CN114597373B - Carbon-silicon composite powder and preparation method and application thereof - Google Patents
Carbon-silicon composite powder and preparation method and application thereof Download PDFInfo
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Abstract
The application relates to the technical field of lithium ion batteries, in particular to carbon-silicon composite powder and a preparation method and application thereof. The carbon-silicon composite powder comprises: a first composite layer and a second composite layer which are sequentially covered on the surface of the nuclear body; the core comprises nanocarbon; the first composite layer comprises a plurality of first vertical graphene nano sheets which are connected with the nucleosome, and a first nano silicon layer filled in the gaps of the first vertical graphene nano sheets; the second composite layer comprises a plurality of second vertical graphene nanoplatelets which are connected with the first nano silicon layer, and a second nano silicon layer filled in the gaps of the second vertical graphene nanoplatelets; along the radial direction of the nucleus body, the size of the first nano silicon layer is not larger than the size of the first vertical graphene nano sheet, and the size of the second nano silicon layer is not larger than the size of the second vertical graphene nano sheet. The carbon-silicon composite powder can obviously inhibit the volume expansion of silicon, and has excellent specific capacity, conductivity, rate capability and electrochemical cycling stability.
Description
Technical Field
The application relates to the technical field of lithium ion batteries, in particular to carbon-silicon composite powder and a preparation method and application thereof.
Background
With the development of social economy, people have increasingly greater demands for energy, and correspondingly have increasingly serious energy crisis and environmental problems, so that the development and utilization of novel clean energy are current and future research hotspots. Under the background, the lithium ion battery has become a main power source of portable consumer electronic products due to the excellent characteristics of high energy density, long cycle life, stable performance, environmental friendliness and the like, and is widely applied to the fields of intelligent devices, new energy automobiles and the like. To accommodate the ever higher energy demands, the high energy density and high power density demands of lithium ion batteries are also increasing. The cathode material is an important component in a lithium ion battery, graphite is the most common cathode material in the market at present, but the theoretical specific capacity is only 372mAh/g, the lithium removal rate is low, and the increasing energy density and power density requirements are not met far. Silicon materials are widely regarded as ideal negative electrode materials of a new generation of lithium ion batteries due to the advantages of abundant reserves, high capacity (4200 mAh/g), low lithium intercalation potential and the like. However, silicon materials have serious volume expansion problems during lithium intercalation, repeated volume expansion causes silicon powder to be broken, electrodes to be broken and lose electrical contact, and the conductivity is low, so that the cycle performance and the rate performance of the silicon materials are affected.
Studies have shown that the smaller the volume of the silicon particles, the more favorable the volume expansion of the dispersed silicon material during lithium deintercalation, and the lower the possibility of crushing the silicon material. However, the smaller the size of the nano-silicon particles, the larger the specific surface area thereof, which will exacerbate the consumption of the electrolyte and lead to a drastic decrease in battery performance. The common solution is to adopt nano silicon and carry out carbon coating on the nano silicon, wherein the carbon coating can reduce the specific surface area of the nano silicon to a certain extent, reduce the consumption of electrolyte and enhance the conductivity of the nano silicon; however, carbon coating is usually easy to jointly coat a plurality of aggregated nano-silicon, so that the volume expansion is increased, and the conductivity (especially the electrochemical cycle performance) is poor; the preparation of the nano silicon is difficult, and the problems of low yield, high price, poor size uniformity and the like exist, so that the industrialized application requirement can not be met. Therefore, how to ensure the dimension of the nano silicon in the electrode material to be as thin as possible, reduce the specific surface area of the silicon material, and ensure the excellent conductivity of the electrode material is a great difficulty in the research of nano silicon cathode materials.
Disclosure of Invention
The invention aims to provide carbon-silicon composite powder, a preparation method and application thereof, and aims to solve the technical problem that the existing lithium ion battery anode material cannot meet the requirements of thinning the size of a silicon material and controlling the specific surface area of the silicon material at the same time, so that the electrochemical performance is poor.
The first aspect of the application provides a carbon-silicon composite powder, which comprises a core body, a first composite layer covered on the surface of the core body and a second composite layer covered on the surface of the first composite layer. The core comprises nanocarbon. The first composite layer comprises a plurality of first vertical graphene nano sheets which are connected with the surface of the nucleosome, and a first nano silicon layer filled in gaps of the plurality of first vertical graphene nano sheets; the first nano-silicon layer has a dimension along the radial direction of the core body that is not greater than the dimension of the first vertical graphene nanoplatelets along the radial direction of the core body. The second composite layer comprises a plurality of second vertical graphene nanoplatelets which are connected with the surface of the first nano silicon layer, and a second nano silicon layer filled in gaps of the plurality of second vertical graphene nanoplatelets; the second nano-silicon layer has a dimension along the radial direction of the core body that is not greater than the dimension along the radial direction of the core body of the second vertical graphene nanoplatelets.
