CN113410445A - Silicon-carbon composite negative electrode material for secondary battery and preparation method thereof - Google Patents

Silicon-carbon composite negative electrode material for secondary battery and preparation method thereof Download PDF

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CN113410445A
CN113410445A CN202110681467.7A CN202110681467A CN113410445A CN 113410445 A CN113410445 A CN 113410445A CN 202110681467 A CN202110681467 A CN 202110681467A CN 113410445 A CN113410445 A CN 113410445A
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silicon
foamed nickel
carbon composite
graphite
nickel
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周海平
张子栋
吴孟强
徐自强
冯婷婷
张庶
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University of Electronic Science and Technology of China
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University of Electronic Science and Technology of China
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Abstract

The invention provides a silicon-carbon composite negative electrode material for a secondary battery, a preparation method of the silicon-carbon composite negative electrode material and a preparation method of a lithium battery. The magnetron sputtering silicon particles are very uniform and have strong binding force, the P-doped silicon has stronger conductivity compared with pure silicon, the performance of the PECVD method is stable in preparing graphite, the graphite film is more uniform and has high adhesion, the external interference is eliminated under the vacuum condition, the silicon particles and the graphite can be effectively compounded in vacuum, the coating effect of the graphite on the silicon particles is very ideal, and the prepared battery has strong circulation stability.

Description

Silicon-carbon composite negative electrode material for secondary battery and preparation method thereof
Technical Field
The invention relates to the technical field of negative electrode materials of secondary batteries, in particular to a silicon-carbon composite negative electrode material for a secondary battery.
Background
With the increase of the demand of human society for energy use, the lithium ion battery with high energy density becomes more and more critical. In order to further improve the energy density of the lithium ion battery, silicon, germanium and tin-based cathode materials are widely concerned; in which silicon is alloyed by Li22Si5The material has very high theoretical specific capacity, and is a promising material for preparing a high-capacity lithium ion battery by replacing the traditional graphite cathode; compared with other alloy types and metal oxide cathode materials, the discharge potential of silicon is lower, so that the silicon can be applied to full batteriesThe method has more potential; in addition, the abundance and non-toxicity of silicon make it more advantageous for commercial applications.
However, silicon can generate a severe volume expansion effect during complete lithiation, so that the electrode material is easy to be powdered to cause an electrical connection problem, and meanwhile, a large amount of lithium ions are consumed in the lithium intercalation/deintercalation process to cause poor performance of a lithium ion battery. In addition, silicon itself has poor electrical conductivity, which makes it weak in lithiation capability and not easy to exhibit a desired specific mass capacity. To solve the above two main problems, a great deal of research has been invested therein, among which silicon carbon composites are emerging due to their potential for commercialization.
The conventional silicon-carbon composite material relies on high-strength heat energy in the preparation process to complete the suitable compounding of the silicon-carbon composite material and the silicon-carbon composite material, such as the processes of coating, overlapping and the like, which needs to consume a large amount of energy, and the compounding consistency is poor, so that the production process cost is high, and the prepared material is unstable in performance.
Disclosure of Invention
Aiming at the problem that the overall performance of the composite material is poor due to the problem of the silicon-carbon composite process in the silicon-carbon negative electrode material, the invention provides a silicon-carbon composite negative electrode material for a secondary battery and a preparation method thereof.
An object of the present invention is to provide a silicon-carbon composite anode material for a secondary battery.
The fluoridized and nitridized amorphous graphite and P-doped silicon double-layer composite structure is used as one of silicon-carbon composite species, when the fluorinated and nitridized amorphous graphite and P-doped silicon double-layer composite structure is applied to a secondary battery, the graphite has stronger electric conduction capability and the silicon has higher theoretical capacity, the composite effect of the graphite and the silicon in a gas phase state is very ideal, and the secondary battery prepared thereafter has strong electric conduction, excellent cycle stability, high capacity and excellent rate capability.
Another object of the present invention is to provide a method for preparing a silicon-carbon composite anode material for a secondary battery.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the silicon-carbon composite negative electrode material is of a composite structure of amorphous graphite and P-doped silicon, and is sequentially foamed nickel and the P-doped silicon coated by the amorphous graphite from bottom to top.
