CN117457865B - Method for preparing composite carbon negative electrode by utilizing ALD technology and composite carbon negative electrode - Google Patents

Method for preparing composite carbon negative electrode by utilizing ALD technology and composite carbon negative electrode Download PDF

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CN117457865B
CN117457865B CN202311376223.3A CN202311376223A CN117457865B CN 117457865 B CN117457865 B CN 117457865B CN 202311376223 A CN202311376223 A CN 202311376223A CN 117457865 B CN117457865 B CN 117457865B
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layer
silicon
porous carbon
metal
negative electrode
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CN117457865A (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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    • C23C16/45523—Pulsed gas flow or change of composition over time
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    • C23C16/45523—Pulsed gas flow or change of composition over time
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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 method for preparing a composite carbon anode by using an ALD technology and the composite carbon anode. The porous carbon substrate comprises a porous carbon substrate and a composite nano coating layer positioned in a porous carbon substrate pore channel, wherein the composite nano coating layer is formed by alternately forming a nano silicon layer and a metal oxide layer, the nano silicon layer and the metal oxide layer are obtained by converting a silicon dioxide layer and a metal layer through a metal thermal reduction reaction, and the silicon dioxide layer and the metal layer are thin films which are alternately deposited in the porous carbon substrate pore channel by an ALD atomic deposition method. Can realize chemical contact of silicon and carbon, effectively improve the cycle life and gram capacity exertion of the silicon-carbon anode material, and avoid the inherent danger of the traditional CVD technology.

Description

Method for preparing composite carbon negative electrode by utilizing ALD technology and composite carbon negative electrode
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 composite carbon anode by utilizing an ALD (atomic layer deposition) technology and the composite carbon anode.
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 li4.4si) 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 only 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 at present. And the problem of high temperature of the reduced silicon.
The invention provides a composite carbon anode prepared by an ALD (atomic layer deposition) technology, which comprises a porous carbon matrix and a composite nano coating layer positioned in a pore canal of the porous carbon matrix, wherein the composite nano coating layer comprises nano silicon and metal oxide, the nano silicon and the metal oxide are obtained by converting a silicon dioxide layer and a metal layer through a metallothermic reduction reaction, and the silicon dioxide layer and the metal layer are thin films alternately deposited in the pore canal of the porous carbon matrix by an ALD atomic deposition method.
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, a pore structure is reserved after the composite nanometer coating layer 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.
The average mesoporous aperture of the composite carbon anode is 33nm, the specific surface area is 27.2m 2/g, and the mass of the nano silicon is 33wt% of the composite carbon anode.
Preferably, the second aspect of the present invention provides a method for preparing the composite carbon negative electrode using ALD technology, comprising the steps of:
S1, putting a porous carbon substrate into an ALD reaction chamber, introducing strong oxidizing gas into the reaction chamber for forming an active layer containing active functional groups containing oxygen on the surface of the porous carbon substrate, and repeatedly and alternately introducing a gas-phase silicon source and the strong oxidizing gas for many times to coat a silicon dioxide layer on the surface of the porous carbon substrate and in the holes;
S2, after the S1 is completed, repeatedly and alternately introducing a gas-phase metal source and a reaction precursor into the reaction chamber for a plurality of times, so as to obtain a metal layer covered on the silicon dioxide layer;
s3, repeating the steps S1 and S2 for a plurality of times to obtain a plurality of silicon dioxide layers and metal layers which are alternately arranged;
and S4, placing the product deposited with the step S3 in a high-temperature furnace, and reducing the silicon dioxide into a nano silicon layer by utilizing a metallothermic reduction reaction.
Preferably, the gas phase silicon source is SiCl 4, the gas phase metal source is Al (CH 3), and the reaction precursor is H 2.
Preferably, the gas phase silicon source is SiCl 4, the gas phase metal source is AlCl 3, and the reaction precursor is AlH 2(tBuN)CH2CH2(NMe2).
Preferably, the gas phase silicon source is SiCl 4, the gas phase metal source is Al (CH 3), the reaction precursor is TiCl 4, and the resulting metal layer is an Al/Ti layer.
Preferably, the gas phase silicon source is SiCl 4, the gas phase metal source is diethyl zinc (DEZ), the reaction precursor is FeCl 3, and the resulting metal layer is a Zn/Fe layer.
Preferably, the gas phase silicon source is SiCl 4, the gas phase metal source is Al (CH 3), the reaction precursor is diethyl zinc (DEZ), and the resulting metal layer is an Al/Zn layer.
Preferably, the gas phase silicon source may be replaced with Si (OMe) 4.
Preferably, the lithium ion battery comprises the composite carbon negative electrode or the composite carbon negative electrode prepared by the preparation method of any one of the composite carbon negative electrodes.
