shell structure;
s4, taking Mg-doped ZnO as a target material, wherein the purity of the target material is more than 3N, putting the redox graphene coated silicon nano core-shell structure composite material into a process cavity of a coating device, vacuumizing the process cavity, and ensuring that the background vacuum degree requirement is better than that of 5 multiplied by 10 -4 Pa; re-introducing process gas (nitrogen) into the process cavity to maintain the air pressure in the process cavity at 0.1Pa, ensuring that the air cleanliness of the coating environment reaches ten thousand levels, the humidity is below 50%, the temperature is 17 ℃, starting a cathode power supply of the coating equipment, and coating the powder, wherein the coating power is 1W/cm 2 And uniformly coating the Mg-doped ZnO target on the surface of the composite material by adopting a constant current mode, wherein the current is 30A, the deposition voltage is 350V, and finally obtaining the silicon-based nano composite anode material jointly coated by redox graphene and Mg-doped ZnO, wherein the thickness of the Mg-doped ZnO film is 150 nm.
Example 3
A preparation method of a silicon-based nanocomposite anode material comprises the following steps:
s1, graphene oxide, styrene-butadiene rubber, sodium carboxymethyl cellulose and silicon nano particles with the particle size of 60nm prepared by a Hummers method are mixed according to a mass ratio of 2:2:3:18 adding the mixture into a ball mill, introducing argon/nitrogen (the ratio is 1:1) inert atmosphere, ball milling for 10 hours under the protection of the argon/nitrogen inert atmosphere, adding the mixture into a vacuum stirrer after ball milling is completed at the speed of 500r/min, injecting deionized water into the stirrer, stirring for 2 hours at the speed of 800r/min, and adjusting the viscosity to 5000 Pa.S, thereby obtaining uniformly-dispersed and good slurry;
s2, filtering the slurry by using a 200-mesh sun screen, adding the obtained uniformly dispersed slurry into a feed barrel, and introducingFeeding the powder into a spray granulation tower through a peristaltic pump, wherein the feeding speed is controlled at 80kg/h of slurry, the air inlet temperature is controlled at 245 ℃, the air outlet temperature is controlled at 110 ℃, the rotating speed of an atomizing disk is controlled at 12000r/min, the negative pressure in the tower is 0.3MPa, and the solid powder with the particle size D50 of 11 mu m and the tap density of 1.40cm is obtained 3 /g；
S3, sieving the obtained powder particles with a 200-mesh sieve, putting the sieve into a graphite crucible, putting the crucible into a microwave sintering furnace protected by nitrogen/hydrogen reducing atmosphere (the volume ratio is 100:8), heating to 300 ℃ at a heating rate of 2 ℃/min, preserving heat for 5min, heating to 450 ℃ at a heating rate of 1.5 ℃/min, calcining for 15min, and cooling to room temperature at a cooling rate of 1.5 ℃/min to obtain the redox graphene-coated silicon nanocomposite with the core-shell structure;
s4, taking Mg-doped ZnO as a target material, wherein the purity of the target material is more than 3N, putting the redox graphene coated silicon nano core-shell structure composite material into a process cavity of a coating device, vacuumizing the process cavity, and ensuring that the background vacuum degree requirement is better than that of 5 multiplied by 10 -4 Pa; re-introducing process gas (nitrogen) into the process cavity to keep the air pressure in the process cavity at 0.5Pa, ensuring that the air cleanliness of the coating environment reaches ten thousand levels, the humidity is below 50%, and the temperature is 20 ℃, starting a cathode power supply of the coating equipment, and performing sputter coating on the powder, wherein the coating power is 3W/cm 2 And uniformly coating the Mg-doped ZnO target on the surface of the composite material by adopting a constant current mode, wherein the current is 50A, the deposition voltage is 350V, and finally obtaining the silicon-based nano composite anode material jointly coated by the redox graphene and the Mg-doped ZnO, wherein the thickness of the Mg-doped ZnO film is 110 nm.
Comparative example
The preparation method of the silicon-based nanocomposite anode material is different from that of example 3 only in that: the step S4 is not included.
The performance of the silicon-based nanocomposite anode materials prepared in examples 1 to 3 of the present invention and comparative examples was examined, and the results are shown in Table 1 and FIG. 1.