Preferably, the silicon-carbon composite anode material for the secondary battery is prepared by the following preparation method:
(1) taking the cleaned foamed nickel as a substrate, and using Ar and H2Etching the surface of the foamed nickel by using plasma;
(2) sputtering silicon particles from the upper part by using a magnetron sputtering method, simultaneously generating graphite in a cavity by adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) method, naturally depositing under gravity, compounding the silicon with the graphite in the process of depositing the silicon on a foamed nickel substrate, coating a layer of graphite on the silicon particles, forming a silicon-carbon compound by coating the amorphous graphite with the magnetron sputtered P-type doped silicon, and depositing on the foamed nickel substrate.
In order to achieve the above object, the present invention also provides a method for preparing a silicon-carbon composite anode material for a secondary battery, comprising the steps of:
(1) taking the cleaned foamed nickel as a substrate, and using Ar and H2Etching the surface of the foamed nickel by using plasma;
(2) sputtering silicon particles from the upper part by using a magnetron sputtering method, simultaneously generating graphite in a cavity by adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) method, naturally depositing under gravity, compounding the silicon with the graphite in the process of depositing the silicon on a foamed nickel substrate, coating a layer of graphite on the silicon particles, forming a silicon-carbon compound by coating the amorphous graphite with the magnetron sputtered P-type doped silicon, and depositing on the foamed nickel substrate.
As a preferable mode, the cleaning of the foamed nickel is to firstly use the foamed nickel with the thickness of 0.8mm, the hole diameter of 0.2mm, the porosity of 93-98 percent and the PPI of 110.
Preferably, the magnetron sputtering mode is radio frequency magnetron sputtering, the output power of a power supply is 100W, the sputtering target is 10-15cm away from the sample table, the flow of introduced argon is 30-50sccm, and the vacuum degree in the cavity is 4.0-20 Pa.
Preferably, the target material for magnetron sputtering is a P-doped silicon target.
Preferably, the step (1) of cleaning the foamed nickel comprises the steps of firstly ultrasonically cleaning the foamed nickel with acetone for 15min, secondly ultrasonically cleaning the foamed nickel with deionized water for 15min, then ultrasonically cleaning the foamed nickel with dilute hydrochloric acid for 15min, then cleaning the foamed nickel with deionized water for 3 times, 15min each time, then ultrasonically cleaning the foamed nickel with ethanol for 15min, and finally drying the foamed nickel in a vacuum oven at 45 ℃ for 2 h.
Preferably, the carbon source for preparing amorphous graphite is methane, and the flow rates of methane and argon gas are 10 to 20sccm and 40 to 60sccm, respectively.
Preferably, the duration of magnetron sputtering and PECVD is 1 h.
The invention also provides a method for preparing the lithium battery by using the silicon-carbon composite negative electrode material, which is characterized by comprising the following steps of:
the method comprises the following steps: taking foamed nickel, and pressing a circular sheet with the diameter of 6.5-8.5mm on a tablet press;
step two: placing the wafer foamed nickel on a sheet punching machine, and flattening the wafer foamed nickel by using the pressure of 18-25 MPa;
step three: taking a pressed foam nickel wafer, firstly ultrasonically cleaning the pressed foam nickel wafer for 10-20 minutes by using acetone, ultrasonically cleaning the pressed foam nickel wafer for 10-20 minutes by using deionized water, then cleaning the pressed foam nickel wafer for 10-20 minutes by using dilute hydrochloric acid with the concentration of 0.01mol/L, ultrasonically cleaning the pressed foam nickel wafer for 3 times by using the deionized water, ultrasonically cleaning the pressed foam nickel wafer for 10-20 minutes by using ethanol, and finally drying the cleaned foam nickel wafer in a vacuum oven at 45 ℃ for 2 hours;
step four: putting the dried foamed nickel on a sample table of a magnetron sputtering device, vacuumizing, and heating the sample table to about 200-400 ℃; introducing argon gas of 10-20sccm and methane of 10-20sccm into the cavity, turning on a power supply of the inductively coupled plasma device to adjust to 300W ionized gas, so that Ar and H2Etching the surface of the foamed nickel by using the plasma, operating the inductively coupled plasma device for 1h, and then closing the inductively coupled plasma device; obtaining the foam nickel PMN etched by the plasma;
