CN114843461A - Preparation method of low-expansion silicon-based composite material - Google Patents
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Abstract
The invention discloses a preparation method of a low-expansion silicon-based composite material, which comprises the following steps of dispersing nano silicon in a carbon source solution to obtain a suspension A; dispersing silica in a carbon source solution to obtain a suspension B, simultaneously injecting the suspension A and the suspension B into an electrostatic spinning jet pipe, carrying out electrostatic spinning, and then carrying out vacuum drying and carbonization to obtain the silica-based composite material. The material prepared by the invention is of a double-layer sunken structure, and can reduce expansion and improve cycle and rate capability.
Description
Technical Field
The invention belongs to the technical field of secondary battery materials, and particularly relates to a preparation method of a low-expansion silicon-based composite material.
Background
The silicon-based material is applied to the high-energy-density lithium ion battery due to the advantages of high energy density, wide material source and the like, and the silicon-based material on the market at present mainly comprises silicon-oxygen-carbon (SiO) x -C) and silicon-carbon (Si-C), the silicon-carbon material having the characteristics of high first efficiency, large expansion and poor cycleThe silicon-oxygen material is suitable for being applied to a quick-charging battery, has the characteristics of good cycle performance, large impedance, low first-time efficiency and the like, and is suitable for being applied to a long-life battery. But the requirements of high energy density, quick charge and long service life of the negative electrode material of the lithium ion battery can not be directly met. One of the reasons that the expansion of silicon and carbon is large, the circulation difference and the silicon and oxygen resistance are large, and the first efficiency is low is that the expansion of the material causes the circulation and the resistance to be increased faster, and further the performance such as multiplying power is influenced. If the material only coats and modifies silicon carbon or silicon oxygen alone at present, the requirement of the market on high-energy quick charge and high first-efficiency of the lithium ion battery cathode can not be met, so that a special coating material and a new process need to be developed, the advantages of the silicon carbon and the silicon oxygen are exerted, the expansion is reduced, the first-time efficiency is improved, and the cycle performance is improved.
Disclosure of Invention
The invention aims to overcome the defects and provides a preparation method of a low-expansion silicon-based composite material which has a double-layer concave structure, can reduce expansion and improve cycle and rate performance.
The preparation method of the low-expansion silicon-based composite material comprises the following steps:
(1) dispersing nano silicon, a dispersing agent and a carbon source in an organic solvent, wherein the weight ratio of nano silicon: dispersing agent: carbon source: the mass ratio of the organic solvent is 100: 0.5-2: 1-10: 500-2000, and the suspension A is prepared by uniformly stirring;
(2) dispersing silica, a dispersing agent and a carbon source in an organic solvent, wherein the silica: dispersing agent: carbon source: the mass ratio of the organic solvent is 100: 0.5-2: 1-10: 500-2000, and the suspension B is prepared by uniformly stirring;
(3) simultaneously injecting the suspension A and the suspension B into a spiral injection pipe, wherein the inner injection liquid is suspension A, the outer injection liquid is suspension B, carrying out electrostatic spinning, the receiving distance is 10-20 cm, the voltage is 15-25 kV, and the solution flow rate is constant and is 0.5-1 mL/L; vacuum drying for 24h at 80 ℃ to obtain a silicon-based precursor material;
(4) and transferring the silicon-based precursor material into a tubular furnace, and calcining the silicon-based precursor material in an inert atmosphere at the calcining temperature of 800-1200 ℃ for 1.0-6.0 h to obtain the silicon-based composite material.
The preparation method of the low-expansion silicon-based composite material comprises the following steps: in the step (1), the carbon source is one of starch, glucose, citric acid, phenolic resin or furfural resin.
The preparation method of the low-expansion silicon-based composite material comprises the following steps: in the step (2), the carbon source is one of polyacrylic acid PAA, polytetrafluoroethylene PTFE, polyimide PI, polyvinyl alcohol PVA or polyacrylonitrile PAN.
The preparation method of the low-expansion silicon-based composite material comprises the following steps: the dispersing agent in the steps (1) and (2) is a complex composed of 30-70% of sodium carboxymethyl cellulose and 30-70% of sodium dodecyl sulfate.
The preparation method of the low-expansion silicon-based composite material comprises the following steps: the organic solvent in the steps (1) and (2) is one of N-methyl pyrrolidone, carbon tetrachloride, cyclohexane or isopropanol.