The nuclear body in the carbon-silicon composite powder provided by the application comprises the nano carbon, and the nano carbon can be used as a conductive matrix, so that conductivity is improved. In the first composite layer, a plurality of first vertical graphene nano sheets are connected with the surface of the nuclear body, gaps are formed among the plurality of first vertical graphene nano sheets, and a first nano silicon layer is filled in the gaps among the plurality of first vertical graphene nano sheets; the size of the first nano silicon layer is not larger than that of the first vertical graphene nano sheets along the radial direction of the nuclear body, so that the first nano silicon layer is separated by a plurality of first vertical graphene nano sheets, the agglomeration of nano silicon materials can be avoided, the size of the nano silicon materials can be further refined to a greater extent, the nano silicon materials are dispersed more uniformly, the specific surface area of the nano silicon materials is not increased, the volume change of the nano silicon materials in the charging and discharging process is effectively reduced, the crushing of electrode materials caused by the overlarge volume change of the silicon materials is avoided, the consumption of electrolyte is reduced, and the cyclic stability and the multiplying power performance of the carbon-silicon composite powder are improved; meanwhile, the first vertical graphene nano sheet has good conductivity and flexibility, so that good electric contact can be formed between the separated nano silicon materials, and the volume expansion phenomenon of the silicon materials during lithium removal can be further effectively restrained. The structure of the second composite layer is the same as that of the first composite layer, so that the second composite layer can further improve the cycle stability, the multiplying power performance and the conductivity of the carbon-silicon composite powder; meanwhile, the arrangement of the second composite layer can also increase the content of nano silicon in the carbon-silicon composite powder, which is beneficial to improving the specific capacity of the carbon-silicon composite powder.
Therefore, the carbon-silicon composite powder provided by the application can obviously inhibit the volume expansion effect of the silicon material in the charge-discharge process, and has excellent specific capacity, conductivity, rate capability and electrochemical cycling stability.
A second aspect of the present application provides a method for preparing the carbon-silicon composite powder provided in the first aspect, including: performing a first deposition reaction on the nuclear body in a first graphene reaction gas, and then performing a second deposition reaction in a first silicon reaction gas to prepare an intermediate; and carrying out a third deposition reaction on the intermediate in the second graphene reaction gas, and then carrying out a fourth deposition reaction in the second silicon reaction gas.
The first graphene reaction gas comprises a first carbon source gas and a first hydrogen gas, and the second graphene reaction gas comprises a second carbon source gas and a second hydrogen gas; the volume ratio of the first carbon source gas to the first hydrogen gas and the volume ratio of the second carbon source gas to the second hydrogen gas are each independently (5:95) - (30:70).
The temperature of the first deposition reaction and the temperature of the third deposition reaction are each independently 1050-1150 ℃, and the time of the first deposition reaction and the time of the third deposition reaction are each independently 1-6h.
The temperature of the second deposition reaction and the temperature of the fourth deposition reaction are each independently 700-800 ℃, and the time of the second deposition reaction and the time of the fourth deposition reaction are each independently 0.5-3h.
The carbon-silicon composite powder prepared by the preparation method of the carbon-silicon composite powder can obviously inhibit the volume expansion effect of a silicon material in the charge-discharge process, has the advantages of excellent specific capacity, conductivity, rate capability, electrochemical cycling stability and the like, and has wide application prospect in the field of lithium batteries; meanwhile, the preparation method of the carbon-silicon composite powder is simple to operate and convenient for industrial mass production.
A third aspect of the present application provides an application of the carbon-silicon composite powder provided in the first aspect in preparing a negative electrode material of a lithium ion battery.
The carbon-silicon composite powder provided by the application is used for a lithium ion battery anode material, can realize excellent specific capacity, conductivity, rate capability and electrochemical cycling stability, and has good application prospect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered limiting the scope, and that other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 shows a schematic structural diagram of the carbon-silicon composite powder provided by the application.
Fig. 2 shows an SEM image of intermediate 1 prepared in example 1 of the present application.
Fig. 3 shows SEM images of intermediate 2 prepared in example 1 of the present application.
Fig. 4 shows SEM images of intermediate 3 prepared in example 1 of the present application.
Fig. 5 shows an SEM image of the carbon-silicon composite powder prepared in example 1 of the present application.
FIG. 6 shows a Raman spectrum of the carbon-silicon composite powder prepared in example 1 of the present application.
Fig. 7 shows an X-ray diffraction pattern of the carbon-silicon composite powder prepared in example 1 of the present application.
Fig. 8 shows a thermogravimetric graph of the carbon-silicon composite powder prepared in example 1 of the present application.
Fig. 9 shows a first charge-discharge specific capacity diagram of a lithium ion button cell prepared using the carbon-silicon composite powder prepared in example 1 of the present application.
Fig. 10 shows a cycle stability diagram of a lithium ion button cell prepared using the carbon-silicon composite powder prepared in example 1 of the present application.
Icon: 100-carbon-silicon composite powder; 110-nucleosome; 120-a first composite layer; 121-a first vertical graphene nanoplatelet; 122-a first nano-silicon layer; 130-a second composite layer; 131-a second vertical graphene nanoplatelet; 132-a second nano-silicon layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The following specifically describes a carbon-silicon composite powder, a preparation method and application thereof.
The present application provides a carbon-silicon composite powder, and fig. 1 shows a schematic structural diagram of a carbon-silicon composite powder 100 provided by the present application. It should be noted that, fig. 1 is only a schematic structural diagram of the carbon-silicon composite powder 100 provided in the present application, rather than a physical diagram, fig. 1 is only for facilitating description and understanding of the structure of the carbon-silicon composite powder 100 provided in the present application, and the proportional relationship, the shape, etc. in fig. 1 do not represent the actual proportional relationship and the shape of the carbon-silicon composite powder 100, and the physical diagram of the carbon-silicon composite powder 100 is referred to fig. 5.