step five: keeping the temperature of 200-400 ℃ unchanged, introducing 40-60sccm of argon and 10-20sccm of methane into the cavity, turning on a magnetron sputtering power supply, adjusting the power supply to 50-300W, adjusting the reflection to 0-2W, simultaneously turning on a power supply of the inductively coupled plasma device, adjusting the power supply to 300W ionized gas, coating graphite with silicon, forming an amorphous graphite-coated P-type doped silicon structure, depositing the amorphous graphite-coated P-type doped silicon structure on a foamed nickel substrate, keeping the inductively coupled plasma device and magnetron sputtering to jointly operate for 1h, and then turning off the inductively coupled plasma device and the magnetron sputtering power supply device; then, the gas flowmeter and the heating device are closed, and the vacuum pump system is kept running; after the heating table is cooled to room temperature, a vacuum pump system is closed, and a sample can be taken out, wherein the obtained sample is the amorphous graphite coated P-type doped silicon-plasma etched foam nickel PMN nickel-based silicon-carbon composite negative electrode material;
step six: putting the prepared nickel-based silicon-carbon composite negative electrode material into a glove box which has the oxygen and water contents lower than 0.1ppm and is filled with argon;
seventhly, adopting a button cell mould of CR2032 type, taking Celgard-2500 as a diaphragm and 1MLiPF6Ethylene carbonate EC dissolved in a volume ratio of 1: the button cell is assembled in a glove box by taking a metal lithium sheet as a counter electrode and taking a diethyl carbonate DEC mixed solution as an electrolyte, wherein the mixed solution comprises a 10% fluoroethylene carbonate FEC additive.
Preferably, the magnetron sputtered silicon target is P-type doped silicon, and the diameter of the target is about 75-80 mm.
Preferably, the power of the magnetron sputtering source is 100W, and the reflection is 0-2W.
Preferably, the flow of argon gas introduced during magnetron sputtering is in the range of 40-60 sccm.
Preferably, the magnetron sputtering time is 1 h.
Preferably, the carbon source for growing graphite by plasma enhanced chemical vapor deposition PECVD is methane.
Preferably, the plasma enhanced chemical vapor deposition PECVD grows graphite by simultaneously introducing at least one of hydrogen or argon in addition to the carbon source gas.
Preferably, the flow rate of the methane introduced by the plasma enhanced chemical vapor deposition PECVD is 10-20 sccm.
Preferably, the power of the power supply of the PECVD method is 300W, and the reflection is 0-10W.
Preferably, the duration of the PECVD is 1 h.
Preferably, the temperature of the sample stage is 200-400 ℃ when the full magnetron sputtering and plasma enhanced chemical vapor deposition PECVD method is adopted.
More preferably, the temperature of the sample stage is 300-400 ℃ in the magnetron sputtering and plasma enhanced chemical vapor deposition PECVD method.
The invention has the beneficial effects that: (1) the magnetron sputtering silicon particles are very uniform and have strong binding force, the P-doped silicon has stronger conductivity compared with pure silicon, (2) the performance of PECVD (plasma enhanced chemical vapor deposition) method in preparing graphite is stable, the graphite film is relatively uniform and has high adhesion, (3) the external interference is eliminated under the vacuum condition, the silicon particles and the graphite can be effectively compounded in vacuum, the coating effect of the graphite on the silicon particles is very ideal, and the prepared battery has strong circulation stability.
Drawings
FIG. 1 is an SEM image of a nickel-based silicon-carbon composite of example 1;
FIG. 2 is a schematic diagram of a plasma and magnetron sputtering integrated system used in the present invention. Wherein, 1 is a plasma generating system, 2 is a magnetron sputtering system, 3 is a quartz tube, 4 is a stainless steel vacuum cavity, 5 is P doped silicon, 6 is amorphous graphite, 7 is amorphous graphite coated with P doped silicon, 8 is a foam nickel substrate, and 9 is a heatable sample stage.
