CN116799178A - Silicon-carbon negative electrode material, preparation method thereof and lithium ion battery - Google Patents
Silicon-carbon negative electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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Abstract
The invention discloses a preparation method of a silicon-carbon anode material, which comprises the following steps: (1) Introducing mixed gas comprising silicon source gas A and nitrogen source gas into a reactor with a built-in porous carbon substrate in inert atmosphere, and obtaining the porous carbon substrate coated with a silicon nitride layer after vapor deposition; in the mixed gas, the flow ratio of the silicon source gas A to the nitrogen source gas is 1-4: 1, a step of; (2) Introducing a silicon source gas B into the reactor, and obtaining a silicon-carbon composite material after secondary vapor deposition; (3) And (3) introducing carbon source gas into the reactor, and coating and post-treating the carbon source gas by high-temperature carbon to obtain the silicon-carbon anode material. The lithium ion battery assembled by the silicon-carbon anode material prepared by the method disclosed by the invention has excellent cycling stability, high reversible specific capacity and high first coulombic efficiency.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a silicon-carbon negative electrode material, a preparation method thereof and a lithium ion battery.
Background
Silicon is the anode material with the maximum theoretical capacity at present, the specific capacity is up to 4200mAh/g, which is far higher than the theoretical capacity of graphite (the theoretical capacity of graphite anode material is only 372 mAh/g), and silicon has the advantages of low lithium intercalation potential and low cost, and is expected to replace graphite to become the anode material of next generation lithium ion battery. However, silicon has the following problems as a negative electrode material: (1) Silicon is accompanied by serious volume expansion and shrinkage in the process of lithium intercalation and deintercalation, so that the material is easy to pulverize and fall off from a current collector to lose electrochemical performance; (2) Forming an unstable solid electrolyte layer (SEI film) on the surface of silicon to cause irreversible decay of capacity; (3) The conductivity of silicon is poor, the capacity is not released effectively under high multiplying power, and the existence of the problems severely limits the application of the silicon-based anode material in lithium ion batteries.
The main methods for reducing the expansion of the silicon material at present are as follows: (1) Coating a carbon material on the surface of the nano silicon material, so that the conductivity of the nano silicon material is improved, and the expansion rate of the nano silicon material is reduced; (2) Preparing a porous template, such as a porous carbon material, embedding a silicon material into the holes, and reducing the expansion rate of the porous template; or preparing porous silicon material to reduce its expansion. The silicon-carbon negative electrode material obtained by compounding porous carbon and silicon and coating the whole of the silicon-carbon negative electrode material with a carbon layer are one of the best schemes for solving the problem of silicon volume expansion. The pores in the porous carbon reserve enough space for the volume expansion of the silicon, so that the original shape of the silicon can be maintained in the volume expansion process; meanwhile, the carbon layer is coated outside, so that huge stress generated in the silicon volume expansion process can be effectively buffered, the silicon-based material is prevented from directly contacting and reacting with electrolyte, and the overall stability of the material is improved.
The scheme has the advantages that the performance of the whole cathode material is improved, but the defects still exist. The carbon coating mainly comprises three technological methods, namely a solid-phase method, a liquid-phase method and a gas-phase method, and the silicon-based material is coated by adopting a chemical gas-phase deposition technology in practical operation in consideration of the difficulty of operation and the uniformity of a final carbon coating layer. The high temperature in the carbon inclusion process can lead to the combination of nano silicon and a porous carbon material serving as a substrate, so that a byproduct SiC is generated, irreversible capacity is generated, and the electrochemical activity of the silicon-carbon composite material is seriously influenced. In order to avoid the above situation, many schemes adopt a low-temperature carbon-coated form, and the generation of silicon carbide is avoided. However, the reaction temperature is low, the carbonization degree of the carbon coating is low, the conductivity is poor, and the electrochemical performance is still poor, so that the actual production requirement cannot be met.