Referring to fig. 1, the carbon-silicon composite powder 100 includes a core body 110, a first composite layer 120 covering the surface of the core body 110, and a second composite layer 130 covering the surface of the first composite layer 120. The core body 110 includes nanocarbon. The first composite layer 120 includes a plurality of first vertical graphene nanoplatelets 121 and a first nano-silicon layer 122; each first vertical graphene nanoplatelet 121 is connected to the surface of the core body 110, and the first nano silicon layer 122 is filled in the gaps of the adjacent first vertical graphene nanoplatelets 121. The second composite layer 130 includes a plurality of second vertical graphene nanoplatelets 131 and a second nano-silicon layer 132; each second vertical graphene nanoplatelet 131 is connected with the surface of the first nano silicon layer 122, and the second nano silicon layer 132 is filled in the gap between the adjacent second vertical graphene nanoplatelets 131.
In the present application, the first vertical graphene nanoplatelets 121 refer to graphene nanoplatelets that are located on the surface of the core body 110 and extend along the radial direction of the core body 110; the second vertical graphene nanoplatelets 131 refer to graphene nanoplatelets located on the surface of the first nano-silicon layer 122 and extending in the radial direction of the integral structure formed by the core body 110 and the first composite layer 120. The number of first vertical graphene nanoplatelets 121 and second vertical graphene nanoplatelets 131 is not limited in the present application.
In the present application, the carbon-silicon composite powder 100 includes a first composite layer 120 and a second composite layer 130. In other embodiments, the number of the first composite layer 120 and the second composite layer 130 in the carbon-silicon composite powder 100 may be adjusted according to practical situations.
The core body 110 includes nano-carbon, which serves as a growth substrate for the first vertical graphene nanoplatelets 121 and the first nano-silicon layer 122, which is advantageous in improving the conductivity of the carbon-silicon composite powder 100. Meanwhile, the volume of the nano carbon is smaller, so that the ratio of the nano carbon in the whole carbon-silicon composite powder 100 is reduced, and the specific capacity and the energy density of the carbon-silicon composite powder 100 are improved.
In this application, the dimension of the first nano-silicon layer 122 along the radial direction of the core body 110 is not greater than the dimension of the first vertical graphene nanoplatelets 121 along the radial direction of the core body 110.
Because gaps are formed among the first vertical graphene nano sheets 121 in the first composite layer 120, a porous structure can be formed among the plurality of first vertical graphene nano sheets 121, the first nano silicon layer 122 is filled in the porous gaps of the plurality of first vertical graphene nano sheets 121, the size of the first nano silicon layer 122 along the radial direction of the core body 110 is not larger than that of the first vertical graphene nano sheets 121 along the radial direction of the core body 110, the first nano silicon layer 122 is ensured to be separated by the plurality of first vertical graphene nano sheets 121, the agglomeration of nano silicon materials in the first nano silicon layer 122 can be avoided, the size of the nano silicon materials in the first nano silicon layer 122 can be further refined to a greater extent, the nano silicon materials are enabled to be more uniform in dispersion, the specific surface area of the nano silicon materials is not increased, the volume change of the nano silicon materials in the charging and discharging process is effectively reduced, the crushing of electrode materials caused by the overlarge volume change of the silicon materials is avoided, the consumption of electrolyte is reduced, and the circulation stability and the performance of the carbon silicon composite powder 100 is facilitated to be improved. If the dimension of the first nano-silicon layer 122 along the radial direction of the core body 110 is greater than the dimension of the first vertical graphene nanoplatelets 121 along the radial direction of the core body 110, it cannot be ensured that the first nano-silicon layer 122 is separated and refined by the first vertical graphene nanoplatelets 121.
In addition, since the first vertical graphene nanoplatelets 121 have good conductivity and flexibility, it is beneficial to ensure that good electrical contact can be formed between the partitioned nano silicon materials in the first nano silicon layer 122 and further effectively inhibit the volume expansion phenomenon of the silicon materials during lithium deintercalation.
In the present application, the dimension of the second nano-silicon layer 132 along the radial direction of the core body 110 is not greater than the dimension of the second vertical graphene nanoplatelets 131 along the radial direction of the core body 110.
Because the structure of the second composite layer 130 is the same as that of the first composite layer 120, the arrangement of the second composite layer 130 can further improve the cycle stability, the rate capability and the conductivity of the carbon-silicon composite powder 100; meanwhile, the second nano silicon layer 132 is arranged in the second composite layer 130, so that the content of nano silicon in the carbon-silicon composite powder 100 can be increased, and the specific capacity of the carbon-silicon composite powder 100 can be further improved.
Further, the size of the first vertical graphene nanoplatelets 121 along the radial direction of the core body 110 is greater than the size of the first nano-silicon layer 122 along the radial direction of the core body 110, so that a "porous" gap is formed between the first vertical graphene nanoplatelets 121 in the first composite layer 120 and the second vertical graphene nanoplatelets 131 in the second composite layer 130, and the average size of the "pores" in the second composite layer 130 is smaller than the average size of the "pores" in the first composite layer 120, so that the size of the second nano-silicon layer 132 in the second composite layer 130 is finer than the size of the first nano-silicon layer 122 in the first composite layer 120, and further, the specific surface area of the nano-silicon material in the second composite layer 130 (i.e. the outer layer of the carbon-silicon composite powder 100) is further effectively reduced, and the inhibition effect on the volume change of the nano-silicon material in the charge-discharge process is further improved.