FIG. 3 is a Raman spectrum of the nickel-based silicon-carbon composite of example 1;
FIG. 4 is a graph of the charge and discharge long cycle time of the nickel-based silicon-carbon composite of example 1 at a certain current density;
Detailed Description
As shown in fig. 2, the plasma and magnetron sputtering integrated system used in the present invention: the device comprises a plasma generating system 1, a magnetron sputtering system 2, a quartz tube 3, a stainless steel vacuum cavity 4, P-doped silicon 5, amorphous graphite 6, amorphous graphite-coated P-doped silicon 7, a foamed nickel substrate 8 and a heatable sample table 9; the plasma generating system 1 mainly comprises a quartz tube 3, a Cu coil, a radio frequency power supply and a radio frequency power supply matcher, and is mainly positioned above the whole integrated system; the magnetron sputtering system 2 is distributed on the left of the integrated system; meanwhile, an air inlet is arranged above the plasma and used for methane inlet, an air inlet is arranged above the magnetron sputtering system or on the left side of the integrated system and used for argon inlet, and an air outlet is arranged below the integrated system and used for pump air exhaust; the quartz tube 3 and the stainless steel vacuum chamber 4 are effectively connected together, and both are in the same vacuum environment.
The invention provides a silicon-carbon composite negative electrode material for a secondary battery, which is a composite structure of amorphous graphite and P-doped silicon, wherein the silicon-carbon composite negative electrode material is formed by sequentially coating P-doped silicon with foamed nickel and amorphous graphite from bottom to top.
Preferably, the silicon-carbon composite anode material for the secondary battery is prepared by the following preparation method:
(1) taking the cleaned foamed nickel as a substrate, and using Ar and H2Etching the surface of the foamed nickel by using plasma;
(2) sputtering silicon particles from the upper part by using a magnetron sputtering method, simultaneously generating graphite in a cavity by adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) method, naturally depositing under gravity, compounding the silicon with the graphite in the process of depositing the silicon on a foamed nickel substrate, coating a layer of graphite on the silicon particles, forming a silicon-carbon compound by coating the amorphous graphite with the magnetron sputtered P-type doped silicon, and depositing on the foamed nickel substrate.
In order to achieve the above object, the present invention further provides a method for preparing a silicon-carbon composite anode material for a secondary battery, comprising the steps of:
(1) taking the cleaned foamed nickel as a substrate, and using Ar and H2Etching the surface of the foamed nickel by using plasma;
(2) sputtering silicon particles from the upper part by using a magnetron sputtering method, simultaneously generating graphite in a cavity by adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) method, naturally depositing under gravity, compounding the silicon with the graphite in the process of depositing the silicon on a foamed nickel substrate, coating a layer of graphite on the silicon particles, forming a silicon-carbon compound by coating the amorphous graphite with the magnetron sputtered P-type doped silicon, and depositing on the foamed nickel substrate.
As a preferable mode, the cleaning of the foamed nickel is to firstly use the foamed nickel with the thickness of 0.8mm, the hole diameter of 0.2mm, the porosity of 93-98 percent and the PPI of 110.
Preferably, the magnetron sputtering mode is radio frequency magnetron sputtering, the output power of a power supply is 100W, the sputtering target is 10-15cm away from the sample table, the flow of introduced argon is 30-50sccm, and the vacuum degree in the cavity is 4.0-20 Pa.
Preferably, the target material for magnetron sputtering is a P-doped silicon target.
Preferably, the step (1) of cleaning the foamed nickel comprises the steps of firstly ultrasonically cleaning the foamed nickel with acetone for 15min, secondly ultrasonically cleaning the foamed nickel with deionized water for 15min, then ultrasonically cleaning the foamed nickel with dilute hydrochloric acid for 15min, then cleaning the foamed nickel with deionized water for 3 times, 15min each time, then ultrasonically cleaning the foamed nickel with ethanol for 15min, and finally drying the foamed nickel in a vacuum oven at 45 ℃ for 2 h.
Preferably, the carbon source for preparing amorphous graphite is methane, and the flow rates of methane and argon gas are 10 to 20sccm and 40 to 60sccm, respectively.
Preferably, the duration of magnetron sputtering and PECVD is 1 h.