In the nano silicon-carbon composite material, nano silicon is physically isolated from a porous carbon matrix through a coating containing transition metal elements, so that silicon carbide generated by reaction of nano silicon particles with the porous carbon matrix in the deposition process is avoided, the generation of irreversible capacity is reduced, and the first cycle efficiency of the battery is improved. The plating layer is a material containing transition metal and prepared by a wet chemical method, and has physical isolation function, but the thickness of the plating layer prepared by wet chemical method is larger, about tens to hundreds of nanometers and even reaches a micron level, the plating layer can also cause the porous structure on the surface of a porous carbon matrix to be closed while having the isolation function, and the porous structure of the porous carbon can not be utilized to play a role in inhibiting the volume expansion of nano silicon, so the cycle stability of the nano silicon-carbon composite material can not be effectively improved, and no cycle stability data (the data is a common characterization parameter for testing the performance of a battery) can be provided from the technical scheme; in addition, the liquid phase coating process is complicated, relates to the use of an organic solvent, can generate three wastes, increases the post-treatment pressure and is not beneficial to large-scale production and application; more importantly, the transition metal-containing plating layers specifically mentioned in the technical scheme comprise various oxide plating layers such as zinc oxide and the like and metal silver plating layers, and the plating layers of the components have no electrochemical activity, and the introduction of the plating layers still can lead to the reduction of the charge-discharge specific capacity of the final assembled battery.
Disclosure of Invention
Aiming at the defects of the prior art, the invention discloses a preparation method of a silicon-carbon negative electrode material, and a lithium ion battery assembled by the prepared silicon-carbon negative electrode material has excellent cycling stability, high reversible specific capacity and high first coulombic efficiency.
The specific technical scheme is as follows:
the preparation method of the silicon-carbon anode material comprises the following steps:
(1) Introducing mixed gas comprising silicon source gas A and nitrogen source gas into a reactor with a built-in porous carbon substrate in inert atmosphere, and obtaining the porous carbon substrate coated with a silicon nitride layer after vapor deposition;
in the mixed gas, the flow ratio of the silicon source gas A to the nitrogen source gas is 1-4: 1, a step of;
(2) Introducing a silicon source gas B into the reactor, and obtaining a silicon-carbon composite material after secondary vapor deposition;
(3) And (3) introducing carbon source gas into the reactor, and coating and post-treating the carbon source gas by high-temperature carbon to obtain the silicon-carbon anode material.
The invention discloses a preparation method of a silicon-carbon anode material, which comprises the steps of firstly forming SiN on the surface of a porous carbon substrate x Then silicon deposition is carried out; finally, the silicon-carbon anode material is obtained through high-temperature carbon coating treatment.
Experiments show that the SiN prepared by the preparation method x The thin layer has moderate thickness, so that the silicon carbide byproduct generated in the process of directly contacting the porous carbon with the silicon at the subsequent high temperature carbon coating process can be effectively avoided, the pore channel structure of the porous carbon substrate can not be blocked, and the subsequently deposited nano silicon particles can not enter the pore channel, so that the effect of buffering the expansion of the silicon by the porous structure can not be exerted. It has been found experimentally that the SiN formed can be controlled by controlling the temperature and time of the vapor deposition in step (1) x Regulating and controlling the thickness of the thin layer; when a thin layer is preparedWhen the thickness is 1-3 nm, the two requirements can be satisfied at the same time.
Preferably:
in the step (1), the vapor deposition temperature is 500-700 ℃ and the time is 2-6 h.
Further preferably, the vapor deposition is carried out at a temperature of 500 to 600 ℃ for a time of 4 to 6 hours.
More preferably, the vapor deposition is carried out at a temperature of 500℃for a period of 4 hours.
