CN117457865A - 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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CN117457865A
CN117457865A CN202311376223.3A CN202311376223A CN117457865A CN 117457865 A CN117457865 A CN 117457865A CN 202311376223 A CN202311376223 A CN 202311376223A CN 117457865 A CN117457865 A CN 117457865A
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layer
silicon
porous carbon
metal
negative electrode
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CN117457865B (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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    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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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
As lithium batteries are widely used in the fields of electric automobiles, wearable devices, energy storage systems and the like, for the following purposesThe demand for high capacity anode materials is 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 full lithiation state li4.4si) and low discharge voltage (average delithiation voltage of Si is 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, and the specific surface area is 27.2m 2 And/g, wherein the mass of the nano silicon is 33wt% of the composite carbon negative electrode.
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 ) The reaction precursor is H 2 。
Preferably, the gas phase silicon source is SiCl 4 The gas phase metal source is AlCl 3 The reaction precursor is AlH 2 ( t BuN)CH 2 CH 2 (NMe 2 )。
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), and 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 was diethyl zinc (DEZ), and the resulting metal layer was an Al/Zn layer.
Preferably, the gas phase silicon source is replaceable 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 diagram of 6 nm SiO formed in a carbon matrix using ALD 2 2.5 nanoAl metal nanolaminate;
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 to enable any person skilled in the art to make and use the teachings of the present 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 specification, the symbol Me represents a methyl group, t Bu represents tert-butyl, t BuN represents tert-butyl nitrogen or NMe 2 Representing a dimethylamino group.
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) N of strong oxidizing gas at 50sccm flow rate 2 Is carried to the ALD reaction chamber at 50-150 ℃ and maintained at 10torr pressure for half an hour, then N 2 The purge time was 90s. The strong oxidizing gas includes O 3 、H 2 O 2 、NO 2 Any one of 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 temperature of the reaction chamber is raised to 250-400 ℃, the pressure of the reaction chamber is maintained at 100torr, and the precursor SiCl is obtained 4 N at a flow rate of 50sccm 2 Is carried into the reaction chamber, adsorbed onto the porous carbon matrix powder for 120 seconds, then is subjected to a pulse of 50sccmN 2 Purging and taking away residual SiCl 4 ,N 2 The purge time was 90s, and the same oxygen source steam was used at 50sccm N 2 Is carried into the reaction chamber and is chemically adsorbed with SiCl on the porous carbon matrix powder 4 React to form SiO 2 For 45s, then excess water and by-products are removed from 50sccm N 2 The purge is taken out of the reaction chamber for 90 seconds, thus completing one ALD deposition cycle;
(6) Repeating the step (5) for 10 times to obtain SiO with the coating layer thickness of 1.2nm 2 A layer. Even if the surface and pores of the porous carbon matrix are coated with SiO 1.2nm thick 2 And the layer is used for reserving holes in the holes of the porous carbon matrix for electrolyte transmission.
(7) Precursor a: al (CH) 3 ) N at a flow rate of 50sccm 2 Is carried by the lower pulse and enters the reaction chamber to be adsorbed on the SiO coating 2 The pulse time was 120s on the porous carbon matrix powder, followed by 50sccm N 2 Purging and carrying away residual Al (CH) 3 ),N 2 Purge time of 90s, precursor B as well：H 2 Is 50sccm N 2 Is carried into the reaction chamber and is chemically adsorbed on the SiO-coated layer 2 Al (CH) on a porous carbon matrix powder 3 ) Reacting to form Al for 45s, and then excessive H 2 By-product is composed of 50sccm N 2 The purge is taken out of the reaction chamber for 90 seconds, thus completing one 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 if SiO is coated 2 The surface and pores of the porous carbon matrix powder were coated with 0.5nm thick Al layer.
(9) Repeating the steps (5) - (8) for 5 times to coat the SiO alternating in the holes of the porous carbon matrix 2 The layers and Al layer together were 8.5nm, leaving at least 33nm of pores for electrolyte transport.
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 is reduced to nano-silicon particles, forming a mixture of silicon-carbon negative electrode material and alumina with porous carbon, such as 6 nm SiO formed in the carbon matrix of fig. 1 2 2.5 nanoAl metal nanolaminate. 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 third aspect also protects the carbon matrix from carbon atoms being converted to CO in the carbothermic reaction without carbothermic reduction 2 When the porous silicon anode material is used, the strength of the carrier limiting the volume expansion of the porous silicon is weakened, so that 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 respectively replaced by AlCl 3 And AlH 2 ( t BuN)CH 2 CH 2 (NMe 2 ) Setting the temperature of the reaction chamber to 100 ℃, and repeating the step (8) for 1 time to obtain the Al layer with the coating layer thickness of 0.4 nm. Repeating the steps (5) - (8) for 5 times to coat the SiO alternating in the holes of the porous carbon matrix 2 The layers and Al layer together are 8nm, leaving at least 34nm of pores for electrolyte transport.