Preferably, the magnetron sputtered silicon target is P-type doped silicon, and the diameter of the target is about 75-80 mm.
Preferably, the power of the magnetron sputtering source is 100W, and the reflection is 0-2W.
Preferably, the flow of argon gas introduced during magnetron sputtering is in the range of 40-60 sccm.
Preferably, the magnetron sputtering time is 1 h.
Preferably, the carbon source for growing graphite by plasma enhanced chemical vapor deposition PECVD is methane.
Preferably, the plasma enhanced chemical vapor deposition PECVD grows graphite by simultaneously introducing at least one of hydrogen or argon in addition to the carbon source gas.
Preferably, the flow rate of the methane introduced by the plasma enhanced chemical vapor deposition PECVD is 10-20 sccm.
Preferably, the power of the power supply of the PECVD method is 300W, and the reflection is 0-10W.
Preferably, the duration of the PECVD is 1 h.
Preferably, the temperature of the sample stage is 200-400 ℃ when the full magnetron sputtering and plasma enhanced chemical vapor deposition PECVD method is adopted.
More preferably, the temperature of the sample stage is 300-400 ℃ in the magnetron sputtering and plasma enhanced chemical vapor deposition PECVD method.
Example 1
The silicon-carbon composite negative electrode material for the secondary battery in this embodiment is a double-layer composite structure with foamed nickel as a substrate, amorphous graphite and P-doped silicon. The manufacturing method comprises the following steps:
the method comprises the following steps: taking foamed nickel, and pressing a circular sheet with the diameter of 6.5-8.5mm on a tablet press;
step two: placing the wafer foamed nickel on a sheet punching machine, and flattening the wafer foamed nickel by using the pressure of 18-25 MPa;
step three: taking a pressed foam nickel wafer, firstly ultrasonically cleaning the pressed foam nickel wafer for 10-20 minutes by using acetone, ultrasonically cleaning the pressed foam nickel wafer for 10-20 minutes by using deionized water, then cleaning the pressed foam nickel wafer for 10-20 minutes by using dilute hydrochloric acid with the concentration of 0.01mol/L, ultrasonically cleaning the pressed foam nickel wafer for 3 times by using the deionized water, ultrasonically cleaning the pressed foam nickel wafer for 10-20 minutes by using ethanol, and finally drying the cleaned foam nickel wafer in a vacuum oven at 45 ℃ for 2 hours;
step four: putting the dried foamed nickel on a sample table of a magnetron sputtering device, vacuumizing, and heating the sample table to about 200-400 ℃; introducing argon gas of 10-20sccm and methane of 10-20sccm into the cavity, turning on a power supply of the inductively coupled plasma device to adjust to 300W ionized gas, so that Ar and H2Etching the surface of the foamed nickel by using the plasma, operating the inductively coupled plasma device for 1h, and then closing the inductively coupled plasma device; obtaining the foam nickel PMN etched by the plasma;
step five: keeping the temperature of 200-400 ℃ unchanged, introducing 40-60sccm of argon and 10-20sccm of methane into the cavity, turning on a magnetron sputtering power supply, adjusting the power supply to 100W, adjusting the reflection to 0-2W, simultaneously turning on a power supply of the inductively coupled plasma device, adjusting the power supply to 300W ionized gas, coating graphite with silicon, forming an amorphous graphite-coated P-type doped silicon structure, depositing the amorphous graphite-coated P-type doped silicon structure on a foamed nickel substrate, keeping the inductively coupled plasma device and magnetron sputtering to jointly operate for 1h, and then turning off the inductively coupled plasma device and the magnetron sputtering power supply; then, the gas flowmeter and the heating device are closed, and the vacuum pump system is kept running; and (3) after the heating table is cooled to room temperature, closing a vacuum pump system, and taking out a sample, wherein the obtained sample is the amorphous graphite coated P-type doped silicon-plasma etched foam nickel PMN nickel-based silicon-carbon composite cathode material, namely the 100-Si @ C-PMN nickel-based silicon-carbon composite cathode material.