Compared with the prior art, the invention has obvious beneficial effects, and the technical scheme can show that: according to the invention, the surfaces of the nano silicon and the silicon oxygen materials are respectively coated with two different carbon sources, and because the different carbon sources have different shrinkage rates in the carbonization stage, a concave structure is formed after carbonization, so that the expansion is reduced; the surface of the nanometer silicon surface of the inner core is coated with the amorphous carbon, and the surface of the silica material of the outer shell is coated with the amorphous carbon, so that the expansion of the inner core can be restrained, the impedance can be reduced, and the cycle performance can be improved. This curved surface structure gives the particles high mechanical strength, which allows high tap and tap densities of the material in the pole piece.
Drawings
FIG. 1 is an SEM image of a silicon-based composite material prepared in example 1.
Detailed Description
Example 1:
a preparation method of a low-expansion silicon-based composite material comprises the following steps:
(1) dispersing 100g of nano silicon, 0.5g of sodium carboxymethylcellulose, 0.5g of sodium dodecyl sulfate and 5g of glucose in 1000ml of N-methylpyrrolidone, and uniformly stirring to obtain a suspension A;
(2) dispersing 100g of silicon oxide, 0.5g of sodium carboxymethylcellulose, 0.5g of sodium dodecyl sulfate and 5g of polyacrylic acid in 1000ml of N-methylpyrrolidone, and uniformly stirring to obtain a suspension B;
(3) simultaneously injecting the suspension A and the suspension B into a spiral injection pipe, wherein the inner injection liquid is the suspension A, the outer injection liquid is the suspension B, carrying out electrostatic spinning (the receiving distance is 15cm, the voltage is 20kV, the solution flow rate is constant and is 1mL/L), and carrying out vacuum drying at 80 ℃ for 24h to obtain a silicon-based precursor material;
(4) and transferring the silicon-based precursor material into a tubular furnace, and calcining for 3h at 1000 ℃ under the inert atmosphere of argon to obtain the silicon-based composite material.
Example 2:
a preparation method of a low-expansion silicon-based composite material comprises the following steps:
(1) dispersing 100g of nano silicon, 0.15g of sodium carboxymethyl cellulose, 0.35g of sodium dodecyl sulfate and 1g of phenolic resin in 500ml of carbon tetrachloride, and uniformly stirring to obtain a suspension A;
(2) dispersing 100g of silica, 0.15g of sodium carboxymethylcellulose, 0.35g of sodium dodecyl sulfate and 1g of polytetrafluoroethylene in 500ml of carbon tetrachloride, and uniformly stirring to obtain a suspension B;
(3) simultaneously injecting the suspension A and the suspension B into a spiral injection pipe, wherein the inner injection liquid is the suspension A, the outer injection liquid is the suspension B, carrying out electrostatic spinning (the receiving distance is 10cm, the voltage is 15kV, the solution flow rate is constant and is 0.5mL/L), and carrying out vacuum drying at 80 ℃ for 24h to obtain a silicon-based precursor material;
(4) and transferring the silicon-based precursor material into a tubular furnace, and calcining for 6 hours at 800 ℃ under the inert atmosphere of argon to obtain the silicon-based composite material.
Example 3:
a preparation method of a low-expansion silicon-based composite material comprises the following steps:
(1) dispersing 100g of nano silicon, 1.4g of sodium carboxymethyl cellulose, 0.6g of sodium dodecyl sulfate and 10g of glucose in 2000ml of cyclohexane, and uniformly stirring to obtain a suspension A;
(2) dispersing 100g of silicon oxide, 1.4g of sodium carboxymethylcellulose, 0.6g of sodium dodecyl sulfate and 10g of polyimide in 2000ml of cyclohexane, and uniformly stirring to obtain a suspension B;
(3) simultaneously injecting the suspension A and the suspension B into a spiral injection pipe, wherein the inner injection liquid is the suspension A, the outer injection liquid is the suspension B, carrying out electrostatic spinning (the receiving distance is 20cm, the voltage is 25kV, the solution flow rate is constant and is 1mL/L), and carrying out vacuum drying at 80 ℃ for 24h to obtain a silicon-based precursor material;
(4) and transferring the silicon-based precursor material into a tubular furnace, and calcining for 1h at 1200 ℃ under the inert atmosphere of argon to obtain the silicon-based composite material.