TABLE 1 cycle performance data for examples 1-3 and comparative examples
| Example 1 | Example 2 | Example 3 | Comparative example | |
| Gram volume | 1400mAh/g | 1250mAh/g | 1500mAh/g | 1650mAh/g |
| First effect | 89.5％ | 88.7％ | 90.0％ | 90.5％ |
| Full power rebound | 68％ | 60％ | 73％ | 80％ |
| Normal temperature cycle performance | 850 weeks @80% | 980 weeks @80% | 750 weeks @80% | 600 weeks @80% |
As can be seen from table 1, as the coating amount increases, the gram capacity of the material decreases, the first effect decreases, the rebound decreases correspondingly, and the cycle performance further improves.
Fig. 1 is an SEM image of a silicon-based nanocomposite anode material prepared in example 3, and it can be seen from the figure that after two coating processes, the surface deposition of the coating layer is relatively uniform, and the improvement of uniformity can suppress the bouncing in combination with the data of the example.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. The preparation method of the silicon-based nanocomposite anode material is characterized by comprising the following steps of:
s1, mixing graphene oxide, a binder, a dispersing agent and silicon nano particles under a protective atmosphere, ball-milling, and then adding deionized water into the mixed materials to obtain slurry;
s2, carrying out spray granulation on the slurry through a spray granulation tower to obtain powder;
s3, calcining the powder in a reducing atmosphere to obtain a silicon nanocomposite coated by the redox graphene with a core-shell structure;
and S4, coating the surface of the silicon nanocomposite coated by the redox graphene by taking Mg-doped ZnO as a target material and adopting a powder magnetron sputtering coating technology to obtain the silicon nanocomposite anode material jointly coated by the Mg-doped ZnO and the redox graphene.
2. The preparation method of the silicon-based nanocomposite anode material according to claim 1, wherein in S1, the mass ratio of graphene oxide, binder, dispersant and silicon nanoparticles is 2:2-3:2-3:18; wherein the graphene oxide is prepared by a Hummers method; the binder is styrene butadiene rubber or polyacrylic acid; the dispersing agent is sodium carboxymethyl cellulose.
3. The method for preparing the silicon-based nanocomposite anode material according to claim 1, wherein in the step S1, ball milling is performed for 4-10 hours, and the ball milling rotating speed is 200-500r/min.
4. The method for preparing a silicon-based nanocomposite anode material according to claim 1, wherein deionized water is added in S1 to adjust the viscosity of the slurry to 3000-5000pa·s.
5. The method for preparing a silicon-based nanocomposite anode material according to claim 1, wherein in S2, the technological parameters of spray granulation are: the feeding speed of the slurry is 50-100kg/h, the air inlet temperature is 230-245 ℃, the air outlet temperature is 110-115 ℃, the rotating speed of an atomizing disk is 12000-14000r/min, and the negative pressure in the tower is 0.2-0.5Mpa; obtaining solid powder with particle size D50 of 10-13 μm and tap density of 1.3-1.4cm 3 /g。
6. The method for preparing the silicon-based nanocomposite anode material according to claim 1, wherein in S3, the powder is subjected to microwave calcination in a microwave sintering furnace at 400-500 ℃ for 15-30min in a reducing atmosphere of a mixed gas of nitrogen and hydrogen; wherein, the volume ratio of nitrogen to hydrogen in the mixed gas is 100:5-10.
7. The method for preparing a silicon-based nanocomposite anode material according to claim 6, wherein the specific operation of microwave calcination is as follows: heating to 300 ℃ at a heating rate of 2 ℃/min, and preserving heat for 5min; then heating to 400-450 ℃ at a heating rate of 1.5 ℃/min, calcining for 15-30min, and finally cooling to room temperature at a cooling rate of 1.5 ℃/min.
8. The preparation method of the silicon-based nanocomposite anode material according to claim 1, wherein in S4, the process parameters of the powder magnetron sputtering coating are as follows: the sputtering power is 1-5w/cm 2 The cathode power supply adopts a constant current mode, the current is 30-45A, the deposition voltage is 350-450V, and the time is 2-10min.
9. The method for preparing a silicon-based nanocomposite anode material according to claim 1, wherein in S4, the thickness of the film layer of the plating film is controlled to be 100-180nm.
10. A silicon-based nanocomposite anode material prepared by the method of any one of claims 1-9.
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