The preparation method of the nickel-based silicon-carbon composite negative electrode material into the lithium battery comprises the following steps:
step six: putting the prepared nickel-based silicon-carbon composite negative electrode material into a glove box which has the oxygen and water contents lower than 0.1ppm and is filled with argon;
seventhly, adopting a button cell mould of CR2032 type, taking Celgard-2500 as a diaphragm and 1MLiPF6Ethylene carbonate EC dissolved in a volume ratio of 1: the button cell is assembled in a glove box by taking a metal lithium sheet as a counter electrode and taking a diethyl carbonate DEC mixed solution as an electrolyte, wherein the mixed solution comprises a 10% fluoroethylene carbonate FEC additive.
A raman spectrum, an SEM spectrum, and a charge-discharge long cycle chart at a certain current density of the silicon-carbon composite negative electrode material described in this example are shown in fig. 2-1.
The cell was tested by a blue tester during the first cycle (0.1A g)-1) The first coulombic efficiency is 79%, and after 500 cycles, the current density is measuredDegree of 2A g-1With a size of 413mA h g of reversible capacity-1。
Example 2
This example provides a method for preparing a silicon-carbon composite anode material for a secondary battery,
this example differs from example 1 in that: and step five, adjusting the power supply to 200W by using a magnetron sputtering power supply.
Step five: keeping the temperature of 200-400 ℃ unchanged, introducing 40-60sccm of argon and 10-20sccm of methane into the cavity, turning on a magnetron sputtering power supply, adjusting the power supply to 200W, adjusting the reflection to 0-2W, simultaneously turning on an ICP power supply of the inductively coupled plasma device, adjusting the ICP power supply to 300W ionized gas, enabling graphite to coat silicon, forming a Si @ C structure, depositing the Si @ C structure on a foamed nickel substrate, keeping the ICP and the magnetron sputtering device to jointly run for 1h, and then turning off the ICP and the magnetron sputtering power supply device. And then the gas flow meter and the heating device are closed, and the vacuum pump system is kept running. After the heating table is cooled to room temperature, a vacuum pump system is closed, and a sample can be taken out, wherein the obtained sample is the amorphous graphite coated P-type doped silicon-plasma etched foam nickel PMN nickel-based silicon-carbon composite negative electrode material; namely the nickel-based silicon-carbon composite cathode material of 200-Si @ C-PMN.
The nickel-based silicon-carbon composite anode material is prepared into a lithium battery as in example 1.
The first coulombic efficiency of the cell was 88.9% (0.1A g) as tested by a blue light tester-1) The specific discharge capacity is 2777.4mA h g-1. At a current density of 2Ag-1After circulating for 500 circles under the size of (2), the reversible capacity of the material is 1721.6mA h g-1。
Example 3
This example provides a method for preparing a silicon-carbon composite anode material for a secondary battery,
this example differs from example 1 in that: in the fifth step, a magnetron sputtering power supply regulates a power supply of 300W;
step five: keeping the temperature of 200-400 ℃ unchanged, introducing 40-60sccm of argon and 10-20sccm of methane into the cavity, turning on a magnetron sputtering power supply, adjusting the power supply to 300W, adjusting the reflection to 0-2W, simultaneously turning on an ICP power supply of an inductively coupled plasma device, adjusting the ICP power supply to 300W ionized gas, enabling graphite to cover silicon, forming a Si @ C structure, depositing the Si @ C structure on a foamed nickel substrate, keeping the ICP device and magnetron sputtering to operate for 1h together, and then turning off the ICP device, the magnetron sputtering power supply and other devices. And then the gas flow meter and the heating device are closed, and the vacuum pump system is kept running. And after the heating table is cooled to room temperature, closing the vacuum pump system, and taking out a sample, wherein the obtained sample is the 300-Si @ C-PMN nickel-based silicon-carbon composite cathode material.
The nickel-based silicon-carbon composite anode material is prepared into a lithium battery as in example 1.
