CN117438558B - Silicon-carbon negative electrode and preparation method thereof - Google Patents

Silicon-carbon negative electrode and preparation method thereof Download PDF

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CN117438558B
CN117438558B CN202311376224.8A CN202311376224A CN117438558B CN 117438558 B CN117438558 B CN 117438558B CN 202311376224 A CN202311376224 A CN 202311376224A CN 117438558 B CN117438558 B CN 117438558B
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silicon
porous carbon
carbon matrix
gas
negative electrode
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CN117438558A (en
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解明
张宣宣
李煜宇
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Ningbo Rouchuang Nanometer Technology Co ltd
Roudian Wuhan Technology Co ltd
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Ningbo Rouchuang Nanometer Technology Co ltd
Roudian Wuhan Technology Co ltd
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Abstract

The invention relates to the technical field of preparation methods of lithium ion battery anode materials, in particular to a silicon-carbon anode and a method for preparing the silicon-carbon anode by depositing a silicon layer in porous carbon by utilizing an ALD technology. The anode material comprises a porous carbon matrix and a nano silicon coating layer positioned in a pore canal of the porous carbon matrix, wherein the nano silicon coating layer is obtained by high-temperature thermal reduction conversion of nano silicon dioxide, the nano silicon dioxide is deposited on the surface of the porous carbon and in the pores by an ALD (atomic layer deposition) technology, and the nano silicon dioxide is deposited on the surface of the porous carbon and in the pores by the ALD technology, so that dangerous silane gas can be avoided, and the safety is improved.

Description

Silicon-carbon negative electrode and preparation method thereof
Technical Field
The invention relates to the technical field of preparation methods of lithium ion battery anode materials, in particular to a method for preparing a silicon-carbon anode by depositing a silicon layer in porous carbon by utilizing an ALD technology.
Background
With the wide application of lithium batteries in the fields of electric automobiles, wearable equipment, energy storage systems and the like, the demand for high-capacity anode materials is continuously increasing. More research is currently being pursued to replace the graphite anode materials that have been developed so far with electrode materials of high theoretical capacity. Among them, the silicon-based anode material is the most attractive alternative because of its very high theoretical capacity 4200mAh g -1 (formation of fully lithiated state Li 4.4 Si) and low discharge voltage (average delithiated voltage of Si of 0.4V). However, the cycle life of the electrode is limited due to cracking and pulverization caused by a large volume change (up to 311%) thereof during charge and discharge.
One key factor limiting the cycle life of silicon-based electrodes is to provide free expansion space for the silicon nanoparticles. Another key factor limiting the cycle life of silicon-based electrodes is the formation of unstable Solid Electrolyte Interfaces (SEI) at the surface of the electrode. If the SEI layer is deformed or broken, new SEI needs to be formed on the electrode surface in the next charging process, which results in poor coulombic efficiency of the battery, and the accumulated Solid Electrolyte Interface (SEI) also hinders the transmission of lithium ions. Much research has been focused on improving the stability of electrodes so that lithium ion batteries have relatively high capacities for tens or even hundreds of cycles.
In the conventional preparation of silicon-carbon negative electrodes (CN 106848268a and CN 110311125A), a CVD (chemical vapor deposition) method is often used to crack silane gas in the pores of graphite, thereby depositing nano silicon particles inside the pores of graphite. However, there is a certain safety hazard in use due to the dangers of silane gas. In addition, in the prior art CN102456876a and CN116730322a, silane gas is cracked on the surface of a porous carbon material by using an artificial porous carbon material, so that nano silicon particles are deposited inside the pores of the porous carbon, but the porous carbon pores are generally in nano level and the pore diameters are unevenly distributed, so that the deposited silicon nano particles are difficult to enter the inside of the pore channels or the pores are easy to be blocked. These problems limit the performance of silicon carbon anode materials. The reversible specific capacity of the silicon-carbon anode material prepared by the method is not more than 1900mAh/g, the capacity retention rate of 100 circles in a cycle is not more than 88%, and the capacity retention rate of 500 weeks in the cycle is not more than 76%.
The prior art is still far from meeting the cycle life required in practical applications. Therefore, the existing preparation technology of the nano silicon-based material applied to the preparation method of the lithium ion battery anode material is still to be improved.