Comparative example:
dispersing 100g of nano silicon, 100g of silicon oxide and 2g of sodium carboxymethylcellulose in 2000ml of N-methylpyrrolidone, uniformly stirring, carrying out spray drying (200 ℃), transferring the obtained material into a tube furnace, and calcining for 3 hours at 1000 ℃ under an argon inert atmosphere to obtain the silicon-based composite material.
Test example 1:
SEM tests were performed on the silicon-based composite material of example 1. The test results are shown in fig. 1. As shown in FIG. 1, the particle size of the silicon-based composite material is 5-15 μm, and the silicon-based composite material has a concave structure.
Test example 2:
the silicon-based composite materials of the examples and the comparative examples were tested for their physical and chemical properties (powder conductivity, tap density) according to the method of the national standard GB/T-243354-2019 graphite-based cathode materials for lithium ion batteries, and the test results are shown in Table 1.
TABLE 1 comparison of the physico-chemical properties of the examples and of the comparative examples
| Sample (I) | Tap density (g/cm3) | Powder conductivity (S/cm) |
| Example 1 | 0.98 | 14.5 |
| Example 2 | 0.97 | 13.3 |
| Example 3 | 0.96 | 11.4 |
| Comparative example | 0.81 | 5.4 |
As can be seen from Table 1: compared with the comparative example, the powder conductivity of the silicon-based composite material is obviously improved, and the reason is that the electrostatic spinning technology is adopted for preparing the composite material, so that the silicon-based composite material has the characteristic of high density, the impedance is reduced, and the tap density is improved.
Test example 3:
the silicon-based composite materials in examples 1-3 and the silicon-based composite material in the comparative example are respectively used as active materials to prepare the pole piece, and the specific preparation method comprises the following steps: adding 9g of active substance, 0.5g of conductive agent SP and 0.5g of binder LA133 into 220mL of deionized water, and uniformly stirring to obtain slurry; and coating the slurry on a copper foil current collector to obtain the copper foil current collector.
The pole pieces using the silicon-based composite materials of examples 1 to 3 as active materials were respectively labeled as a to C, and the pole pieces using the silicon-based composite materials of comparative examples as active materials were respectively labeled as D. And then, the prepared pole piece is used as a negative pole, and the pole piece, a lithium piece, electrolyte and a diaphragm are assembled into a button cell in a glove box with the argon and water contents lower than 0.1 ppm. Wherein the diaphragm is celAn egr 2400; the electrolyte is LiPF 6 Solution of (2), LiPF 6 Is 1.2mol/L, and the solvent is a mixed solution of Ethylene Carbonate (EC) and diethyl carbonate (DMC) (weight ratio is 1: 1). The button cells are labeled a-1, B-1, C-1, and D-1, respectively. And then testing the performance of the button cell by adopting a blue light tester under the following test conditions: and (3) carrying out charge and discharge at a multiplying power of 0.1C, wherein the voltage range is 0.005-2V, the cycle is stopped after 3 weeks, and then the full-electricity expansion of the negative pole piece is tested, and the test results are shown in table 2.
Table 2 results of performance testing
As can be seen from table 2, compared with the comparative example, the first efficiency of the silicon-based composite material of the present invention is significantly improved and the expansion thereof is significantly reduced, because the amorphous carbon obtained by carbonizing two different carbon sources at high temperature has a concave structure, which can reduce the expansion of the material, and meanwhile, the material structure prepared by the electrostatic spinning technology has the advantages of high density, low impedance, and improved gram volume performance of the material.
Test example 4:
the silicon-based composite materials of examples 1 to 3 and the comparative example were doped with 90% of artificial graphite as a negative electrode material and a positive electrode ternary material (LiNi) 1/3 Co 1/3 Mn 1/3 O 2 ) The electrolyte and the diaphragm are assembled into the 5Ah soft package battery. Wherein the diaphragm is celegard 2400, and the electrolyte is LiPF 6 Solution (solvent is mixture of EC and DEC at volume ratio of 1:1, LIPF 6 The concentration of (1.3 mol/L). The prepared soft package batteries are respectively marked as A-2, B-2, C-2 and D-2.
