CN114864915B - Preparation method of porous silicon/carbon nano tube composite material - Google Patents
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Abstract
The invention provides a preparation method of a porous silicon/carbon nano tube composite material, which comprises the following steps of firstly preparing a porous silicon material, then soaking the porous silicon material in nickel nitrate solution, then uniformly doping a catalyst nickel nitrate between porous silicon through hydrothermal reaction, drying at a low temperature, finally depositing carbon source gas on the surface of the porous silicon through a vapor deposition method to generate carbon nano tubes, and then carrying out acid washing and drying to obtain the porous silicon/carbon nano tube composite material. According to the preparation process, the carbon nanotubes growing on the surface of the porous silicon vertically grow on the surface of the porous silicon by utilizing the self-catalysis of the nickel, so that the intercalation channels of lithium ions in the charge and discharge processes are improved, the quick charge performance of the porous silicon material is improved, and meanwhile, the characteristics of good liquid absorption performance and low expansion of the porous silicon material are utilized, so that the cycle performance of the porous silicon material is improved.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a preparation method of a porous silicon/carbon nano tube composite material.
Background
With the requirements of the electric automobile on the endurance mileageThe negative electrode material is required to have higher energy density, and the silicon-carbon material becomes the first choice material of the next generation lithium ion battery due to the advantages of high specific capacity, wide sources of raw materials and the like, but the defects of poor conductivity, large expansion and the like of the silicon-carbon material affect the rate charging, cycle and low-temperature performance of the lithium ion battery. One of the current measures for improving the conductivity of the silicon-carbon material is to coat the surface of the silicon material with carbon and dope the silicon material with metal/nonmetal, and the measure for reducing the expansion of the silicon-carbon material is to nano-scale and porous the silicon-carbon material. For example, patent application CN201610164963.4 discloses a porous silicon-carbon composite material, a preparation method and application thereof, which are mainly realized by placing magnesium silicide powder in CO 2 And carrying out heat treatment at 700-900 ℃ in Ar mixed atmosphere, and then carrying out acid washing and post-treatment to obtain the porous silicon-carbon composite material, wherein the prepared material is improved in cycle performance, but the expansion improvement result of the material is not shown, and meanwhile, the conductivity of the porous silicon-carbon material prepared by the method is not obviously improved. The carbon nano tube is deposited on the surface of the silicon carbon at present mainly by a CVD method, the uniformity of the deposition on the surface of the carbon nano tube is poor, and the surface binding force between the carbon nano tube and silicon is poor, so that the carbon nano tube is easy to fall off in the charge-discharge cycle process, and the cycle performance of the carbon nano tube is fast attenuated.
Disclosure of Invention
Aiming at the problems of poor silicon-carbon binding force, uneven carbon distribution on the surface of silicon and large expansion force of the existing silicon-carbon composite material, the invention adopts the nickel nitrate catalyst doped in porous silicon and takes the nickel nitrate catalyst as a matrix to grow the carbon nano tube so as to improve the growth mode of the carbon nano tube and the binding force of the silicon and the carbon, and finally improve the conductivity and the cycle performance of the silicon-carbon composite material.
The invention provides a preparation method of a porous silicon/carbon nano tube composite material, which comprises the following steps:
(1) Preparation of porous silicon:
grinding metal magnesium and silicon dioxide in a high-speed grinding machine, transferring into a tube furnace, heating to 400-600 ℃ under argon atmosphere for thermal reduction, adding into a nitric acid solution for soaking for 24 hours, pickling to remove the metal magnesium, and drying to obtain porous silicon A, wherein the mass ratio of each component is metal magnesium to silicon dioxide= (2-4): 1;
(2) Preparation of a nickel doped porous silicon composite material:
preparing nickel nitrate solution with the mass concentration of 1-5%, adding porous silicon A, uniformly stirring, adding graphene solution and urea, transferring to a high-pressure reaction kettle, reacting for 1-12 hours at 150-200 ℃ through hydrothermal reaction, and filtering and drying to obtain a nickel doped porous silicon composite material B, wherein the mass ratio of each component is nickel nitrate, porous silicon A, graphene and urea= (1-5) 100 (0.5-2) 0.1-0.5;
(3) Preparation of porous silicon/carbon nanotube composite material:
transferring the nickel-doped porous silicon composite material B into a tube furnace, firstly introducing inert gas to remove air in the tube, then introducing carbon source gas, heating to 600-1000 ℃, preserving heat for 1-6 h, stopping introducing the carbon source gas, introducing the inert gas, naturally cooling to room temperature, and then pickling and drying to obtain the porous silicon/carbon nano tube composite material.