Disclosure of Invention
The invention aims to solve the problems that the silicon-carbon negative electrode has low reversible specific capacity, low cyclic capacity retention rate, unsafe preparation method and uncontrollable silicon deposition in the preparation method.
The invention provides a silicon-carbon anode, which comprises a porous carbon matrix and a nano silicon coating layer positioned in pore channels of the porous carbon matrix, wherein the nano silicon coating layer is obtained by high-temperature thermal reduction conversion of nano silicon dioxide, and the nano silicon dioxide is a thin film deposited on the surface of the porous carbon and in the pores by an ALD technology.
Preferably, the average mesoporous pore diameter of the porous carbon matrix is 50nm, the pore diameter of the connecting pores is 10nm, the pore diameter of the porous carbon matrix is distributed in 10-100 nanometers, a pore structure is reserved after nano silicon dioxide is deposited on the inner wall of the porous carbon matrix, and the volume of the pore structure is at least 2/3 of the space of the mesoporous of the porous carbon matrix. .
Preferably, the pore size distribution of the porous carbon matrix is 10-100 nm, the average mesoporous pore size is 50nm, the pore size of the connecting pores is 10nm, and the specific surface area is 60m 2/g.
Preferably, the average mesoporous aperture of the silicon-carbon anode is 40-46 nm, and the mass of the nano silicon is 10-25wt% of the silicon-carbon anode.
Preferably, the method comprises the following steps:
S1, placing a porous carbon matrix into an ALD reaction chamber, introducing strong oxidizing gas into the reaction chamber, and forming an active layer containing active functional groups containing oxygen on the surface of the porous carbon matrix;
S2, repeatedly introducing a gas-phase silicon-containing precursor and a second precursor into the reaction chamber for multiple times, and coating a silicon dioxide layer on the surface of the porous carbon matrix and in the holes;
S3, placing the porous carbon matrix deposited with the silicon dioxide in a high-temperature furnace, and performing heat treatment under inert gas or nitrogen or reducing gas;
the gas phase silicon-containing precursor is a silicon halide and a silicon organic complex.
Preferably, the strong oxidizing gas is a gas capable of forming an active layer containing an oxygen-containing active functional group on the surface of the porous carbon matrix, and the strong oxidizing gas and the second precursor are one or a combination of at least 2 of water, hydrogen peroxide, oxygen, ozone and atomic oxygen; the gas phase silicon-containing precursor is one of SiCl 4、Si(OMe)4 z.
The strong oxidizing gas is a gas capable of forming an active layer containing an oxygen-containing active functional group on the surface of the porous carbon matrix, the strong oxidizing gas is one or a combination of at least 2 of water, hydrogen peroxide, oxygen, ozone and atomic oxygen, the gas phase silicon-containing precursor is Si (O tPe)3 OH, the second precursor AlMe 3), the strong oxidizing gas is a gas capable of forming an active layer containing an oxygen-containing active functional group on the surface of the porous carbon matrix, and the strong oxidizing gas is one or a combination of at least 2 of water, hydrogen peroxide, oxygen, ozone and atomic oxygen.
Preferably, the silicon dioxide layer is 10nm or less.
Preferably, the temperature of the reduced nano-silicon particles of the high temperature furnace species is 1600 ℃.
Preferably, the lithium ion battery comprises the silicon-carbon negative electrode material or the silicon-carbon negative electrode material prepared by the preparation method of the silicon-carbon negative electrode material.
Compared with the prior art, the beneficial effects of the technical scheme are as follows:
1. the ALD technology is adopted to deposit silicon dioxide nano particles on the surface and in the holes of the porous carbon, so that dangerous silane gas can be avoided, and the safety is improved.
2. ALD has the characteristics of self-limiting and controllable growth, and can deposit silicon dioxide in holes with high length-diameter ratio, so that the silicon dioxide can be deposited on the wall inside the holes, and the size of the silicon dioxide is regulated according to the size of the holes, so that the holes are prevented from being blocked.
3. The nano silicon particles formed by carbothermic reduction form chemical contact with the porous carbon and can enter the pore canal of the porous carbon, so that gram capacity exertion of the silicon-carbon negative electrode material is improved.