Compared with the prior art, the beneficial effects of the technical scheme are as follows:
1. Silicon dioxide nano-particles and metal nano-particles with strong reducibility are deposited on the surface and inside the holes of the porous carbon by adopting an ALD technology, and then the silicon dioxide is reduced into nano-silicon particles by utilizing a metallothermic reaction, so that a mixture of a silicon-carbon anode material and a metal oxide is formed. Compared with the traditional physical mixing method, the method can realize chemical contact of silicon and carbon, and effectively improve the cycle life and gram capacity exertion of the silicon-carbon anode material.
2. ALD has the characteristics of self-limiting and controllable property, is suitable for being deposited in holes with high length-diameter ratio, can deposit silicon dioxide on the wall inside the pore canal of porous carbon, and can adjust the size of the silicon dioxide according to the pore size so as to avoid blocking the holes. This has significant advantages over conventional CVD methods, which are difficult to achieve deposition within nano-scale holes.
3. The invention avoids the use of dangerous silane gas and reduces the risk and potential safety hazard of operation. The silicon dioxide is reduced by adopting a metallothermic reaction to form nano silicon particles, so that the nano silicon particles can form chemical contact with the porous carbon and can be deposited inside pore channels of the porous carbon. Meanwhile, the metal oxide can effectively limit the volume expansion of silicon and avoid unnecessary side reactions with the organic electrolyte.
4. Compared with the traditional preparation method of the silicon-carbon anode material, the preparation method has better cycle life and gram capacity exertion, and has obvious superiority in the aspects of operation safety and silicon volume expansion control.
Drawings
FIG. 1 is a 6 nm SiO 2/2.5 nm Al metal nanolaminate formed in a carbon matrix using ALD;
FIG. 2 is a graph of cycle retention of a silicon carbon composite anode at a current density of 200 mA/g;
FIG. 3 is a graph of the cycle retention of a commercial silicon carbon composite anode at a current density of 200 mA/g.
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.
The technical scheme of the invention is described in detail below with reference to the examples and the accompanying drawings.
Throughout the present description, the symbols Me represent methyl, t Bu represent tert-butyl, t BuN represent tert-butyl nitrogen, NMe 2 represents dimethylamino.
Example 1: preparation method of silicon-carbon composite anode material
The embodiment relates to a method for preparing a silicon-carbon composite anode material, which comprises the steps of depositing alternating layers of nano silicon dioxide and nano strong-reducibility metal on the surface and in holes of porous carbon by utilizing an ALD technology, and reducing the silicon dioxide into a nano silicon layer by utilizing a metallothermic reaction to form a mixture of the silicon-carbon anode material and metal oxide.
Step 1: preparation of porous carbon matrix
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 substrate is placed in an ALD reaction chamber and then successive ALD deposition processes are performed by a silicon source and a metal source supplied in the ALD reactor, respectively. During ALD deposition, a silicon source and a metal source are alternately supplied to the porous carbon surface and inside the pores to form silica nanoparticles and highly reducing metallic aluminum or magnesium or zinc nanoparticles. ALD is self-limiting and growth controllable, so that silicon dioxide and metal can be deposited inside the pores of the porous carbon, and the size of the silicon dioxide and the metal can be adjusted according to the pore size, so that the pores are prevented from being blocked. When the pore diameter of the porous carbon matrix is mainly distributed in 30-100 nanometers, a deposition layer is formed in the pore wall, a pore structure is reserved, and the volume of the pore structure is at least 2/3 of the space of the mesoporous of the porous carbon matrix. The pore structure is used 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) And (5) repeating the step (5) for 10 times to obtain the SiO 2 layer with the coating layer thickness of 1.2 nm. Even if SiO 2 layers with the thickness of 1.2nm are coated on the surface and the holes of the porous carbon matrix, holes are reserved in the holes of the porous carbon matrix for electrolyte transmission.
(7) Precursor a: al (CH 3) is pulsed into the reaction chamber under the carrying of N 2 with the flow rate of 50sccm, adsorbed on the SiO 2 coated porous carbon matrix powder for 120 seconds, then purged with 50sccm N 2 and carrying away the rest of the Al (CH 3),N2 purge time is 90 seconds, likewise the precursor B: H 2 plasma is pulsed into the reaction chamber under the carrying of 50sccm N 2 and reacts with Al (CH 3) chemisorbed on the SiO 2 coated porous carbon matrix powder to form Al for 45 seconds, then excess H 2 and byproducts are carried out of the reaction chamber by 50sccm N 2 purge time is 90 seconds, thus completing an ALD deposition cycle;
(8) Repeating the step (7) for 3 times to obtain an Al layer with the thickness of the coating layer of 0.5 nm. Even though the surface and pores of the porous carbon matrix powder coated with SiO 2 are coated with a 0.5nm thick Al layer.