In a preferred embodiment of the present invention, the carbon source gas in step (3) is one of acetylene, methane and ethylene.
In a preferred embodiment of the present invention, in step (1), the milling time is 1 to 48 hours.
In a preferred embodiment of the present invention, in step (1), the time of thermal reduction is 1 to 48 hours.
In a preferred embodiment of the invention, in step (1) and step (3), HCl is used in a concentration of 0.1mol/L for pickling.
The beneficial effects are that:
1) Doping nickel nitrate catalyst into the pores or the surface of porous silicon by a hydrothermal method, then taking the porous silicon as a matrix, growing carbon nanotubes on the surface of the porous silicon, wherein the growing mode of the final carbon nanotubes is that the final carbon nanotubes are perpendicular to the surface of the porous silicon to form a cluster structure, so that on one hand, the transmission rate of lithium ions is improved, the expansion is reduced and the cycle performance of the porous silicon is improved in the charge and discharge process; on the other hand, the clustered structure of the carbon nano tube has high specific surface area, so that the liquid absorption and retention capacity of the material is improved, and the cycle performance is further improved;
2) The porous silicon is prepared by magnesium reduction and acid washing, and has the advantages of simple preparation process and little influence of excessive magnesium on the capacity and performance of the material.
Drawings
The invention may be better understood by reference to the following description of an embodiment of the invention, taken in conjunction with the accompanying drawings in which:
fig. 1 is an SEM image of the porous silicon/carbon nanotube composite material prepared in example 1.
Detailed Description
Example 1
1) Preparation of porous silicon:
grinding 30g of metal magnesium and 10g of silicon dioxide in a high-speed grinding machine for 2 hours, transferring into a tube furnace, heating to 500 ℃ under argon atmosphere for thermal reduction for 24 hours, adding into a nitric acid solution, soaking for 24 hours, pickling with 0.1mol/L HCL, washing with deionized water, removing metal magnesium, and drying to obtain porous silicon A;
2) Preparation of a nickel doped porous silicon composite material:
3g of nickel nitrate is added into 100ml of deionized water to prepare a nickel nitrate solution with the mass concentration of 3%, then 100g of porous silicon A is added, after uniform stirring, 100ml of graphene solution with the mass concentration of 1% and 0.3g of urea are added, then the mixture is transferred into a high-pressure reaction kettle and reacted for 6 hours at the temperature of 180 ℃, and then the mixture is filtered and dried in vacuum to obtain a nickel-doped porous silicon composite material B;
3) Preparation of porous silicon/carbon nanotube composite material:
transferring the nickel-doped porous silicon composite material B into a tube furnace, firstly introducing argon inert gas to remove air in the tube, then introducing methane gas, heating to 800 ℃, preserving heat for 3 hours, stopping introducing methane gas, introducing argon inert gas, naturally cooling to room temperature, then adopting HCL with the concentration of 0.1mol/L for pickling, and drying to obtain the porous silicon/carbon nanotube composite material.
Example 2
1) Preparation of porous silicon:
grinding 20g of metal magnesium and 10g of silicon dioxide in a high-speed grinding machine for 1h, transferring into a tube furnace, heating to 400 ℃ under argon atmosphere for thermal reduction for 1h, adding into a nitric acid solution, soaking for 24h, pickling with 0.1mol/L HCL, removing metal magnesium, and drying to obtain porous silicon A;
2) Preparation of a nickel doped porous silicon composite material:
adding 1g of nickel nitrate into 100ml of deionized water to prepare a nickel nitrate solution with the mass concentration of 1%, adding 100g of porous silicon A, uniformly stirring, adding 50ml of graphene solution with the mass concentration of 1% and 0.1g of urea, transferring into a high-pressure reaction kettle, reacting at the temperature of 150 ℃ for 1h, filtering, and drying to obtain a nickel-doped porous silicon composite material B;
3) Preparation of porous silicon/carbon nanotube composite material:
transferring the nickel-doped porous silicon composite material B into a tube furnace, firstly introducing argon inert gas to remove air in the tube, then introducing ethylene carbon source gas, heating to 600 ℃, preserving heat for 6 hours, stopping introducing the ethylene carbon source gas, introducing argon inert gas, naturally cooling to room temperature, then adopting HCL with the concentration of 0.1mol/L for pickling, and drying to obtain the porous silicon/carbon nanotube composite material.