4. Compared with the traditional method of the silicon-carbon anode material, the technical scheme has higher safety, better controllability and higher gram capacity playing effect.
Drawings
FIG. 1 is a scanning electron microscope image of the silicon nanoparticles formed after 15 rounds of silica coated reduction in example 1;
FIG. 2 is a scanning electron microscope image of the silicon nanoparticles formed after 30 rounds of silica coated reduction in example 2;
FIG. 3 is a scanning electron microscope image of the silicon nanoparticles formed after 50 rounds of silica coated reduction in example 3;
FIG. 4 is a cycle curve of porous carbon at a current density of 100 mA/g;
Fig. 5 is a cycle curve of a commercial silicon carbon/silicon carbon negative electrode material.
Detailed Description
The following description provides specific applications and requirements of the application to enable any person skilled in the art to make and use the application. Various modifications to the disclosed embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the disclosure. Thus, the present disclosure is not limited to the embodiments shown, but is to be accorded the widest scope consistent with the claims.
Throughout the present specification, the symbol Me represents methyl, O t Pe represents tert-pentoxy.
The technical scheme of the invention is described in detail below with reference to the examples and the accompanying drawings.
Example 1: preparation method of silicon-carbon anode material
The embodiment relates to a method for preparing a silicon-carbon negative electrode material, which utilizes ALD technology to deposit silicon dioxide nano particles on the surface and in holes of porous carbon, and then utilizes high-temperature thermal reduction to convert silicon dioxide into nano silicon particles.
Step 1: preparation of porous carbon matrix
Firstly, preparing a porous carbon matrix, wherein the pore diameter of the porous carbon matrix is mainly distributed in 10-100 nanometers, and preferably the pore diameter of the porous carbon matrix is mainly distributed in 30-50 nanometers. The porous carbon matrix used in this example had an average mesoporous pore diameter of 50nm, a connecting pore diameter of 10nm and a specific surface area of 60m 2/g.
Step 2: ALD deposited silicon dioxide
The porous carbon matrix is placed in an ALD reaction chamber, the oxidized porous carbon matrix is pretreated, and then the silica nanoparticles are deposited by an ALD technique. ALD is self-limiting and growth controllable, so that silicon dioxide can be deposited in holes of porous carbon, when the pore diameter of a porous carbon matrix is mainly distributed in 30-100 nanometers, a deposition layer is formed in the hole wall, and at least 2/3 of the holes in the space are reserved for electrolyte transmission.
(1) Placing the porous carbon matrix powder into a porous container with a micropore size;
(2) Placing the porous container into an ALD reaction chamber, vacuumizing, replacing nitrogen for three times, heating the reaction chamber to 50-150 ℃, and maintaining the reaction chamber at the pressure of 10 torr;
(3) The powder is suspended and fully mixed in the porous cavity by adopting a nitrogen fluidization mode, wherein the fluidization pressure is 10torr, and the flow rate of nitrogen is 50sccm;
(4) The strong oxidizing gas is pulsed into the ALD reaction chamber with the N 2 at a flow rate of 50sccm, the temperature range is 50-150 ℃, the gas pressure is kept at 10torr for half an hour, and then the purging time of N 2 is 90s. The strong oxidizing gas includes any one of O 3、H2O2、NO2 and oxygen atoms. The strong oxidizing gas forms an active layer containing active functional groups containing oxygen on the surface of the porous carbon matrix.
(5) Heating the reaction chamber to 250-400 ℃, maintaining the pressure of the reaction chamber at 100torr, enabling a precursor SiCl 4 to enter the reaction chamber under the carrying of N 2 with the flow rate of 50sccm, adsorbing the precursor SiCl 4 on porous carbon matrix powder, enabling the pulse time to be 120s, then flushing with 50sccmN 2 and taking away the residual SiCl 4,N2 for 90s, enabling oxygen source steam to enter the reaction chamber under the carrying of 50sccm N 2, enabling the oxygen source steam to react with SiCl 4 which is chemically adsorbed on the porous carbon matrix powder, generating SiO 2 for 45s, enabling excessive water and byproducts to be carried out of the reaction chamber through 50sccm N 2, and enabling the flushing time to be 90s, thus completing an ALD deposition cycle;
(6) Repeating the step (5) for 15 times to obtain the SiO 2 layer with the coating layer thickness of 1.7 nm. Even though the surface and the holes of the porous carbon matrix are coated with a SiO 2 layer with the thickness of 1.7nm, the holes of the porous carbon matrix still retain a hole structure, the volume of the hole structure is at least 2/3 of the space of the mesoporous of the porous carbon matrix, and the holes are used for electrolyte transmission.