It has also been found through experiments that the prepared SiN can be obtained by controlling the flow ratio of the silicon source gas A and the nitrogen source gas in the mixed gas introduced in the step (1) x The value of x in the thin layer is regulated, and further experiments show that when the flow ratio of the silicon source gas A to the nitrogen source gas is controlled to be 1-4: 1 SiN to be prepared x The numerical value of x in the thin layer is controlled to be 0.4-1.2, and the SiN is prepared at the moment x The thin layer can isolate, and meanwhile, silicon in the components can be continuously combined with lithium ions, so that certain capacity and first effect are provided. If the value of x exceeds 1.35, the composition of the thin layer prepared is Si 3 N 4 The thin layer can only play a role in isolation, and does not contribute to capacity and first effect.
Preferably:
in the mixed gas, the flow ratio of the silicon source gas A to the nitrogen source gas is 1.5-4: 1, a step of;
further preferably 1.5:1.
it has also been unexpectedly found in experiments that by forming SiN on the surface of porous carbon substrates x The thin layer further enhances the mechanical strength of the porous carbon substrate, plays a certain role in relieving the volume expansion and contraction of nano silicon in the lithium intercalation and deintercalation process, limits the growth of silicon crystal grains (the controllable silicon crystal domain is lower than 5 nm), and improves the cycle stability of the finally prepared cathode material.
In step (1):
the nitrogen source gas is selected from ammonia gas;
the silicon source gas A is selected from one or more of monosilane, disilane, dichlorosilane and trichlorosilane.
In the step (2):
the silicon source gas B is selected from one or more of monosilane, disilane, dichlorosilane and trichlorosilane;
the temperature of the secondary vapor deposition is 500-700 ℃ and the time is 2-12 h;
the deposited silicon content can be regulated and controlled by controlling the temperature and time of the secondary vapor deposition.
Further preferably, the temperature of the secondary vapor deposition is 500-700 ℃ and the time is 8-12 h;
the silicon content obtained by deposition under the above preferred deposition conditions can ensure that the final assembled battery has high specific capacity, high initial efficiency and excellent cycling stability.
In the step (3):
the carbon source gas is selected from alkane gas with a cracking temperature of 400-800 ℃, and is specifically selected from common types such as acetylene, ethylene and the like;
the temperature of the high-temperature carbon coating is 800-1200 ℃ and the time is 1-3;
the post-treatment comprises scattering, sieving and demagnetizing.
The invention also discloses the silicon-carbon anode material prepared by the method, and the lithium ion battery assembled by the anode material has excellent cycling stability, high reversible specific capacity and high first coulomb efficiency.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a silicon-carbon anode material with a silicon nitride isolation layer, which comprises the steps of firstly forming SiN with proper composition on the surface of a porous carbon substrate x Then silicon deposition is carried out; finally, the silicon-carbon anode material is obtained through high-temperature carbon coating treatment; siN of the appropriate composition x The thin layer of (2) has the following multiple functions: 1. plays an isolating role, and prevents the deposited silicon and the carbon substrate from reacting in the subsequent high-temperature carbonization process; meanwhile, the porous silicon pore channel structure is not blocked, and the expansion of the porous silicon is buffered fully; 2. the silicon in the thin layer can be continuously combined with lithium ions to provide certain capacity and first effect; 3. the thin layerThe method can further inhibit the volume expansion of silicon, limit the growth of silicon grains, and has certain help to improve the circulation stability.
The lithium ion battery assembled by the silicon-carbon anode material prepared by the method has excellent cycling stability, high reversible specific capacity and high first coulombic efficiency.
Drawings
FIG. 1 is a TEM image of a porous carbon substrate coated with a silicon nitride layer prepared in step (2) of example 1;
FIG. 2 is an XRD pattern of the silicon carbon negative electrode material prepared in example 1;
fig. 3 to 4 are TEM images of the porous carbon substrate coated with the silicon nitride layer prepared in step (2) of comparative example 2 at different magnifications.
Detailed Description
The present invention will be described in further detail with reference to examples and comparative examples, but embodiments of the present invention are not limited thereto.