Example 3
1) Preparation of porous silicon:
grinding 40g of magnesium metal and 10g of silicon dioxide in a high-speed grinding machine for 48 hours, transferring into a tube furnace, heating to 600 ℃ under argon atmosphere for thermal reduction for 48 hours, adding into a nitric acid solution, soaking for 24 hours, pickling with 0.1mol/L HCL, removing magnesium metal, and drying to obtain porous silicon A;
2) Preparation of a nickel doped porous silicon composite material:
adding 5g of nickel nitrate into 100ml of deionized water to prepare a nickel nitrate solution with the mass concentration of 5%, adding 100g of porous silicon A, uniformly stirring, adding 200ml of graphene solution with the mass concentration of 1% and 0.5g of urea, transferring into a high-pressure reaction kettle, reacting at the temperature of 200 ℃ for 12 hours, filtering, and drying to obtain a nickel-doped porous silicon composite material B;
3) Preparation of porous silicon/carbon nanotube composite material:
transferring the nickel-doped porous silicon composite material B into a tube furnace, firstly introducing argon inert gas to remove air in the tube, then introducing acetylene carbon source gas, heating to 1000 ℃, preserving heat for 1h, stopping introducing the acetylene carbon source gas, introducing argon inert gas, naturally cooling to room temperature, then adopting HCL with the concentration of 0.1mol/L for pickling, and drying to obtain the porous silicon/carbon nanotube composite material.
Comparative example
Transferring commercially available nano silicon into a tube furnace, introducing argon inert gas to remove air in the tube, introducing acetylene carbon source gas, heating to 1000 ℃, preserving heat for 1h, stopping introducing the acetylene carbon source gas, introducing the argon inert gas, and naturally cooling to room temperature to obtain the porous silicon/carbon composite material.
Sem test
SEM test was performed on the porous silicon/carbon nanotube composite material obtained in example 1, and the test results are shown in fig. 1. As can be seen from FIG. 1, the particle size distribution of the material is uniform and reasonable, the particle size is between 5 and 10 mu m, and the surface of the material is provided with a hole structure.
2. Button cell testing
The porous silicon/carbon nanotube composite materials obtained in examples 1 to 3 and comparative example were assembled into a button cell as a negative electrode material for lithium ion batteries.
The preparation method comprises the following steps: adding binder, conductive agent and solvent into the negative electrode material of lithium ion battery, stirring and pulping, coating on copper foil, drying and rolling to obtain the negative electrode plate, wherein the binder is LA132, the conductive agent is conductive carbon black (SP), the solvent is N-methylpyrrolidone (NMP), the negative electrode material, SP,LA132 and NMP are used in the proportion of 95g to 1g to 4g to 220mL, and LiPF is used in the electrolyte 6 As electrolyte, a mixture of EC and DEC in a volume ratio of 1:1 is used as a solvent, a metal lithium sheet is used as a counter electrode, and a polypropylene (PP) film is used as a diaphragm. The button cell assembly was performed in an argon filled glove box. Electrochemical performance is carried out on a Wuhan blue electric CT2001A type battery tester, the charge-discharge voltage range is 0.005V-2.0V, and the charge-discharge rate is 0.1C. The test results are shown in Table 1.
As can be seen from the data in table 1, the specific capacity and the first efficiency of the silicon-carbon composite anode materials prepared in examples 1 to 3 of the present invention are significantly better than those of the comparative examples. The nickel doped anode material provided by the invention improves the conductivity of the material, and simultaneously the carbon nano tube grows on the anode material to improve the conductivity of the material, so that the gram capacity of the anode material is improved, the first efficiency of the anode material is improved, and meanwhile, the carbon nano tube vertically grows to have a high specific surface area, so that the specific surface area of the composite material is improved.
3. Soft package battery test
The porous silicon/carbon nanotube composite materials of examples 1 to 3 and comparative example were doped with 90% of artificial graphite as a negative electrode material to prepare a negative electrode sheet using ternary material Li (Ni 0.6 Co 0.2 Mn 0.2 ）O 2 As positive electrode material, liPF in electrolyte 6 As an electrolyte, a mixture of Ethylene Carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1:1 was used as a solvent, and Celgard 2400 membrane was used as a separator to prepare a 5Ah pouch cell, labeled C1, C2, C3, and D1.