The oxygen source steam is any one of water, hydrogen peroxide, oxygen, ozone and atomic oxygen.
Step 3: high temperature thermal reduction
The porous carbon substrate deposited with silica is placed in a high temperature furnace and heat treated under an inert gas or nitrogen or a reducing gas. At high temperatures (e.g., 1600 ℃), silica is reduced to nano-silicon particles and comes into chemical contact with the porous carbon matrix. So that the nano silicon particles can enter the pore canal of the porous carbon, and the gram capacity of the silicon carbon anode material is improved.
Example 2: preparation method of silicon-carbon anode material
Step 1: preparation of porous carbon matrix
The porous carbon matrix used in this example had an average mesoporous pore diameter of 50nm, a connecting pore diameter of 10nm and a specific surface area of 60m 2/g.
Step 2: ALD deposits silicon dioxide;
(1) Placing the porous carbon matrix powder into a porous container with a micropore size;
(2) Placing the porous container into an ALD reaction chamber, vacuumizing, replacing nitrogen for three times, heating the reaction chamber to 50-150 ℃, and maintaining the reaction chamber at the pressure of 10 torr;
(3) The powder is suspended and fully mixed in the porous cavity by adopting a nitrogen fluidization mode, wherein the fluidization pressure is 10torr, and the flow rate of nitrogen is 50sccm;
(4) The strong oxidizing gas is pulsed into the ALD reaction chamber with the N 2 at a flow rate of 50sccm, the temperature range is 50-150 ℃, the gas pressure is kept at 10torr for half an hour, and then the purging time of N 2 is 90s. The strong oxidizing gas includes any one of O 3、H2O2、NO2 and oxygen atoms. The strong oxidizing gas forms an active layer containing active functional groups containing oxygen on the surface of the porous carbon matrix.
(5) The reaction chamber is heated to 250-400 ℃, the reaction chamber is maintained at the pressure of 100torr, a precursor Si (OMe) 4 is pulsed into the reaction chamber under the carrying of N 2 with the flow rate of 50sccm and is adsorbed on the porous carbon matrix powder, the pulse time is 120s, then 50sccmN 2 is used for flushing and taking away the residual Si (OMe) 4,N2 for 90s, water vapor is also pulsed into the reaction chamber under the carrying of 50sccm N 2 and reacts with Si (OMe) 4 which is chemically adsorbed on the porous carbon matrix powder to generate SiO 2 for 45s, then excessive water and byproducts are carried out of the reaction chamber by 50sccm N 2 for 90s, and thus an ALD deposition cycle is completed;
(6) And (3) repeating the step (5) for 30 times to obtain the SiO 2 layer with the coating layer thickness of 4 nm. Even though the surface and pores of the porous carbon matrix are coated with a 4nm thick SiO 2 layer, pores of at least 40nm remain in the pores of the porous carbon matrix for electrolyte transport.
Step 3: high temperature thermal reduction
The porous carbon substrate deposited with silica is placed in a high temperature furnace and heat treated under an inert gas or nitrogen or a reducing gas. At high temperatures (e.g., 1600 ℃), silica is reduced to nano-silicon particles and comes into chemical contact with the porous carbon matrix. So that the nano silicon particles can enter the pore canal of the porous carbon, and the gram capacity of the silicon carbon anode material is improved. A scanning electron microscope image of the silicon carbon anode material is shown in fig. 2.
Example 3: preparation method of silicon-carbon anode material
Step 1: preparation of porous carbon matrix
The average mesoporous pore diameter of the porous carbon matrix is 50nm, the pore diameter of the connecting pores is 10nm, and the specific surface area is 60m 2/g.