The following performance tests were performed on the pouch cells:
(1) dissecting and testing the thickness D1 of the negative pole piece of the soft package battery A-2-D-2 with constant volume, then circulating each soft package battery for 100 times (1C/1C @25 +/-3 ℃ @2.5-4.2V), fully charging the soft package battery, dissecting again to test the thickness D2 of the negative pole piece after circulation, and then calculating the expansion rate (the expansion rate is equal to the expansion rate of the negative pole piece after circulation)
) The test results are shown in Table 3.
TABLE 3 negative pole piece expansion ratio test results
| Lithium ion battery | D1(μm) | D2(μm) | Swelling ratio (%) |
| A-2 | 112 | 158.5 | 41.52 |
| B-2 | 111 | 158.0 | 42.34 |
| C-2 | 112 | 160.4 | 43.21 |
| D-2 | 110 | 189.5 | 71.00 |
As can be seen from Table 3, the expansion rate of the negative electrode plate of the soft-package lithium ion battery adopting the silicon-based composite material is obviously lower than that of the comparative example. The reason is that the silicon-based composite material has high compactness and the fibrous concave structure of the silicon-based composite material reduces the expansion of the silicon-based composite material.
(2) And (3) carrying out cycle performance test and rate test on the soft package batteries A-2-D-2, wherein the cycle test conditions are as follows: the charge-discharge voltage range is 2.5-4.2V, the temperature is 25 +/-3.0 ℃, and the charge-discharge multiplying power is 0.5C/1.0C. The multiplying power test conditions are as follows: the material was tested for constant current ratio at 2C and the results are shown in table 4.
TABLE 4 results of the cycle performance test
As can be seen from table 4, the cycle performance of the soft-package lithium ion battery prepared by using the silicon-based composite material of the present invention is superior to that of the comparative example at each stage of the cycle, because the outer shell of the silicon-based composite material of the present invention has the recessed carbon-based material for reducing the expansion, the expansion is reduced, and the cycle performance is improved; meanwhile, the fibrous structure reduces the impedance and improves the quick filling performance.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are within the scope of the present invention without departing from the technical spirit of the present invention.
Claims (5)
1. A preparation method of a low-expansion silicon-based composite material comprises the following steps:
(1) dispersing nano silicon, a dispersing agent and a carbon source in an organic solvent, wherein the weight ratio of nano silicon: dispersing agent: carbon source: the mass ratio of the organic solvent is 100: 0.5-2: 1-10: 500-2000, and the suspension A is prepared by uniformly stirring;
(2) dispersing silica, a dispersing agent and a carbon source in an organic solvent, wherein the silica: dispersing agent: carbon source: the mass ratio of the organic solvent is 100: 0.5-2: 1-10: 500-2000, and the suspension B is prepared by uniformly stirring;
(3) simultaneously injecting the suspension A and the suspension B into a spiral injection pipe, wherein the inner injection liquid is suspension A, the outer injection liquid is suspension B, carrying out electrostatic spinning, the receiving distance is 10-20 cm, the voltage is 15-25 kV, and the solution flow rate is constant and is 0.5-1 mL/L; vacuum drying at 80 ℃ for 24h to obtain a silicon-based precursor material;
(4) and transferring the silicon-based precursor material into a tubular furnace, and calcining the silicon-based precursor material in an inert atmosphere at the calcining temperature of 800-1200 ℃ for 1.0-6.0 h to obtain the silicon-based composite material.
2. A method of making a low expansion silicon-based composite material as claimed in claim 1 wherein: in the step (1), the carbon source is one of starch, glucose, citric acid, phenolic resin or furfural resin.
3. A method of making a low expansion silicon-based composite material as claimed in claim 1 wherein: in the step (2), the carbon source is one of polyacrylic acid PAA, polytetrafluoroethylene PTFE, polyimide PI, polyvinyl alcohol PVA or polyacrylonitrile PAN.
4. A method of making a low expansion silicon-based composite material as claimed in claim 1 wherein: the dispersing agent in the steps (1) and (2) is a complex composed of 30-70% of sodium carboxymethyl cellulose and 30-70% of sodium dodecyl sulfate.
5. A method of making a low expansion silicon-based composite material as claimed in claim 1 wherein: the organic solvent in the steps (1) and (2) is one of N-methyl pyrrolidone, carbon tetrachloride, cyclohexane or isopropanol.
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