In the embodiment of the present application, the dimension of the first vertical graphene nanoplatelets 121 along the radial direction of the core body 110 is 10-200nm, and the dimension of the first nano-silicon layer 122 along the radial direction of the core body 110 is 8-180nm, so that the dimension of the first vertical graphene nanoplatelets 121 along the radial direction of the core body 110 can be ensured to be larger than the dimension of the first nano-silicon layer 122 along the radial direction of the core body 110. As an example, the first vertical graphene nanoplatelets 121 may have a size of 10nm, 20nm, 30nm, 50nm, 80nm, 100nm, 150nm, 180nm, 200nm, or the like along the radial direction of the core body 110; the first nano-silicon layer 122 may have a dimension along the radial direction of the core body 110 of 8nm, 10nm, 30nm, 50nm, 80nm, 100nm, 150nm, 180nm, or the like.
Further, the dimension of the second vertical graphene nanoplatelets 131 along the radial direction of the core body 110 is greater than the dimension of the second nano-silicon layer 132 along the radial direction of the core body 110. Since the second vertical graphene nanoplatelets 131 have flexible flexibility, the size of the second vertical graphene nanoplatelets 131 along the radial direction of the core body 110 is larger than the size of the second nano-silicon layer 132 along the radial direction of the core body 110, so that even if the second nano-silicon layer 132 undergoes volume expansion during lithium deintercalation to cause the size of the second nano-silicon layer 132 to increase along the radial direction of the core body 110, the second nano-silicon layer 132 is still separated by the second vertical graphene nanoplatelets 131, thereby further inhibiting the volume change of the nano-silicon material during charge and discharge.
In the embodiment of the present application, the dimension of the second vertical graphene nanoplatelets 131 along the radial direction of the core body 110 is 10-200nm, and the dimension of the second nano-silicon layer 132 along the radial direction of the core body 110 is 5-150nm, so that the dimension of the second vertical graphene nanoplatelets 131 along the radial direction of the core body 110 can be ensured to be larger than the dimension of the second nano-silicon layer 132 along the radial direction of the core body 110. As an example, the second vertical graphene nanoplatelets 131 may have a size of 10nm, 20nm, 30nm, 50nm, 80nm, 100nm, 150nm, 180nm, 200nm, or the like along the radial direction of the core body 110; the first nano-silicon layer 122 may have a dimension along the radial direction of the core body 110 of 5nm, 10nm, 30nm, 50nm, 80nm, 100nm, 150nm, or the like.
In the present application, the D50 of the nanocarbon is 10 to 300nm, and if the D50 of the nanocarbon is too small, it is not advantageous to provide enough space for the growth of the first vertical graphene nanoplatelets 121 and the first nano-silicon layer 122; if the D50 of the nanocarbon is too large, the specific capacity and energy density of the carbon-silicon composite powder 100 are not improved. As an example, the D50 of the nanocarbon may be 10nm, 30nm, 100nm, 200nm, 300nm, or the like.
In embodiments of the present application, the nanocarbon comprises at least one of conductive carbon black, nano amorphous carbon particles, nano graphite particles, nano carbon fibers, and carbon nanotubes.
Further, when the nanocarbon is selected from conductive carbon black, nano amorphous carbon particles or nano graphite particles, the D50 of the nanocarbon is 10 to 100nm; as an example, when the nanocarbon is selected from conductive carbon black, nano amorphous carbon particles, or nano graphite particles, D50 of the nanocarbon may be 10nm, 30nm, 50nm, 100nm, or the like.
When the nano carbon is selected from nano carbon fiber, D50 of the nano carbon is 10-300nm; as an example, when the nanocarbon is selected from the group consisting of nanocarbon fibers, D50 of the nanocarbon may be 10nm, 30nm, 80nm, 100nm, 200nm, 300nm, or the like.
When the nano carbon is selected from carbon nano tubes, the D50 of the nano carbon is 10-100nm; as an example, when the nanocarbon is selected from carbon nanotubes, D50 of the nanocarbon may be 10nm, 30nm, 50nm, 80nm, 100nm, or the like.
In the present application, the distance between two adjacent first vertical graphene nanoplatelets 121 and the distance between two adjacent second vertical graphene nanoplatelets 131 are each independently 5 to 200nm. If the distance between two adjacent first vertical graphene nanoplatelets 121 is too small, the filling of the first nano silicon layer 122 is not facilitated, so that the specific capacity of the carbon-silicon composite powder 100 is too low; if the distance between two adjacent first vertical graphene nano sheets 121 is too large, the volume of the first nano silicon layer 122 filled in the gap between two adjacent first vertical graphene nano sheets 121 is too large, which is not beneficial to control the volume change of the nano silicon material in the charge and discharge process, resulting in poor battery cycle performance. The distance between two adjacent second vertical graphene nanoplatelets 131 is set identically.