Step 2: ALD deposited silicon dioxide
(1) Placing the porous carbon matrix powder into a porous container with a micropore size;
(2) Placing the porous container into an ALD reaction chamber, vacuumizing, replacing nitrogen for three times, heating the reaction chamber to 50-150 ℃, and maintaining the reaction chamber at the pressure of 10 torr;
(3) The powder is suspended and fully mixed in the porous cavity by adopting a nitrogen fluidization mode, wherein the fluidization pressure is 10torr, and the flow rate of nitrogen is 50sccm;
(4) The strong oxidizing gas is pulsed into the ALD reaction chamber with the N 2 at a flow rate of 50sccm, the temperature range is 50-150 ℃, the gas pressure is kept at 10torr for half an hour, and then the purging time of N 2 is 90s. The strong oxidizing gas includes any one of O 3、H2O2、NO2 and oxygen atoms. The strong oxidizing gas forms an active layer containing active functional groups containing oxygen on the surface of the porous carbon matrix.
(5) Heating the reaction chamber to 250-400 ℃, maintaining the pressure of the reaction chamber at 100torr, enabling a precursor Si (OMe) 4 to enter the reaction chamber under the carrying of N 2 with the flow rate of 50sccm, adsorbing the precursor Si (OMe) 4 on the porous carbon matrix powder, enabling the pulse time to be 120s, then flushing with 50sccmN 2 and taking away the residual Si (OMe) 4,N2, enabling water vapor to enter the reaction chamber under the carrying of 50sccm N 2, enabling the water vapor to react with SiCl 4 which is chemically adsorbed on the porous carbon matrix powder, generating SiO 2 for 45s, enabling excessive water and byproducts to be carried out of the reaction chamber through 50sccm N 2, enabling the flushing time to be 90s, and completing an ALD deposition cycle;
(6) And (5) repeating the step (5) for 50 times to obtain the SiO 2 layer with the coating layer thickness of 5.6 nm. Even though the surface and pores of the porous carbon matrix are coated with a 5.6nm thick SiO 2 layer, pores of at least 38nm remain in the pores of the porous carbon matrix for electrolyte transport.
Step 3: high temperature thermal reduction
The porous carbon substrate deposited with silica is placed in a high temperature furnace and heat treated under an inert gas or nitrogen or a reducing gas. At high temperatures (e.g., 1600 ℃), silica is reduced to nano-silicon particles and comes into chemical contact with the porous carbon matrix. So that the nano silicon particles can enter the pore canal of the porous carbon, and the gram capacity of the silicon carbon anode material is improved. A scanning electron microscope image of the silicon carbon anode material is shown in fig. 3.
Example 4: preparation method of silicon-carbon anode material
Step 1: preparation of porous carbon matrix
First, a porous carbon substrate is prepared.
The porous carbon matrix used in this example had an average mesoporous pore diameter of 50nm, a connecting pore diameter of 10nm and a specific surface area of 60m 2/g.
Step 2: ALD deposited silicon dioxide
(1) Placing the porous carbon matrix powder into a porous container with a micropore size;
(2) Placing the porous container into an ALD reaction chamber, vacuumizing, replacing nitrogen for three times, heating the reaction chamber to 50-150 ℃, and maintaining the reaction chamber at the pressure of 10 torr;
(3) The powder is suspended and fully mixed in the porous cavity by adopting a nitrogen fluidization mode, wherein the fluidization pressure is 10torr, and the flow rate of nitrogen is 50sccm;
(4) The strong oxidizing gas is pulsed into the ALD reaction chamber with the N 2 at a flow rate of 50sccm, the temperature range is 50-150 ℃, the gas pressure is kept at 10torr for half an hour, and then the purging time of N 2 is 90s. The strong oxidizing gas includes any one of O 3、H2O2、NO2 and oxygen atoms. The strong oxidizing gas forms an active layer containing active functional groups containing oxygen on the surface of the porous carbon matrix.
