CN111403694A - Preparation method of carbon-coated porous silicon negative electrode material - Google Patents
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Abstract
The invention relates to the technical field of lithium ion batteries, and provides a preparation method of a carbon-coated porous silicon negative electrode material, which aims to solve the problems that the cycle life of a battery is too low and the like due to large volume change in the lithium desorption and insertion process of a silicon-based negative electrode material of a lithium ion battery. And changing the concentration of the electrolyte and the current density to carry out secondary etching on the porous silicon material so as to promote the stripping of the porous silicon film, and carrying out ultrasonic stripping by using an ultrasonic cell crusher to obtain the porous silicon material. And finally, coating the surface of the porous silicon material by using sugar alcohol, and performing heat treatment to obtain the carbon-coated porous silicon material. The prepared porous silicon-based composite material has the characteristics of good conductivity, high specific capacity, small volume change and the like.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a carbon-coated porous silicon negative electrode material.
Background
There are dozens of materials used for lithium ion secondary batteries, such as positive and negative electrode active materials, electrolytes, electrolyte additives, polymer diaphragms, positive and negative electrode conductive additives, positive and negative current collectors, and the like. The materials have different influences on the safety performance of the battery, but the materials have the largest influence, namely the positive electrode material, the negative electrode material, the diaphragm material and the electrolyte material, and the four materials are the key points for the safety performance research of the lithium ion battery. The lithium battery cathode material is currently the most critical link in the lithium ion battery industry. The research on the negative electrode material is still in the initial stage relative to the positive electrode material of the lithium battery, and the lithium ion negative electrode material mainly comprises a carbon-based material, a silicon-based material, a transition metal oxide material and the like, wherein the theoretical specific capacity of the semiconductor silicon material which is concerned is up to 4200mAh g-1Far higher than the theoretical specific capacity (372mAh g) of the carbon material-1) However, such materials have not been put into practical use so far, and the main reason is that the silicon negative electrode has a large volume change (up to 300%) during the lithium deintercalation process, so that the silicon material structure collapses, and the cycle life of the battery is reduced. Meanwhile, the silicon material is used as a semiconductor material, so that the intrinsic conductivity is low and the conductivity is poor. At present, some reports have been made on the optimization and improvement technology of silicon-based negative electrode materials, for example, patent CN109763134A reports a preparation method of porous silicon, in which an author presses and forms silicon dioxide powder into a block, then sinters and forms the block into a porous electrode, and after electrolysis, the porous silicon material is obtained after cleaning with a hydrochloric acid solution and treatment with a hydrofluoric acid solution. The method has the advantages of conveniently regulating and controlling the form of the porous silicon, having cheap and easily obtained raw materials, relatively low reaction temperature, easily regulating the form of the porous silicon, being convenient for large-scale production and the like. However, the preparation process of the material involves more complicated sintering and electrolysis processes, so that the material is not beneficial to large-scale industrial production, and the sizes and the distribution of holes are not uniform and are not easy to control.
Disclosure of Invention
In order to solve the problems of the lithium ion battery silicon-based negative electrode material that the volume change is large in the lithium releasing and embedding process, the battery cycle life is too short, and the like, the invention provides a preparation method of a carbon-coated porous silicon negative electrode material.
The technical scheme of the invention is realized by a method for compensating material expansion by utilizing a buffer framework, and the preparation method of the carbon-coated porous silicon negative electrode material comprises the following steps:
(1) etching porous silicon pore channels: performing electrochemical etching under high current density by taking a platinum sheet as a cathode, a silicon wafer as an anode and a high-concentration hydrofluoric acid ethanol solution as electrolyte; the silicon-based material has a uniform and compact tubular porous structure, and the volume expansion during charging and discharging is mainly performed in the radial direction of the tubular structure, so that the damage of the volume expansion during charging and discharging on the porous silicon structure can be effectively reduced. Meanwhile, the porosity, thickness, pore diameter and pore wall thickness can be controlled by processing parameters.
The internal gaps of the porous silicon can reserve buffer space for volume expansion in the lithium silicon alloying process, and relieve the internal mechanical stress of the material.
Preferably, the volume ratio of hydrofluoric acid to ethanol in the high-concentration hydrofluoric acid ethanol solution is 4: 1-1: 4, and the high current density is 100-500 mA-cm-2To ensure the depth of the hole and the etching speed.
Preferably, the etching time is 100s to 1000s, the time is too short, the porous silicon film is too thin, the yield is low, the time is too long, the pore diameter is further enlarged, and the pore density is reduced.
Preferably, the silicon wafer is a boron-doped silicon wafer, the resistivity is 0.001 Ω -1 Ω, and P-type silicon has relatively good conductivity.