(9) And (3) repeating the steps (5) to (8) for 5 times, coating the holes of the porous carbon matrix with alternating SiO 2 layers and Al layers which are 8.5nm in total, and reserving holes of at least 33nm for electrolyte transmission.
Step 3: high temperature thermal reduction
Silica was reduced to nano-silicon particles using aluminothermic at 600 ℃. Specifically, the porous carbon material deposited by ALD is placed in a high temperature reactor, and then aluminum is thermally reacted with silicon dioxide by heating the reactor. At high temperatures (e.g., 600 ℃) the silica will be reduced to nano-silicon particles, forming a mixture of silicon carbon negative electrode material and alumina with porous carbon, such as the 6 nm SiO 2/2.5 nm Al metal nanolaminate formed in the carbon matrix of fig. 1. The nano silicon particles can enter the pore canal of the porous carbon, so that gram capacity of the silicon carbon anode material is improved. In this embodiment, on one hand, the reaction temperature is reduced by metal reduction of the silicon dioxide, and on the other hand, the remaining metal oxide layer can bind the tubular silicon material to enable the silicon to extend along the length direction of the mesopores to limit radial volume expansion. The carbon matrix is also protected without carbothermic reduction in the third aspect, so that the strength of the carrier limiting the volume expansion of the porous silicon is weakened when carbon atoms are converted into CO 2 in the carbothermic reaction, and the performance and the cycle life of the silicon-carbon anode material are improved.
Example 2
Based on the embodiment 1, the precursor A and the precursor B in the steps (7) - (8) in the embodiment 1 are replaced by AlCl 3 and AlH 2(tBuN)CH2CH2(NMe2 respectively, the temperature of a reaction chamber is set to be 100 ℃, and the step (8) is repeated for 1 time to obtain the Al layer with the coating layer thickness of 0.4 nm. And (3) repeating the steps (5) to (8) for 5 times, coating the holes of the porous carbon matrix with alternating SiO 2 layers and Al layers for 8nm, and reserving holes of at least 34nm for electrolyte transmission.
Example 3
Based on the embodiment 1, the precursor B in the steps (7) - (8) in the embodiment 1 is replaced by TiCl 4, the temperature of the reaction chamber is set to 250 ℃, and the step (8) is repeated for 2 times to obtain the Al layer with the coating layer thickness of 0.5 nm. And (3) repeating the steps (5) to (8) for 5 times, coating the holes of the porous carbon matrix with alternating SiO 2 layers and Al/Ti layers for 8.5nm, and reserving holes of at least 33nm in the holes of the porous carbon matrix for electrolyte transmission.
Example 4
Based on the embodiment 1, the number of repeated coating times in the step (6) in the embodiment 1 is changed to 20, the precursor A and the precursor B in the steps (7) to (8) in the embodiment 1 are respectively replaced by diethyl zinc (DEZ) and FeCl 3, the temperature of a reaction chamber is set to 260 ℃, and the step (8) is repeated for 1 time to obtain a Zn/Fe layer with the coating layer thickness of 0.9 nm. Repeating the steps (5) - (8) for 3 times, coating the holes of the porous carbon matrix with alternating SiO 2 layers and Zn/Fe layers for 8.5nm, and reserving holes of at least 33nm in the holes of the porous carbon matrix for electrolyte transmission.
Example 5
Based on the embodiment 1, the precursor B in the steps (7) - (8) in the embodiment 1 is replaced by diethyl zinc (DEZ)), the temperature of a reaction chamber is set to 150 ℃, and the step (8) is repeated for 3 times to obtain the Al/Zn layer with the coating layer thickness of 0.45 nm. And (3) repeating the steps (5) to (8) for 5 times, coating the holes of the porous carbon matrix with alternating SiO 2 layers and Al/Zn layers for 8.5nm, and reserving holes of at least 33nm in the holes of the porous carbon matrix for electrolyte transmission.
Example 6
In example 1, the precursor SiCl 4 in step (5) can also be replaced with Si (OMe) 4.
The electrochemical performance test was performed on the assembled button cell using the silicon-carbon composite anode materials prepared in examples 1 to 6 and a commercial silicon-carbon composite anode (Bei Terui brand silicon-carbon composite anode, BSO-2), respectively.
The preparation method of the button cell comprises the following steps:
A composite silicon carbon negative electrode material, carbon black and polyacrylic acid (PAA) were mixed in a ratio of 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.
Constant current charge/discharge testing was performed at room temperature using a LAND CT2001A battery test system with a charge/discharge voltage window of 0.01-1V and a current density of 200 mA/g.