(5) The reaction chamber is heated to 300 ℃, the reaction chamber is maintained at a pressure of 100torr, the precursor tri (tert-pentoxy) silanol (Si (O tPe)3 OH) is pulsed into the reaction chamber with 50sccm flow rate N 2, adsorbed on the porous carbon substrate powder for 120 seconds, then purged with 50sccmN 2 and carrying away the remaining Si (O tPe)3OH ,N2 purge time is 90 seconds, also AlMe 3 is pulsed into the reaction chamber with 50sccm N 2 and reacts with Si (O tPe)3 OH) chemisorbed on the porous carbon substrate powder to form SiO 2 for 45 seconds, then excess water and byproducts are purged out of the reaction chamber with 50sccm N 2 for 90 seconds, thus completing an ALD deposition cycle;
(6) Repeating the step (5) for 3 times to obtain the SiO 2 layer with the coating layer thickness of 9 nm. Even though the surface and pores of the porous carbon matrix are coated with a 9nm thick SiO 2 layer, pores of at least 40nm remain in the pores of the porous carbon matrix for electrolyte transport.
And (3) when the temperature of the reaction chamber in the steps (5) - (6) is controlled at 150 ℃, repeating the step (5) once, wherein the thickness of the coating layer is about 16 nanometers. And (3) when the temperature of the reaction chamber in the steps (5) - (6) is controlled at 200 ℃, repeating the step (5) once, wherein the thickness of the coating layer is about 12 nanometers.
Step 3: high temperature thermal reduction
The porous carbon substrate deposited with silica is placed in a high temperature furnace and heat treated under an inert gas or nitrogen or a reducing gas. At high temperatures (e.g., 1600 ℃), silica is reduced to nano-silicon particles and comes into chemical contact with the porous carbon matrix. So that the nano silicon particles can enter the pore canal of the porous carbon, and the gram capacity of the silicon carbon anode material is improved.
The thicker the silicon coated by the porous carbon matrix in the above embodiment, the higher the mass ratio of the active material in the composite material, the larger the specific capacity of the battery, but the more pore volume is occupied when more silicon is deposited in the pores of the porous carbon matrix, and the cycle capacity retention rate is reduced when the silicon-carbon composite anode material is cycled and the silicon expands and fills the space in the pores. Therefore, when the sediment of silicon in the pore space of the porous carbon matrix only occupies less than 1/3 of the volume, the large volume change of the silicon in the charge-discharge process can not cause the cracking and crushing of the porous carbon matrix, so that the cycle life of the electrode is influenced. And the mesoporous for electrolyte transmission can not be blocked due to the volume expansion of silicon.
The electrochemical performance of the assembled button cell was tested using a porous carbon matrix, the silicon carbon composite negative electrode materials prepared in examples 1 to 3, and a commercial silicon carbon composite negative electrode (Bei Terui brand silicon carbon composite negative electrode, BSO-2), respectively.
The preparation method of the button cell comprises the following steps: a negative electrode material, carbon black, and polyacrylic acid (PAA) were mixed at 8:1:1, and dispersing in deionized water to form uniform slurry. The slurry was then cast onto copper foil by doctor blade method and dried in vacuo at 60 ℃ for 12h to obtain a negative electrode tab.
2016-Type coin cells were assembled in glove boxes filled with inert gas, wherein the levels of both H 2 O and O 2 were below 0.1 ppm. 1M LiPF 6 (EC: EMC: DMC=1:1:1, vol%) and 3% FEC were used as electrolyte and PP separator.
The constant current charge/discharge test was performed at room temperature using the LAND CT2001A battery test system, with a charge/discharge voltage window of 0.01-1V and a current density of 100 mA/g, and the results are shown in FIG. 4-FIG. 5. The porous silicon content in the silicon-carbon composite anode material prepared in example 2 is 25wt%, the average mesoporous pore diameter of the porous silicon is 40nm, the specific surface area is 138.8m 2/g, the initial discharge specific capacity of the porous silicon is 3200mAh/g, and the specific capacity retention rate is 90% after 500 times of cyclic charge and discharge. The porous silicon content in the silicon-carbon composite anode material prepared in example 1 is 10wt%, the average mesoporous aperture of the porous silicon is 46nm, the specific surface area is 314.5m 2/g, the initial discharge specific capacity of the porous silicon is 2500mAh/g, and the specific capacity retention rate is 96.1% after 500 times of cyclic charge and discharge. The porous silicon content in the silicon-carbon composite anode material prepared in example 3 is 35wt%, the average mesoporous pore diameter of the porous silicon is 38nm, and the specific surface area is 27.2m 2/g.