Example 1
(1) 100g of a porous carbon substrate (d50=6.5 μm, span value<1.5, specific surface area of 800m 2 Per g, average pore diameter of 5nm and pore volume of 1.0cm 3 /g) placing in a deposition furnace at a temperature of 500 ℃;
(2) The composition was monosilane at a total flow rate of 10L/min: ammonia = 3:2, introducing the mixed gas into a deposition furnace, and continuously introducing the gas for 4 hours to obtain a porous carbon substrate coated with a silicon nitride layer;
FIG. 1 is a TEM image of a porous carbon substrate coated with a silicon nitride layer prepared in step (2), which can be found by observing the TEM image, the thickness of the coating layer is uniform and is about 2nm;
(3) After the silicon nitrogen deposition is finished, introducing monosilane into a deposition furnace at a flow rate of 20L/min, and continuously introducing air for 10 hours;
(4) After the deposition is finished, heating to 850 ℃ at a speed of 5 ℃/min, introducing acetylene at a flow speed of 1L/min for high-temperature carbon coating, continuously introducing air for 2 hours, cooling to room temperature, and scattering, screening, demagnetizing and the like the material to obtain a silicon-carbon anode material; the mass of the carbon coating layer is controlled to be 5 weight percent of the mass of the finally prepared silicon-carbon anode material.
Fig. 2 is an XRD pattern of the silicon carbon negative electrode material prepared in this example, and it was observed that nitrogen element was successfully doped into the product.
Example 2
The preparation process was essentially the same as in example 1, except that:
the duration of ventilation in step (2) was replaced with 6h.
The thickness of the silicon nitride layer of the porous carbon substrate coated with the silicon nitride layer prepared in the step (2) was about 3nm through TEM test.
Example 3
The preparation process was essentially the same as in example 1, except that:
the duration of ventilation in step (2) was replaced with 2h.
The thickness of the silicon nitride layer of the porous carbon substrate coated with the silicon nitride layer prepared in the step (2) was about 1nm through TEM test.
Comparative example 1
The preparation process was essentially the same as in example 1, except that:
the duration of aeration in step (2) was replaced with 0.5h.
The thickness of the silicon nitride layer of the porous carbon substrate coated with the silicon nitride layer prepared in the step (2) was 0.3nm through TEM test.
Comparative example 2
The preparation process was essentially the same as in example 1, except that:
the duration of ventilation in step (2) was replaced with 8h.
Fig. 3 and 4 are TEM images of the porous carbon substrate coated with the silicon nitride layer prepared in the step (2) of the comparative example under different magnifications, and it can be found that the thickness of the silicon nitride layer is about 5 to 6nm by observing the images, and the blocking of the pore structure in the porous carbon substrate is obviously observed.
Example 4
The preparation process was essentially the same as in example 1, except that:
in the step (2), the volume ratio composition of the introduced mixed gas is replaced by monosilane: ammonia = 4:1.
example 5
The preparation process was essentially the same as in example 1, except that:
in the step (2), the volume ratio composition of the introduced mixed gas is replaced by monosilane: ammonia = 2.5:2.5.
comparative example 3
The preparation process was essentially the same as in example 1, except that:
in the step (2), the volume ratio composition of the introduced mixed gas is replaced by monosilane: ammonia = 4.5:0.5.
comparative example 4
The preparation process was essentially the same as in example 1, except that:
in the step (2), the volume ratio composition of the introduced mixed gas is replaced by monosilane: ammonia = 1:4.
comparative example 5
The preparation process was essentially the same as in example 1, except that:
step (2) is removed, and the porous carbon substrate is directly subjected to silicon deposition.
Comparative example 6
The preparation process was essentially the same as in example 1, except that:
in step (4), the carbon-coated temperature was replaced with 600 ℃.
Comparative example 7
The preparation process is substantially the same as comparative example 5, except that:
the carbon coated temperature was replaced with 600 ℃.
Example 6
The preparation process is essentially the same as in example 1, except that:
the duration of ventilation in step (3) was replaced with 8h.