It should be noted that, in the present application, the distance between two adjacent first vertical graphene nanoplatelets 121 refers to an average distance between free ends of the two adjacent first vertical graphene nanoplatelets 121 away from the core body 110; the distance between two adjacent second vertical graphene nanoplatelets 131 refers to an average distance between free ends of the two adjacent second vertical graphene nanoplatelets 131 away from the first nano-silicon layer 122.
As an example, the distance between the adjacent two first vertical graphene nanoplatelets 121 and the distance between the adjacent two second vertical graphene nanoplatelets 131 may each be independently 5nm, 10nm, 20nm, 30nm, 50nm, 80nm, 100nm, 150nm, 180nm, 200nm, or the like.
The carbon-silicon composite powder 100 provided by the application has at least the following advantages:
the carbon-silicon composite powder 100 provided by the application can remarkably inhibit the volume expansion effect of a silicon material, and has excellent specific capacity, conductivity, rate capability and electrochemical cycling stability.
The application also provides a preparation method of the carbon-silicon composite powder, which comprises the following steps: forming a first composite layer on the surface of the nuclear body by adopting a chemical vapor deposition method to prepare an intermediate; and forming a second composite layer on the surface of the first composite layer.
Specifically, the preparation method for forming the first composite layer on the surface of the core body comprises the following steps: and performing a first deposition reaction on the nuclear body in the first graphene reaction gas, and then performing a second deposition reaction on the nuclear body in the first silicon reaction gas. The first deposition reaction causes the surface of the nucleus to grow a plurality of first vertical graphene nanoplatelets, and the second deposition reaction causes the first nano-silicon layer to be deposited in the gaps of the plurality of first vertical graphene nanoplatelets on the surface of the nucleus.
In the present application, the first graphene reaction gas includes a first carbon source gas and a first hydrogen gas. The presence of the first hydrogen gas may provide conditions for the growth of the first vertical graphene nanoplatelets on the surface of the core.
Further, the volume ratio of the first carbon source gas to the first hydrogen is (5:95) - (30:70), and under the above ratio, the first vertical graphene nanoplatelets which can be distributed at intervals can be ensured to grow on the surface of the nuclear body, and a space is provided for the deposition of the first nano silicon layer.
As an example, the volume ratio of the first carbon source gas to the first hydrogen gas may be 5: 95. 10: 90. 12: 88. 20: 80. 25:75 or 30:70, etc.
In the present application, the first carbon source gas may be selected from at least one of alkane, alkene, alkyne, benzene, and ketone. Further, the first carbon source gases may each be independently selected from at least one of methane, ethane, propane, ethylene, propylene, acetylene, propyne, benzene, and acetone. The first carbon source gas is not limited to the above, and may be other carbon source gases.
In this application, the first silicon reactant gas comprises a first silicon source gas. Further, the first silicon source gas may be selected from at least one of silane, silicon tetrachloride, trichlorosilane, and dichlorosilane. The first silicon source gas is not limited to the above, and may be other silicon source gases.
Still further, the first silicon reactant gas may further comprise a third hydrogen gas, the first silicon source gas and the third hydrogen gas being in a volume ratio of (5:95) - (30:70). As an example, the volume ratio of the first silicon source gas and the third hydrogen gas is 5: 95. 10: 90. 12: 88. 20: 80. 25:75 or 30:70, etc.
In the application, the temperature of the first deposition reaction is 1050-1150 ℃, the first deposition reaction is 1-6h, the second deposition reaction is 700-800 ℃, the time of the second deposition reaction is 0.5-3h, and under the reaction conditions, the size of the first vertical graphene nano sheets in the first composite layer formed on the surface of the core body along the radial direction of the core body is larger than the size of the first nano silicon layers along the radial direction of the core body, so that the first nano silicon layers are ensured to be separated by the first vertical graphene nano sheets which are distributed at intervals.
As an example, the temperature of the first deposition reaction may be 1050 ℃, 1080 ℃, 1100 ℃, 1020 ℃, 1050 ℃, 1080 ℃, 1150 ℃, or the like; the time of the first deposition reaction may each independently be 1h, 1.5h, 2h, 2.5h, 4h, or 6h, etc.; the temperature of the second deposition reaction may be 700 ℃, 720 ℃, 780 ℃, 800 ℃, or the like, and the time of the second deposition reaction may be 0.5h, 0.8h, 1h, 1.5h, 2h, 3h, or the like.
In this application, the method for forming the second composite layer on the surface of the first composite layer is the same as the method for forming the first composite layer on the surface of the core body, and includes: and carrying out a third deposition reaction on the intermediate in the second graphene reaction gas, and then carrying out a fourth deposition reaction in the second silicon reaction gas.
In the present application, the second graphene reaction gas includes a second carbon source gas and a second hydrogen gas.
Further, the volume ratio of the second carbon source gas to the second hydrogen gas is (5:95) - (30:70); as an example, the volume ratio of the second carbon source gas to the second hydrogen gas may be 5: 95. 10: 90. 12: 88. 20: 80. 25:75 or 30:70, etc.
In the present application, the second carbon source gas may be selected from at least one of alkane, alkene, alkyne, benzene, and ketone. Further, the second carbon source gas may be selected from at least one of methane, ethane, propane, ethylene, propylene, acetylene, propyne, benzene, and acetone.