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. Repeating the steps (5) - (8) for 5 times to coat the SiO alternating in the holes of the porous carbon matrix 2 The layers and Al/Ti layers together were 8.5nm, leaving at least 33nm of pores within the pores of the porous carbon matrix for electrolyte transport.
Example 4
Based on example 1, the number of repeated coating times in the step (6) in example 1 is changed to 20, and the precursor A and the precursor B in the steps (7) to (8) in example 1 are respectively replaced by diethyl zinc (DEZ) and FeCl 3 The temperature of the reaction chamber is set to 260 ℃, and the Zn/Fe layer with the coating layer thickness of 0.9nm is obtained by repeating the step (8) for 1 time. Repeating the steps (5) - (8) for 3 times to coat the SiO alternating in the holes of the porous carbon matrix 2 The layers and Zn/Fe layers together were 8.5nm, with pores of at least 33nm reserved in the pores of the porous carbon matrix for electrolyte transport.
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. Repeating the steps (5) - (8) for 5 times to coat the SiO alternating in the holes of the porous carbon matrix 2 The layers and Al/Zn layers together were 8.5nm, leaving at least 33nm of pores in the pores of the porous carbon matrix for electrolyte transport.
Example 6
In example 1, the precursor SiCl in step (5) 4 Can also be replaced by Si (OMe) 4 。
The electrochemical performance of the assembled button cell was tested using the silicon carbon composite negative electrode materials prepared in examples 1 to 6 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 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.
Assembling 2016 type button cell in a glove box filled with inert gas, wherein H 2 O and O 2 The content of (2) is less than 0.1 ppm. LiPF with 1M 6 (EC: EMC: dmc=1:1:1, vol%) and 3% FEC 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 silicon-carbon composite anode material prepared in example 1 had a porous silicon content of 35wt%, an average mesoporous pore diameter of 33nm, and a specific surface area of 27.2m 2 The specific capacity of porous silicon after the initial discharge is 3540mAh/g, and the specific capacity retention rate is 99% after 500 times of charge and discharge at 1C rate as shown in FIG. 2. 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 of the invention can precisely control the deposition thickness of silicon dioxide in the pore structure of the porous carbon matrix, so as to lead the silicon dioxide to be oxidizedThe deposition volume of silicon in the pore structure is precisely controlled below 1/3 of the pore structure volume, so that cracking and crushing of a porous carbon matrix caused by large volume change of silicon in the charge-discharge process are avoided, meanwhile, the mesoporous structure of a silicon material is reserved after silicon dioxide is deposited by an ALD atomic deposition technology, the holes of porous carbon are prevented from being blocked, electrolyte is transmitted, and the performance and the cycle life of a silicon-carbon anode material are improved. In addition, the metal layer reduces the reaction temperature by reducing silicon dioxide through metal on one hand, and the reserved metal oxide layer can restrict tubular silicon material to ensure that silicon extends along the length direction of the mesoporous to limit radial volume expansion on the other hand, and the third aspect does not use a carbothermic reduction mode to further protect a carbon matrix and avoid carbon atoms from being converted into CO in carbothermic reaction 2 The strength of the carrier limiting the volume expansion of the porous silicon is weakened, so that 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 and a specific surface area of 27.2m 2 /g, the mass of the nano silicon is the complex33wt% of a carbon-containing 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 vapor phase silicon source is SiCl 4 The gas phase metal source is Al (CH) 3 ) The reaction precursor is H 2 。
5. The method of claim 3 wherein the vapor phase silicon source is SiCl 4 The gas phase metal source is AlCl 3 The reaction precursor is AlH 2 ( t BuN)CH 2 CH 2 (NMe 2 )。
6. The method of claim 3 wherein the vapor 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 vapor phase silicon source is SiCl 4 The gas phase metal source is diethyl zinc (DEZ), and the reaction precursor is FeCl 3 And the resulting metal layer is a Zn/Fe layer.
8. The method of claim 3 wherein the vapor phase silicon source is SiCl 4 The gas phase metal source is Al (CH) 3 ) The reaction precursor was diethyl zinc (DEZ), and the resulting metal layer was 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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