The cell was tested by a blue tester at a current density of 2A g-1After circulating for 500 circles under the size of (2), the reversible capacity of the material is 687.9mA h g-1。
Example 4
The embodiment provides a preparation method of a silicon-carbon composite anode material for a secondary battery;
this example differs from example 1 in that: step five: a magnetron sputtering power supply, and a regulating power supply 50W;
step five: keeping the temperature of 200-400 ℃ unchanged, introducing 40-60sccm of argon and 10-20sccm of methane into the cavity, turning on a magnetron sputtering power supply, adjusting the power supply to 50W, adjusting the reflection to 0-2W, simultaneously turning on an ICP power supply of the inductively coupled plasma device, adjusting the ICP power supply to 300W of ionized gas, enabling graphite to coat silicon, forming a Si @ C structure, depositing the Si @ C structure on a foamed nickel substrate, keeping the ICP device and the magnetron sputtering device to jointly run for 1h, and then turning off the ICP device, the magnetron sputtering power supply device and other devices. And then the gas flow meter and the heating device are closed, and the vacuum pump system is kept running. And after the heating table is cooled to room temperature, closing the vacuum pump system, and taking out a sample, wherein the obtained sample is the 50-Si @ C-PMN nickel-based silicon-carbon composite cathode material.
The nickel-based silicon-carbon composite anode material is prepared into a lithium battery as in example 1.
Testing by blue electric testerAfter the battery is cycled for 500 circles, the current density of the battery is 2Ag-1Has a reversible capacity of 864.5mAh g-1。
Through the embodiment, the silicon-carbon composite negative electrode material effectively compounds silicon and carbon in a vacuum gas phase state in the preparation process, so that P-type doped silicon is ideally coated by amorphous graphite, and the reversible capacity and the capacity retention rate of the P-type doped silicon have excellent performances.
While the present invention has been particularly shown and described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. A silicon-carbon composite anode material for a secondary battery, characterized in that: the silicon-carbon composite negative electrode material is of a composite structure of amorphous graphite and P-doped silicon, and the silicon-carbon composite negative electrode material sequentially comprises foamed nickel and the amorphous graphite coated with the P-doped silicon from bottom to top.
2. The silicon-carbon composite anode material for a secondary battery according to claim 1, characterized by being obtained by the following production method:
(1) taking the cleaned foamed nickel as a substrate, and using Ar and H2Etching the surface of the foamed nickel by using plasma;
(2) sputtering silicon particles from the upper part by using a magnetron sputtering method, simultaneously generating graphite in a cavity by adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) method, naturally depositing under gravity, compounding the silicon with the graphite in the process of depositing the silicon on a foamed nickel substrate, coating a layer of graphite on the silicon particles, forming a silicon-carbon compound by coating the amorphous graphite with the magnetron sputtered P-type doped silicon, and depositing on the foamed nickel substrate.
3. A preparation method of a silicon-carbon composite negative electrode material for a secondary battery is characterized by comprising the following steps:
(1) taking the cleaned foamed nickel as a substrate, and using Ar and H2Etching the surface of the foamed nickel by using plasma;
(2) sputtering silicon particles from the upper part by using a magnetron sputtering method, simultaneously generating graphite in a cavity by adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) method, naturally depositing under gravity, compounding the silicon with the graphite in the process of depositing the silicon on a foamed nickel substrate, coating a layer of graphite on the silicon particles, forming a silicon-carbon compound by coating the amorphous graphite with the magnetron sputtered P-type doped silicon, and depositing on the foamed nickel substrate.
4. The method of claim 3, wherein the silicon-carbon composite negative electrode material comprises: the specific method for cleaning the foamed nickel is to firstly use the foamed nickel with the thickness of 0.8mm, the hole diameter of 0.2mm, the porosity of 93-98 percent and the PPI of 110.
5. The method of claim 3, wherein the silicon-carbon composite negative electrode material comprises: the magnetron sputtering mode is radio frequency magnetron sputtering, the output power of a power supply is 100W, the sputtering target material is 10-15cm away from the sample table, the flow of introduced argon is 30-50sccm, and the vacuum degree in the cavity is 4.0-20 Pa.
6. The method of claim 3, wherein the silicon-carbon composite negative electrode material comprises: the target material of magnetron sputtering is P-doped silicon target.