In the application, the temperature of the third deposition reaction is 1050-1150 ℃, the time of the third deposition reaction is 1-6h, the temperature of the fourth deposition reaction is 700-800 ℃, and the time of the fourth deposition reaction is 0.5-3h. Under the reaction conditions, the dimension of the second vertical graphene nano sheets along the radial direction of the nuclear body can be made to be larger than the dimension of the second nano silicon layers along the radial direction of the nuclear body, so that the second nano silicon layers are ensured to be separated by the second vertical graphene nano sheets which are distributed at intervals. And the sites for forming the first vertical graphene nano sheets on the surface of the nucleosome and the sites for forming the second vertical graphene nano sheets on the surface of the first nano silicon layer are random by adopting a chemical vapor deposition method, so that a porous gap is formed between the first vertical graphene nano sheets in the first composite layer and the second vertical graphene nano sheets in the second composite layer, and the size of the second nano silicon layer can be further thinned.
As an example, the temperature of the third deposition reaction may be 1050 ℃, 1080 ℃, 1100 ℃, 1020 ℃, 1050 ℃, 1080 ℃, 1150 ℃, or the like; the time of the third deposition reaction may be 1h, 1.5h, 2h, 2.5h, 4h, or 6h, etc.; the temperature of the fourth deposition reaction may be 700 ℃, 720 ℃, 780 ℃, 800 ℃, or the like; the time for the fourth deposition reaction may be 0.5h, 0.8h, 1h, 1.5h, 2h, 3h, or the like.
In this application, the second silicon reactant gas includes a second silicon source gas.
Further, the second silicon source gases are each independently selected from at least one of silane, silicon tetrachloride, trichlorosilane, and dichlorosilane.
Still further, the second silicon reactant gas further comprises a fourth hydrogen gas, the volume ratio of the second silicon source gas to the fourth hydrogen gas being (5:95) - (30:70); as an example, the volume ratio of the second silicon source gas and the fourth hydrogen gas is 5: 95. 10: 90. 12: 88. 20: 80. 25:75 or 30:70, etc.
The preparation method of the carbon-silicon composite powder provided by the application has at least the following advantages:
the carbon-silicon composite powder prepared by the preparation method of the carbon-silicon composite powder can obviously inhibit the volume expansion effect of a silicon material in the charge-discharge process, has the advantages of excellent specific capacity, conductivity, rate capability, electrochemical cycling stability and the like, and has wide application prospect in the field of lithium batteries; meanwhile, the preparation method of the carbon-silicon composite powder is simple to operate and convenient for industrial mass production.
The application also provides application of the carbon-silicon composite powder in preparing lithium ion battery anode materials.
The carbon-silicon composite powder provided by the application is used for a lithium ion battery anode material, can realize excellent specific capacity, conductivity, rate capability and electrochemical cycling stability, and has good application prospect.
The characteristics and properties of the carbon-silicon composite powder and the preparation method thereof are described in further detail below with reference to examples.
Example 1
The embodiment provides a carbon-silicon composite powder and a preparation method thereof, and the method comprises the following steps:
(1) Placing conductive carbon black with D50 of 50nm in CH 4 And H is 2 In a mixed atmosphere of (2) CH is regulated 4 And H is 2 The volume ratio of (2) is 10:90, heating to 1100 ℃, and preserving heat for 4 hours to prepare an intermediate 1;
(2) Placing the intermediate 1 obtained in the step (1) in SiH 4 And H is 2 In a mixed atmosphere of (2) SiH is adjusted 4 And H is 2 Is 20:80, heating to 750 ℃, and preserving heat for 1.5h to obtain an intermediate 2;
(3) Placing the intermediate 2 prepared in the step (2) on CH 4 And H is 2 In a mixed atmosphere of (2) CH is regulated 4 And H is 2 The volume ratio of (2) is 10:90, heating to 1100 ℃, and preserving heat for 4 hours to prepare an intermediate 3;
(4) Placing the intermediate 3 obtained in the step (3) in SiH 4 And H is 2 In a mixed atmosphere of (2) SiH is adjusted 4 And H is 2 Is 20:80, heating to 750 ℃, and preserving heat for 1.5h to obtain the carbon-silicon composite powder.
Example 2
The embodiment provides a carbon-silicon composite powder and a preparation method thereof, and the method comprises the following steps:
(1) Placing conductive carbon black with D50 of 10nm in CH 4 And H is 2 In a mixed atmosphere of (2) CH is regulated 4 And H is 2 The volume ratio of (2) is 5:95, heating to 1050 ℃, and preserving heat for 1h to obtain an intermediate 1;
(2) Placing the intermediate 1 obtained in the step (1) in SiH 4 And H is 2 In a mixed atmosphere of (2) SiH is adjusted 4 And H is 2 The volume ratio of (2) is 5:95, heating to 700 ℃, and preserving heat for 0.5h to prepare an intermediate 2;
(3) Preparing the step (2)The intermediate 2 obtained is placed in CH 4 And H is 2 In a mixed atmosphere of (2) CH is regulated 4 And H is 2 The volume ratio of (2) is 5:95, heating to 1050 ℃, and preserving heat for 1h to obtain an intermediate 3;
(4) Placing the intermediate 3 obtained in the step (3) in SiH 4 And H is 2 In a mixed atmosphere of (2) SiH is adjusted 4 And H is 2 The volume ratio of (2) is 5:95, heating to 700 ℃, and preserving heat for 0.5h to obtain the carbon-silicon composite powder.