Example 7
The preparation process is essentially the same as in example 1, except that:
the duration of ventilation in step (3) was replaced with 12h.
Application example
Batteries were assembled with the products prepared in each example and each comparative example as negative electrode materials, respectively.
(1) Preparing a positive electrode plate: the positive electrode active material nickel cobalt lithium manganate (NCM 811), a conductive agent SuperP, a carbon nano tube and a binder polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 97:1:0.5:1.5 and N-methyl pyrrolidone (NMP) are uniformly mixed to prepare positive electrode slurry (the solid content is 70wt percent), the positive electrode slurry is coated on the front and back surfaces of a current collector aluminum foil, the positive electrode slurry is dried at 100 ℃ and then subjected to cold pressing at room temperature under 4MPa, and then subjected to trimming, cutting, slitting and welding of electrode lugs to prepare the positive electrode plate.
(2) Preparing a negative electrode plate: under the protection of nitrogen, the solvent N-methyl pyrrolidone (NMP) and the binder PVDF are stirred and mixed uniformly, then the conductive agent SuperP is added and stirred uniformly, and then the negative electrode active material is added and stirred uniformly sufficiently, so as to prepare the negative electrode slurry (the solid content is 50 wt%).
The negative electrode active material was obtained by sufficiently mixing the silicon carbon negative electrode materials prepared in the above examples and comparative examples, respectively, with graphite so that the gram capacity of the prepared negative electrode material was 450 mAh/g.
The negative electrode slurry is coated on the front and back surfaces of a current collector copper foil, dried at 100 ℃, cold-pressed at room temperature under 4MPa, cut, sliced and striped, and electrode lugs are welded to prepare the negative electrode plate.
(3) Assembly of lithium ion batteries
Sequentially stacking the prepared positive plate, the membrane and the negative plate by taking the PE porous polymeric film as the membrane, enabling the membrane to be positioned between the positive plate and the negative plate, and winding to obtain a bare cell; and (3) placing the bare cell in an aluminum plastic shell package, and drying at 100 ℃ under the relative vacuum pressure of-0.95 multiplied by 105Pa until the moisture is below 100 ppm. Injecting an electrolyte into the dried bare cell, wherein the electrolyte consists of Ethylene Carbonate (EC), ethylmethyl carbonate (EMC) and diethyl carbonate (DEC) (EC: EMC: DEC volume ratio=1:1:1) and LiPF 6 (1.0M), packaging, standing, forming (0.02C constant current charging for 2h and 0.1C constant current charging for 2 h), shaping, and testing capacity (capacity division) to obtain soft-package liquid lithium ion battery.
When the batteries are assembled, five batteries are prepared in each group of tests, five groups of data are tested together, and the average value of the five groups of data is taken as the final performance.
The battery cycle performance was tested on a new power plant, specifically:
at 25 ℃,0.1C to 0.005V, then 0.08C to 0.001V, 0.05C to 0.001V, 0.02C to 0.001V, and standing for 10min; charging to 1.5V at 0.1C, standing for 10min, recording the charge-discharge capacity after the first cycle, and calculating the first coulomb efficiency; and (3) circulating for 100 times in the above way, recording the charge and discharge capacity after 100 times, calculating to obtain the capacity retention rate after 100 times of circulation, wherein the capacity retention rate after 500 times of circulation is tested in the same way as the calculation process, and the test results are shown in the table 1 below.
TABLE 1
As can be seen from the data of comparative examples 1 and 2, the electrochemical performance of the lithium ion batteries assembled in comparative examples 1 and 2, respectively, is significantly reduced, and the reason for this analysis may be that when the deposited silicon nitride layer is too thin or not deposited completely (comparative example 1), the effect of the deposited silicon nitride layer as an insulating layer cannot be fully exerted; however, when the deposited silicon nitride layer is too thick (comparative example 2), although sufficient isolation can be achieved, the too thick silicon nitride layer also blocks the porous carbon pore structure, resulting in a failure of some of the deposited silicon to enter the porous carbon pore structure.