The porous silicon content in the silicon-carbon composite anode material prepared in example 1 is 35wt%, the average mesoporous pore diameter of the porous silicon is 33nm, the specific surface area is 27.2m 2/g, the initial discharge specific capacity of the porous silicon is 3540mAh/g, and as shown in fig. 2, after 500 times of charge and discharge are cycled at 1C, the specific capacity retention rate is 99%. Whereas the cycle retention of the commercial silicon carbon composite anode at a current density of 200mA/g was 80.8% as shown in fig. 3.
Through the embodiment, silicon dioxide and metal aluminum or magnesium or zinc nano particles with strong reducibility can be deposited in the porous carbon anode material, the silicon dioxide is reduced into nano silicon particles by utilizing aluminothermic reaction, magnesian reaction or zincate reaction, a mixture of porous silicon or aluminum oxide or zinc oxide with 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 porous carbon matrix also improves the electron conductivity and ion conductivity of the material. 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. In addition, the metal layer reduces the reaction temperature by metal to reduce silicon dioxide on one hand, and the reserved metal oxide layer can restrict tubular silicon material to enable silicon to extend along the length direction of mesopores to limit radial volume expansion on the other hand, and the carbon matrix is protected without carbothermic reduction in the third aspect, so that the strength of a carrier limiting the volume expansion of porous silicon is prevented from weakening when carbon atoms are converted into CO 2 in carbothermic reaction, and the performance and the cycle life of the silicon-carbon anode material are improved. The method uses ALD technology, avoids using dangerous silane gas, and can control the deposition position and size of silicon dioxide, and avoid blocking the holes of porous carbon.

Claims (9)

1. The composite carbon negative electrode is characterized by comprising a porous carbon matrix and a composite nano coating layer positioned in a pore channel of the porous carbon matrix, wherein the composite nano coating layer comprises nano silicon and metal oxide, the nano silicon and metal oxide are obtained by converting a silicon dioxide layer and a metal layer through a metal thermal reduction reaction, the silicon dioxide layer and the metal layer are thin films which are alternately deposited in the pore channel of the porous carbon matrix by an ALD atomic deposition method, the average mesoporous pore diameter of the porous carbon matrix is 50nm, the pore diameter of a connecting pore is 10nm, the pore diameter of the porous carbon matrix is distributed in 30-100 nanometers, a pore structure is reserved after the composite nano coating layer 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 mesoporous space of the porous carbon matrix.
2. The composite carbon negative electrode according to claim 1, wherein the composite carbon negative electrode has an average mesoporous pore diameter of 33nm, a specific surface area of 27.2m 2/g, and the mass of the nano-silicon is 33wt% of the composite carbon negative electrode.
3. A method for preparing the composite carbon negative electrode according to any one of claims 1 to 2 by using an ALD technique, comprising the steps of:
S1, putting a porous carbon substrate into an ALD reaction chamber, introducing strong oxidizing gas into the reaction chamber for forming an active layer containing active functional groups containing oxygen on the surface of the porous carbon substrate, and repeatedly and alternately introducing a gas-phase silicon source and the strong oxidizing gas for many times to coat a silicon dioxide layer on the surface of the porous carbon substrate and in the holes;
S2, after the S1 is completed, repeatedly and alternately introducing a gas-phase metal source and a reaction precursor into the reaction chamber for a plurality of times, so as to obtain a metal layer covered on the silicon dioxide layer;
s3, repeating the steps S1 and S2 for a plurality of times to obtain a plurality of silicon dioxide layers and metal layers which are alternately arranged;
s4, placing the product deposited with the step S3 in a high-temperature furnace, and reducing silicon dioxide into a nano silicon layer by utilizing a metallothermic reduction reaction;
The gas phase silicon source is SiCl 4 or Si (OMe) 4.
4. The method of claim 3 wherein the gas phase silicon source is SiCl 4, the gas phase metal source is Al (CH 3), and the reaction precursor is H 2.
5. The method of claim 3 wherein the gas phase silicon source is SiCl 4, the gas phase metal source is AlCl 3, and the reaction precursor is AlH 2(tBuN)CH2CH2(NMe2).
6. The method of claim 3 wherein the gas phase silicon source is SiCl 4, the gas phase metal source is Al (CH 3), the reaction precursor is TiCl 4, and the resulting metal layer is an Al/Ti layer.
7. The method of claim 3, wherein the gas phase silicon source is SiCl 4, the gas phase metal source is diethyl zinc (DEZ), the reaction precursor is FeCl 3, and the resulting metal layer is a Zn/Fe layer.
8. The method of claim 3, wherein the gas phase silicon source is SiCl 4, the gas phase metal source is Al (CH 3), the reaction precursor is diethyl zinc (DEZ), and the resulting metal layer is an Al/Zn layer.
9. A lithium ion battery, characterized in that the lithium ion battery comprises the composite carbon negative electrode according to any one of claims 1 to 2 or the composite carbon negative electrode prepared by the preparation method of the composite carbon negative electrode according to any one of claims 3 to 8.
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