Through the embodiment, the silicon dioxide nano particles can be deposited in the silicon-carbon anode material and converted into the nano silicon particles by high-temperature thermal reduction, so that the porous silicon with a high specific surface is formed, the pore structure of the porous carbon matrix plays a role in buffering the volume expansion period of the porous silicon in the charge-discharge process, the volume expansion of the porous silicon is reduced, and the electronic conductivity and the ionic conductivity of the material are also improved by the porous carbon matrix. The ALD atomic deposition technology can accurately control the deposition thickness of silicon dioxide in the pore structure of the porous carbon matrix, so that the deposition volume of the silicon dioxide in the pore structure is accurately controlled below 1/3 of the pore structure volume, cracking and crushing of the porous carbon matrix caused by large volume change of silicon in the charge-discharge process are avoided, meanwhile, the ALD atomic deposition technology also reserves the mesoporous structure of the silicon material after the silicon dioxide is deposited, avoids blocking the holes of the porous carbon, transmits electrolyte, and improves the performance and the cycle life of the silicon-carbon anode material. The method uses ALD technology, avoids the use of hazardous silane gases, and allows control of the deposition location and size of the silicon dioxide.

Claims (8)

1. The silicon-carbon negative electrode is characterized by comprising a porous carbon matrix and a nano silicon coating layer positioned in pore channels of the porous carbon matrix, wherein the nano silicon coating layer is obtained by high-temperature thermal reduction conversion of nano silicon dioxide, and the nano silicon dioxide is a film deposited on the surface of the porous carbon and in the pores by an ALD (atomic layer deposition) technology; the average mesoporous pore diameter of the porous carbon matrix is 50nm, the pore diameter of the connecting pores is 10nm, the pore diameter of the porous carbon matrix is distributed in 30-100 nanometers, and at least 2/3 of space is reserved after the nano silicon dioxide is deposited on the inner wall of the porous carbon matrix.
2. The silicon-carbon negative electrode according to claim 1, wherein the average mesoporous pore diameter of the silicon-carbon negative electrode is 40-46 nm, and the mass of the nano silicon is 10-25 wt% of the silicon-carbon negative electrode.
3. A method of preparing the silicon-carbon anode of claim 1 by depositing a silicon layer in porous carbon using ALD technique, comprising the steps of:
S1, placing a porous carbon matrix into an ALD reaction chamber, introducing strong oxidizing gas into the reaction chamber, and forming an active layer containing active functional groups containing oxygen on the surface of the porous carbon matrix;
S2, repeatedly introducing a gas-phase silicon-containing precursor and a second precursor into the reaction chamber for multiple times, and coating a silicon dioxide layer on the surface of the porous carbon matrix and in the holes;
S3, placing the porous carbon matrix deposited with the silicon dioxide in a high-temperature furnace, and performing heat treatment under inert gas or nitrogen or reducing gas;
the gas phase silicon-containing precursor is a silicon halide and a silicon organic complex.
4. The method of claim 3, wherein the strong oxidizing gas is a gas capable of forming an active layer containing an oxygen-containing active functional group on the surface of the porous carbon substrate, and the strong oxidizing gas and the second precursor are one or a combination of at least 2 of water, hydrogen peroxide, oxygen, ozone, atomic oxygen; the gas phase silicon-containing precursor is one of SiCl 4、Si(OMe)4.
5. The method of claim 3, wherein the strong oxidizing gas is a gas that forms an active layer containing oxygen-containing active functional groups on the surface of the porous carbon substrate, the strong oxidizing gas is one or a combination of at least 2 of water, hydrogen peroxide, oxygen, ozone, atomic oxygen, and the gas phase silicon-containing precursor is Si (O tPe)3OH,Si(OtPe)3 OH is tris (t-pentoxy) silanol, and the second precursor AlMe 3.
6. The method of any one of claims 4 or 5, wherein the silicon dioxide layer is 10nm or less.
7. The method of claim 6, wherein the temperature of the reduced nano-silicon particles in the high temperature furnace is 1600 ℃.
8. A lithium ion battery, characterized in that the lithium ion battery comprises the silicon-carbon negative electrode material according to any one of claims 1-2 or the silicon-carbon negative electrode material prepared by the preparation method of the silicon-carbon negative electrode material according to any one of claims 3-7.
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