3.1 liquid absorbing Capacity and liquid Retention testing
3.1.1 liquid absorbent Capacity
And (3) adopting a 1mL burette, sucking electrolyte VmL, dripping one drop on the surface of the pole piece, timing until the electrolyte is absorbed, recording time t, and calculating the liquid suction speed V/t of the pole piece. The test results are shown in Table 2.
3.1.2 liquid retention test
Calculating theoretical liquid absorption m1 of the pole piece according to the pole piece parameters, weighing the weight m2 of the pole piece, then placing the pole piece into electrolyte for soaking for 24 hours, weighing the weight m3 of the pole piece, calculating the liquid absorption m3-m2 of the pole piece, and calculating according to the following formula: retention = (m 3-m 2) ×100%/m1. The test results are shown in Table 2.
As can be seen from Table 2, the liquid absorption and retention capacities of the silicon-carbon composite anode materials obtained in examples 1-3 are significantly higher than those of the comparative examples, because the example materials have high specific surface areas, thereby improving the liquid absorption and retention capacities of the materials.
3.2 testing of pole piece resistivity and rebound Rate
3.2.1 Pole piece resistivity test
The resistivity of the pole pieces was measured using a resistivity tester, and the test results are shown in table 3.
3.2.2 Pole piece rebound Rate test
Firstly, testing the average thickness D1 of a pole piece by adopting a thickness gauge, then placing the pole piece in a vacuum drying oven at 80 ℃ for drying for 48 hours, testing the thickness D2 of the pole piece, and calculating according to the following formula: rebound rate= (D2-D1) ×100%/D1. The test results are shown in Table 3.
3.3 cycle Performance test
The cycle performance of the battery was tested at 25.+ -. 3 ℃ with a charge/discharge rate of 1C/1C and a voltage range of 2.5V-4.2V. The test results are shown in Table 3.
As can be seen from the data in table 3, the negative electrode sheets prepared by using the porous silicon/carbon nanotube composite materials obtained in examples 1 to 3 have significantly lower rebound rate than the negative electrode sheets prepared by using the porous silicon/carbon nanotube composite material of the present invention. The porous material of the material is uniformly distributed, and the nickel doping is carried out, so that the number of the micron holes of the porous material is increased, the rebound of the pole piece is reduced, and the conductivity of the pole piece is improved.
As can be seen from table 3, the cycle performance of the battery prepared from the silicon-carbon composite anode material provided by the invention is obviously better than that of the comparative example. This is because the porous silicon/carbon nanotube composite material provided by the invention has low rebound rate and low impedance, and improves the structural stability of the material in the circulation process, thereby improving the circulation performance.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (5)
1. The preparation method of the porous silicon/carbon nano tube composite material is characterized by comprising the following steps of:
(1) Preparation of porous silicon:
grinding metal magnesium and silicon dioxide in a high-speed grinding machine, transferring to a tube furnace, heating to 400-600 ℃ under argon atmosphere for thermal reduction, adding into a nitric acid solution for soaking for 24 hours, pickling to remove the metal magnesium, and drying to obtain porous silicon A, wherein the mass ratio of each component is metal magnesium to silicon dioxide= (2-4): 1;
(2) Preparation of a nickel doped porous silicon composite material:
preparing nickel nitrate solution with the mass concentration of 1-5%, adding the porous silicon A, stirring uniformly, adding graphene solution and urea, transferring to a high-pressure reaction kettle, reacting for 1-12 h at 150-200 ℃ through hydrothermal reaction, and filtering and drying to obtain the nickel-doped porous silicon composite material B, wherein the mass ratio of each component is nickel nitrate, porous silicon A, graphene and urea= (1-5): 100 (0.5-2): 0.1-0.5);
(3) Preparation of porous silicon/carbon nanotube composite material:
transferring the nickel-doped porous silicon composite material B into a tube furnace, firstly introducing inert gas to remove air in the tube, then introducing carbon source gas, heating to 600-1000 ℃, preserving heat for 1-6 h, stopping introducing the carbon source gas, introducing the inert gas, naturally cooling to room temperature, and then pickling and drying to obtain the porous silicon/carbon nanotube composite material.
2. The production method according to claim 1, wherein in the step (3), the carbon source gas is one of acetylene, methane and ethylene.
3. The method according to claim 1, wherein in the step (1), the time for grinding is 1 to 48 hours.
4. The process according to claim 1, wherein in the step (1), the time for thermal reduction is 1 to 48 hours.
5. The process according to claim 1, wherein in step (1) and step (3), the acid washing is performed with HCl having a concentration of 0.1 mol/L.
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