Example 3
The embodiment provides a carbon-silicon composite powder and a preparation method thereof, and the method comprises the following steps:
(1) Placing conductive carbon black with D50 of 100nm in CH 4 And H is 2 In a mixed atmosphere of (2) CH is regulated 4 And H is 2 Is 30 volume ratio: 70, heating to 1150 ℃, and preserving heat for 6 hours to prepare an intermediate 1;
(2) Placing the intermediate 1 obtained in the step (1) in SiH 4 And H is 2 In a mixed atmosphere of (2) SiH is adjusted 4 And H is 2 Is 30 volume ratio: 70, heating to 800 ℃, and preserving heat for 1.5h to prepare an intermediate 2;
(3) Placing the intermediate 2 prepared in the step (2) on CH 4 And H is 2 In a mixed atmosphere of (2) CH is regulated 4 And H is 2 Is 30 volume ratio: 70, heating to 1150 ℃, and preserving heat for 6 hours to prepare an intermediate 3;
(4) Placing the intermediate 3 obtained in the step (3) in SiH 4 And H is 2 In a mixed atmosphere of (2) SiH is adjusted 4 And H is 2 Is 30 volume ratio: 70, heating to 800 ℃, and preserving heat for 1.5h to obtain the carbon-silicon composite powder.
Comparative example 1
Comparative example 1 provides a carbon-silicon composite powder and a method for preparing the same, and the comparative example 1 is different from example 1 in that the step of preparing the carbon-silicon composite powder does not include step (3) and step (4).
Comparative example 2
Comparative example 2 provides a carbon-silicon composite powder and a preparation method thereof, and the preparation of the carbon-silicon composite powder of comparative example 2 adopts the following steps: placing conductive carbon black with D50 of 50nm in SiH 4 And H is 2 In a mixed atmosphere of (2) SiH is adjusted 4 And H is 2 Is 20:80, heating to 750 ℃, and preserving heat for 0.5h to obtain the carbon-silicon composite powder.
Comparative example 3
Comparative example 3 provides a carbon-silicon composite powder and a method for preparing the same, and the comparative example 3 is different from example 1 in that the heat preservation time in the step (1) and the step (2) is 2h, and the heat preservation time in the step (3) and the step (4) is 4h.
Test example 1
The intermediate 1, intermediate 2 and intermediate 3 prepared in example 1 were subjected to Scanning Electron Microscope (SEM) characterization, and the characterization results are shown in fig. 2, 3 and 4, respectively. The carbon-silicon composite powder prepared in example 1 was subjected to Scanning Electron Microscope (SEM) characterization, raman spectrum characterization, X-ray diffraction characterization and thermogravimetric analysis, and the characterization results are shown in fig. 5, 6, 7 and 8, respectively. And the carbon-silicon composite powder prepared in example 1 was used to prepare a lithium ion button cell, and the first charge-discharge specific capacity and the cycling stability of the cell were tested, and the test results are shown in fig. 9 and 10, respectively. The preparation method of the lithium ion button cell comprises the following steps: mixing the carbon-silicon composite powder with a conductive agent SP, a thickener CMC and a binder SBR, coating the mixture on a copper foil current collector, and vacuum drying and cutting the mixture to obtain an electrode plate; the obtained electrode plate is used as a working electrode, a metal lithium foil is used as a reference electrode and a counter electrode, a lithium ion button cell is assembled in a glove box, a used diaphragm is a Celgard 2325 polymer porous membrane, and an electrolyte is 1.0M LiPF6 solution.
Analysis of results: as can be seen from fig. 2 to 5, the surface of the intermediate 1 is provided with a plurality of vertical graphene sheets, the vertical graphene sheets of the intermediate 1 are internally deposited with a nano silicon layer to form the intermediate 2, the height of the nano silicon layer does not exceed the height of the vertical graphene sheets, the surface of the intermediate 3 is provided with a plurality of vertical graphene nano sheets, the vertical graphene sheets of the intermediate 3 are internally deposited with a nano silicon layer to form the carbon silicon composite powder, and the height of the nano silicon layer does not exceed the height of the vertical graphene sheets, so that the carbon silicon composite powder capable of thinning the nano silicon layer and not increasing the specific surface area can be prepared by adopting the preparation method of the carbon silicon composite powder.
As can be seen from FIG. 6, at a wavelength of 1580cm -1 The graphene has obvious characteristic G peak at 1350cm wavelength -1 The graphene has obvious D peak at 2700cm wavelength -1 A 2D peak with obvious graphene appears nearby, the peak intensity of the 2D peak is similar to that of the G peak, and the wavelength is 510cm -1 A distinct characteristic peak belonging to silicon is arranged on the left and right; as can be seen from fig. 7, diffraction peaks of graphene appear near 26 °, diffraction peaks of silicon appear at 28 °, 47 °, 56 °, 69 °, 76 °, respectively, corresponding to (111), (220), (311), (400), (331) crystal planes of silicon, respectively; the carbon-silicon composite powder prepared in example 1 contains graphene and silicon.
As can be seen from fig. 8, the carbon-silicon composite powder prepared in example 1 starts to exhibit a thermal weight loss around 600 ℃ and reaches a maximum value around 760 ℃ with a thermal weight loss mass ratio of 36%, from which it can be calculated that the silicon content is about 64%.