7. The method of preparing a silicon-carbon composite anode material for a secondary battery according to claim 3, wherein: the step (1) of cleaning the foamed nickel comprises the steps of firstly ultrasonically cleaning the foamed nickel with acetone for 15min, secondly ultrasonically cleaning the foamed nickel with deionized water for 15min, then ultrasonically cleaning the foamed nickel with dilute hydrochloric acid for 15min, then cleaning the foamed nickel with deionized water for 3 times, each time for 15min, then ultrasonically cleaning the foamed nickel with ethanol for 15min, and finally drying the foamed nickel in a vacuum oven at 45 ℃ for 2 h.
8. The method of claim 3, wherein the silicon-carbon composite negative electrode material comprises: the carbon source for preparing the amorphous graphite is methane, and the flow rates of the introduced methane and argon are 10-20sccm and 40-60sccm respectively.
9. The method of claim 3, wherein the silicon-carbon composite negative electrode material comprises: the duration of the magnetron sputtering and the PECVD method is 1 h.
10. A method for preparing a lithium battery by using a silicon-carbon composite negative electrode material is characterized by comprising the following steps:
the method comprises the following steps: taking foamed nickel, and pressing a circular sheet with the diameter of 6.5-8.5mm on a tablet press;
step two: placing the wafer foamed nickel on a sheet punching machine, and flattening the wafer foamed nickel by using the pressure of 18-25 MPa;
step three: taking a pressed foam nickel wafer, firstly ultrasonically cleaning the pressed foam nickel wafer for 10-20 minutes by using acetone, ultrasonically cleaning the pressed foam nickel wafer for 10-20 minutes by using deionized water, then cleaning the pressed foam nickel wafer for 10-20 minutes by using dilute hydrochloric acid with the concentration of 0.01mol/L, ultrasonically cleaning the pressed foam nickel wafer for 3 times by using the deionized water, ultrasonically cleaning the pressed foam nickel wafer for 10-20 minutes by using ethanol, and finally drying the cleaned foam nickel wafer in a vacuum oven at 45 ℃ for 2 hours;
step four: putting the dried foamed nickel on a sample table of a magnetron sputtering device, vacuumizing, and heating the sample table to about 200-400 ℃; introducing argon gas of 10-20sccm and methane of 10-20sccm into the cavity, turning on a power supply of the inductively coupled plasma device to adjust to 300W ionized gas, so that Ar and H2Etching the surface of the foamed nickel by using the plasma, operating the inductively coupled plasma device for 1h, and then closing the inductively coupled plasma device; obtaining the foamed nickel after plasma etching;
step five: keeping the temperature of 200-400 ℃ unchanged, introducing 40-60sccm of argon and 10-20sccm of methane into the cavity, turning on a magnetron sputtering power supply, adjusting the power supply to 50-300W, adjusting the reflection to 0-2W, simultaneously turning on a power supply of the inductively coupled plasma device, adjusting the power supply to 300W ionized gas, coating graphite with silicon, forming an amorphous graphite-coated P-type doped silicon structure, depositing the amorphous graphite-coated P-type doped silicon structure on a foamed nickel substrate, keeping the inductively coupled plasma device and magnetron sputtering to jointly operate for 1h, and then turning off the inductively coupled plasma device and the magnetron sputtering power supply device; then, the gas flowmeter and the heating device are closed, and the vacuum pump system is kept running; after the heating table is cooled to room temperature, a vacuum pump system is closed, and a sample can be taken out, wherein the obtained sample is the amorphous graphite coated P-type doped silicon-plasma etched foam nickel-based silicon-carbon composite negative electrode material;
step six: putting the prepared nickel-based silicon-carbon composite negative electrode material into a glove box which has the oxygen and water contents lower than 0.1ppm and is filled with argon;
seventhly, adopting a button cell mould of CR2032 type, taking Celgard-2500 as a diaphragm and 1MLiPF6Ethylene carbonate EC dissolved in a volume ratio of 1: the button cell is assembled in a glove box by taking a metal lithium sheet as a counter electrode and taking a diethyl carbonate DEC mixed solution as an electrolyte, wherein the mixed solution comprises a 10% fluoroethylene carbonate FEC additive.
CN202110681467.7A 2021-06-18 2021-06-18 Silicon-carbon composite negative electrode material for secondary battery and preparation method thereof Pending CN113410445A (en)

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Application publication date: 20210917