2) Stripping porous silicon: transferring the porous silicon wafer etched in the step (1) into a low-concentration hydrofluoric acid ethanol solution, performing electrochemical etching under low current density, performing ultrasonic stripping, and washing to obtain porous silicon powder; after the concentration of hydrofluoric acid and the current density are changed, secondary etching is carried out, the connection between the porous silicon material and the silicon wafer can be damaged by the secondary etching under low-concentration electrolyte and low-current density, and the porous silicon material can be conveniently stripped from the silicon wafer.
Preferably, the volume ratio of hydrofluoric acid to ethanol in the low-concentration hydrofluoric acid ethanol solution is 1: 10-1: 30, and the low current density is 1-20 mA-cm-2。
Preferably, the etching time is 10-200 s.
Preferably, an ultrasonic cell crusher is used for carrying out ultrasonic stripping to prepare the porous silicon powder, the ultrasonic power is 500-1000W, and the ultrasonic time is 300-3000S. The porous film on the silicon wafer is not easy to fall off after secondary etching, and high-power ultrasound is needed so as to obtain porous silicon powder with openings at two ends.
3) Carbon coating: mixing and stirring sugar alcohol and porous silicon powder, polymerizing and coating, and carbonizing at high temperature to obtain the carbon-coated porous silicon negative electrode material.
The coating structure is to coat a carbon layer on the surface of the active material silicon, so that the volume effect of the silicon is relieved, and the conductivity of the silicon is enhanced. The carbon material is used for carrying out surface coating modification on silicon, so that the embedding depth of lithium is limited, the volume change of silicon in the charging and discharging process is relieved, the integral conductivity of the material is improved, and the agglomeration of silicon particles is avoided.
Preferably, the mass ratio of the sugar alcohol to the silicon powder is 0.01-0.05: 1. The sugar alcohol mainly plays a role in providing a carbon source, the sugar alcohol is too much, agglomeration is easy to occur after sintering, the carbon layer outside the silicon powder is too thick, the lithium ion is blocked from being de-embedded on the porous silicon, and the battery capacity cannot be high. If the amount is too small, a certain amount of coating is not achieved, lithium ions are too deeply deintercalated to cause a large change in volume, and dispersion is also not facilitated.
Preferably, the polymerization temperature is 50 to 100 ℃ and the polymerization time is 1 to 10 hours.
Preferably, the carbonization temperature is 500-1000 ℃, and the carbonization time is 1-5 hours. Further optimizing the carbonization temperature and time finds that the porous silicon/carbon composite material has the best performance at the carbonization temperature of 800 ℃.
The carbon-based negative electrode material has small volume change in the charging and discharging processes and good cycle stability, and is a mixed conductor of ions and electrons; in addition, silicon and carbon have similar chemical properties and can be tightly combined.
In the Si/C composite system, Si particles are used as active substances to provide lithium storage capacity; the C can buffer the volume change of the silicon cathode in the charging and discharging process, improve the conductivity of the Si-based material and avoid the agglomeration of Si particles in the charging and discharging cycle. Therefore, the Si/C composite material combines the advantages of the Si/C composite material and the Si/C composite material, and shows high specific capacity and long cycle life.
The porous silicon negative electrode material prepared by the preparation method of the carbon-coated porous silicon negative electrode material is applied to a lithium ion battery. The silicon-carbon composite material formed by porous silicon has a more stable structure in the circulation process. Research shows that in the porous silicon/carbon composite material, the pore channel structure uniformly distributed in the silicon particles can provide a rapid ion transmission channel, and the large specific surface area increases the material reaction activity, so that the porous silicon/carbon composite material has excellent rate performance and has remarkable advantage in the aspect of quick charge performance of a battery.
The invention provides a method for preparing a novel porous silicon-based material by three steps: namely, a porous silicon film with a certain thickness is etched on a silicon wafer in hydrofluoric acid ethanol solution with a certain concentration by an electrochemical etching method. And changing the concentration of the electrolyte and the current density to carry out secondary etching on the porous silicon material so as to promote the stripping of the porous silicon film, and carrying out ultrasonic stripping by using an ultrasonic cell crusher to obtain the porous silicon material. And finally, coating the surface of the porous silicon material by using sugar alcohol, and performing heat treatment to obtain the carbon-coated porous silicon material.
Compared with the prior art, the invention has the beneficial effects that:
(1) the prepared carbon-coated porous silicon negative electrode material has the characteristics of good conductivity, high specific capacity, small volume change and the like;
(2) the invention has simple and easy process and low cost, effectively solves the problem of structural damage caused by volume expansion, and improves the service life and the use safety of the battery.