As can be seen from the data of comparative examples 1 and 3 and 5, the coating layer formed when the nitrogen doping content is extremely low (comparative example 3) is close to the silicon layer alone, and similar to the result that no coating layer is deposited in comparative example 5, the reversible specific capacity and the first effect data are remarkably reduced due to the formation of SiC at high temperature; meanwhile, when the coating layer is a silicon nitride layer, the silicon crystal domain can be further limited, and the assembled battery has more excellent cycle stability.
Comparative example 1 and comparative example 4 it can be found that the battery assembled in comparative example 4The reversible specific capacity and the initial efficiency were lower than those of example 1, probably because the composition of the silicon nitride thin layer formed after the nitrogen doping amount was increased was Si 3 N 4 The thin layer can only play a role in isolation, and does not contribute to capacity and first effect.
Comparative example 1 and comparative examples 6 and 7 it was found that the conductivity of the assembled batteries of comparative examples 6 and 7 was significantly inferior to that of example 1.
The foregoing discloses preferred embodiments, but the scope of the present invention is not limited thereto, and those skilled in the art will readily appreciate from the foregoing embodiments that various extensions and modifications can be made without departing from the spirit of the present invention.
Claims (10)
1. The preparation method of the silicon-carbon anode material is characterized by comprising the following steps of:
(1) Introducing mixed gas comprising silicon source gas A and nitrogen source gas into a reactor with a built-in porous carbon substrate in inert atmosphere, and obtaining the porous carbon substrate coated with a silicon nitride layer after vapor deposition;
in the mixed gas, the flow ratio of the silicon source gas A to the nitrogen source gas is 1-4: 1, a step of;
(2) Introducing a silicon source gas B into the reactor, and obtaining a silicon-carbon composite material after secondary vapor deposition;
(3) And (3) introducing carbon source gas into the reactor, and coating and post-treating the carbon source gas by high-temperature carbon to obtain the silicon-carbon anode material.
2. The method for producing a silicon-carbon negative electrode material according to claim 1, wherein in step (1):
the nitrogen source gas is selected from ammonia gas;
the silicon source gas A is selected from one or more of monosilane, disilane, dichlorosilane and trichlorosilane;
the temperature of the vapor deposition is 500-700 ℃ and the time is 2-6 h.
3. The method for producing a silicon-carbon negative electrode material according to claim 1, wherein in step (2):
the silicon source gas B is selected from one or more of monosilane, disilane, dichlorosilane and trichlorosilane;
the temperature of the secondary vapor deposition is 500-700 ℃ and the time is 2-12 h.
4. The method for producing a silicon-carbon negative electrode material according to claim 1, wherein in step (3):
the carbon source gas is selected from alkane gas with the cracking temperature of 400-800 ℃;
the temperature of the high-temperature carbon coating is 800-1200 ℃;
the post-treatment comprises scattering, sieving and demagnetizing.
5. The method for producing a silicon-carbon negative electrode material according to any one of claims 1 to 4, wherein in step (1):
in the mixed gas, the flow ratio of the silicon source gas A to the nitrogen source gas is 1.5-4: 1.
6. the method for preparing a silicon-carbon negative electrode material according to claim 5, wherein the vapor deposition temperature is 500-600 ℃ and the time is 4-6 h.
7. The method for preparing a silicon-carbon anode material according to claim 6, wherein the flow ratio of the silicon source gas a to the nitrogen source gas in the mixed gas is 1.5:1.
8. the method for preparing a silicon-carbon negative electrode material according to claim 1, wherein the temperature of the secondary vapor deposition is 500-700 ℃ for 8-12 hours.
9. A silicon carbon negative electrode material prepared according to the method of any one of claims 1 to 8.
10. Use of the silicon-carbon negative electrode material according to claim 9 in a lithium ion battery.
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