Drawings
Fig. 1 is an SEM image of the carbon-coated porous silicon negative electrode material prepared in example 1;
Detailed Description
The present invention will be described in further detail below with reference to examples and the accompanying drawings, in which the starting materials are commercially available or can be prepared by conventional methods.
Example 1
1) Cleaning a P-type silicon wafer (with the resistivity of 0.001 omega cm), connecting the P-type silicon wafer serving as an anode and a platinum electrode serving as a cathode to a constant current meter, adding an electrolyte with the volume ratio of HF to EtOH being 3: 1 into a reaction container, and adding 250 mA/cm of the electrolyte-2The electrochemical etching is performed for 500 s.
2) The etched silicon wafer was etched at a rate of 10mA cm-2The current density of (3) was twice etched for 50 seconds with an electrolyte solution having a volume ratio of HF to EtOH of 1: 10. Then, the porous silicon powder is obtained by ultrasonic 3000s stripping with the power of 500W of the ultrasonic cell crusher.
3) Ultrasonically dispersing 1 g of porous silicon powder into 100 g of water, adding 0.01 g of sugar alcohol, mixing and stirring uniformly, polymerizing for 6 hours at 90 ℃, separating, putting into a tubular furnace, and calcining for 5 hours at 500 ℃ under the argon atmosphere to obtain the carbon-coated porous silicon negative electrode material 1.
An SEM image of the carbon-coated porous silicon anode material 1 is shown in fig. 1.
Example 2
1) Cleaning a P-type silicon wafer (with the resistivity of 1 omega cm), connecting the P-type silicon wafer to a constant current instrument by taking the silicon wafer as an anode and a platinum electrode as a cathode, adding electrolyte with the volume ratio of HF to EtOH of 2: 1 into a reaction container, and adding electrolyte with the volume ratio of 100mA cm-2The electrochemical etching is carried out for 1000 s.
2) The etched silicon wafer was heated at a temperature of 1mA cm-2The current density of (3) and the volume ratio of HF to EtOH is 1: 15, and the secondary etching is carried out for 100 s. Then, the porous silicon powder is obtained by ultrasonic stripping for 300s with the power of 1000W of the ultrasonic cell crusher.
3) Ultrasonically dispersing 0.5 g of porous silicon powder into 50 g of water, adding 0.02 g of sugar alcohol, uniformly mixing and stirring, polymerizing for 1 hour at 100 ℃, separating, putting into a tubular furnace, and calcining for 3 hours at 600 ℃ under the argon atmosphere to obtain the carbon-coated porous silicon negative electrode material 2.
Example 3
1) Cleaning a P-type silicon wafer (with the resistivity of 0.05 omega cm), connecting the P-type silicon wafer to a constant current instrument by taking the silicon wafer as an anode and a platinum electrode as a cathode, adding electrolyte with the volume ratio of HF to EtOH being 1:4 into a reaction container, and adding electrolyte with the volume ratio of 500mA cm-2The electrochemical etching is performed for 100 s.
2) Etching the silicon wafer at 20 mA/cm-2The current density of (3) and the volume ratio of HF to EtOH is 1: 20, and the secondary etching is carried out for 10 s. Then, ultrasonic stripping is carried out for 1000s by using the power of 800W of the ultrasonic cell crusher to prepare the porous silicon powder.
3) Ultrasonically dispersing 1 g of porous silicon powder into 100 g of water, adding 0.05 g of sugar alcohol, mixing and stirring uniformly, polymerizing for 10 hours at 50 ℃, centrifugally separating, putting into a tubular furnace, and calcining for 1 hour at 1000 ℃ under argon atmosphere to obtain the carbon-coated porous silicon negative electrode material 3.
Example 4
1) Cleaning a P-type silicon wafer (with the resistivity of 0.1 omega cm), connecting the P-type silicon wafer to a constant current instrument by taking the silicon wafer as an anode and a platinum electrode as a cathode, adding an electrolyte with the volume ratio of HF to EtOH of 1:1 into a reaction container, and adding 200 mA/cm-2The electrochemical etching is performed for 600 s.
2) The etched silicon wafer was etched at a rate of 15mA cm-2The current density of (3) and the volume ratio of HF to EtOH is 1:30, and the secondary etching is carried out for 200 s. Then, ultrasonic wave 500s stripping is carried out by using 1000W power of an ultrasonic cell crusher to prepare the porous silicon powder.
3) Ultrasonically dispersing 2 g of porous silicon powder into 200 g of water, adding 0.06 g of sugar alcohol, mixing and stirring uniformly, polymerizing for 4 hours at 80 ℃, centrifugally separating, putting into a tubular furnace, and calcining for 2 hours at 700 ℃ under the argon atmosphere to obtain the carbon-coated porous silicon negative electrode material 4.
Example 5
1) Cleaning a P-type silicon wafer (with the resistivity of 0.5 omega cm), connecting the P-type silicon wafer serving as an anode and a platinum electrode serving as a cathode to a constant current meter, and adding electrolyte with the volume ratio of HF to EtOH being 1:3 into a reaction container to obtain the P-type silicon wafer400mA·cm-2The electrochemical etching was performed for 400 s.
2) The etched silicon wafer was heated at 5mA · cm-2The current density of (3) and the volume ratio of HF to EtOH is 1:10, and the secondary etching is carried out for 150 s. Then, ultrasonic 1500s stripping is carried out by using 600W power of an ultrasonic cell crusher to prepare the porous silicon powder.
3) Ultrasonically dispersing 1 g of porous silicon powder into 100 g of water, adding 0.02 g of sugar alcohol, mixing and stirring uniformly, polymerizing for 5 hours at 60 ℃, centrifugally separating, putting into a tubular furnace, and calcining for 2 hours at 900 ℃ under an argon atmosphere to obtain the carbon-coated porous silicon negative electrode material 5.
Test example
The carbon-coated porous silicon negative electrode materials 1 to 5 prepared in the above examples 1 to 5 were assembled into a 2032 type button cell, and the performance test results are shown in table 1:
TABLE 1
The capacity retention rate of a 2032 type button cell assembled in example 1 after being cycled 500 times is shown in table 1, which indicates that the retention rate of the cell capacity is still higher after the button cell is used for many times, and through calculation, the cycle life of the button cell assembled by the carbon-coated porous silicon negative electrode material prepared in the application is 8 years on average, and is obviously prolonged compared with the cycle life of a conventional button cell which is 3-5 years.
The porous silicon-based composite material prepared by the invention has the characteristics of good conductivity, high specific capacity, long cycle life and the like.
Claims (10)
1. A preparation method of a carbon-coated porous silicon negative electrode material is characterized by comprising the following steps:
(1) etching porous silicon pore channels: performing electrochemical etching under high current density by taking a platinum sheet as a cathode, a silicon wafer as an anode and a high-concentration hydrofluoric acid ethanol solution as electrolyte;
(2) stripping porous silicon: transferring the porous silicon wafer etched in the step (1) into a low-concentration hydrofluoric acid ethanol solution, performing electrochemical etching under low current density, performing ultrasonic stripping, and washing to obtain porous silicon powder;
(3) carbon coating: mixing and stirring sugar alcohol and porous silicon powder, polymerizing and coating, and carbonizing at high temperature to obtain the carbon-coated porous silicon negative electrode material.
2. The method for preparing the carbon-coated porous silicon negative electrode material according to claim 1, wherein the volume ratio of hydrofluoric acid to ethanol in the high-concentration hydrofluoric acid ethanol solution in the step (1) is 4: 1-1: 4, and the high current density is 100-500 mA.cm-2。
3. The preparation method of the carbon-coated porous silicon anode material according to claim 1 or 2, wherein the etching time in the step (1) is 100 s-1000 s.
4. The method for preparing the carbon-coated porous silicon negative electrode material according to claim 1, wherein the volume ratio of hydrofluoric acid to ethanol in the low-concentration hydrofluoric acid ethanol solution in the step (2) is 1:10 to 1:30, and the low current density is 1 to 20 mA-cm-2。
5. The preparation method of the carbon-coated porous silicon anode material as claimed in claim 1 or 4, wherein the etching time in the step (2) is 10-200 s.
6. The preparation method of the carbon-coated porous silicon negative electrode material according to claim 1, wherein the ultrasonic power in the step (2) is 500-1000W, and the ultrasonic time is 300-3000S.
7. The method for preparing the carbon-coated porous silicon anode material according to claim 1, wherein the mass ratio of the sugar alcohol to the silicon powder in the step (3) is 0.01-0.05: 1.
8. The method for preparing the carbon-coated porous silicon anode material according to claim 1, wherein the polymerization temperature in the step (3) is 50-100 ℃ and the polymerization time is 1-10 hours.
9. The method for preparing the carbon-coated porous silicon negative electrode material according to claim 1, wherein the carbonization temperature in the step (3) is 500-1000 ℃ and the carbonization time is 1-5 hours.
10. Use of a porous silicon negative electrode material obtained by the method of preparing a carbon-coated porous silicon negative electrode material according to any one of claims 1 to 9 in a lithium ion battery.
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| CN112614973A (en) * | 2020-12-07 | 2021-04-06 | 惠州市豪鹏科技有限公司 | Silicon-carbon negative electrode material and preparation method thereof, negative plate and lithium ion battery |
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