As can be seen from fig. 9 and 10, the lithium ion button cell prepared by using the carbon-silicon composite powder prepared in example 1 has a specific capacity of 1800mAh/g for the first discharge, a first coulomb efficiency of 88.7%, and a capacity retention rate of 84.7% when the carbon-silicon composite powder is subjected to 300 times of charge-discharge cycles at a current density of 1C, which indicates that the carbon-silicon composite powder prepared in example 1 is beneficial to ensuring a high capacity and good cycle stability of the cell.
Test example 2
The carbon-silicon composite powders prepared in examples 1 to 3 and comparative examples 1 to 3 were tested for tap density, specific surface area, and silicon content; and lithium ion button cells were prepared using the carbon-silicon composite powders prepared in examples 1 to 3 and comparative examples 1 to 3, and the first discharge specific capacity, the first coulomb efficiency and the charge-discharge cycle performance of the cells were tested, and the test results are shown in table 1; the lithium ion button cell was prepared in the same manner as in test example 1, and the cycle retention was 300 times at a current density of 1C for charge-discharge cycle performance.
TABLE 1
As can be seen from table 1: the lithium ion button cell prepared by the carbon-silicon composite powder of the examples 1-3 has better comprehensive electrical properties than the lithium ion button cell prepared by the carbon-silicon composite powder of the comparative examples 1-3.
As can be seen from the comparison of example 1 and comparative example 1, the cyclic stability of the battery is not greatly affected by the preparation of the carbon-silicon composite powder by using only the steps (1) and (2), but the specific charge and discharge capacity of the battery is obviously reduced, and the first coulombic efficiency of the battery is reduced to some extent, which indicates that the specific capacity of the lithium ion battery can be improved by sequentially preparing the first composite layer and the second composite layer with the vertical graphene nano-sheets and the nano-silicon layer on the surface of the conductive carbon black.
As can be seen from the comparison of the example 1 and the comparative example 2, when the silicon layer is directly deposited on the surface of the conductive carbon black, the specific capacity and the cycle stability of the lithium ion battery are both poor, which indicates that the nano silicon layer is deposited by utilizing the gaps between the vertical graphene sheets, thereby being beneficial to improving the specific capacity and the cycle stability of the lithium ion battery.
As can be seen from example 1 and comparative example 3, when the vertical graphene growth time is reduced and the nano silicon deposition time is increased, the silicon content in the carbon-silicon composite powder can be increased, the specific capacity of the battery is increased, but excessive silicon deposition can cause the thickness of the silicon layer to be too large and not be effectively separated by graphene nano sheets, the silicon layer with a nano-scale dispersion structure cannot be effectively formed, and the cycle stability of the lithium ion battery is obviously improved; the time of vertical graphene growth and the time of nano silicon deposition defined by the application are favorable for improving the cycle stability of the lithium ion battery.
In conclusion, the carbon-silicon composite powder provided by the application can obviously inhibit the volume expansion effect of the silicon material in the charge-discharge process, and has excellent specific capacity, conductivity, rate capability and electrochemical cycle stability.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the same, but rather, various modifications and variations may be made by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.
Claims (17)
1. A carbon-silicon composite powder, comprising: the nuclear body comprises a nuclear body, a first composite layer covered on the surface of the nuclear body and a second composite layer covered on the surface of the first composite layer;
the core comprises nanocarbon;
the first composite layer comprises a plurality of first vertical graphene nano sheets which are connected with the surface of the nuclear body, and a first nano silicon layer filled in gaps of the plurality of first vertical graphene nano sheets; the first nano-silicon layer has a dimension along the radial direction of the core body that is not greater than the dimension of the first vertical graphene nanoplatelets along the radial direction of the core body;
the second composite layer comprises a plurality of second vertical graphene nanoplatelets which are connected with the surface of the first nano silicon layer and a second nano silicon layer filled in gaps of the plurality of second vertical graphene nanoplatelets; the second nano-silicon layer has a dimension along the radial direction of the core body that is not greater than the dimension of the second vertical graphene nanoplatelets along the radial direction of the core body.
2. The carbon-silicon composite powder of claim 1, wherein the nano carbon comprises at least one of conductive carbon black, nano amorphous carbon particles, nano graphite particles, nano carbon fibers, and carbon nanotubes.
3. The carbon-silicon composite powder according to claim 2, wherein the D50 of the nanocarbon is 10 to 300nm.
4. The carbon-silicon composite powder according to claim 2, wherein the D50 of the conductive carbon black, the nano amorphous carbon particles or the nano graphite particles is 10 to 100nm.
5. The carbon-silicon composite powder according to claim 2, wherein the D50 of the carbon nanofibers is 10-300nm.
6. The carbon-silicon composite powder according to claim 2, wherein the D50 of the carbon nanotubes is 10-100nm.
7. The carbon-silicon composite powder according to claim 1, wherein a distance between two adjacent first vertical graphene nanoplatelets and a distance between two adjacent second vertical graphene nanoplatelets are each independently 5 to 200nm.
8. The carbon-silicon composite powder of claim 1, wherein a dimension of the first vertical graphene nanoplatelets along a radial direction of the core is greater than a dimension of the first nano-silicon layer along the radial direction of the core.
9. The carbon-silicon composite powder according to claim 8, wherein the first vertical graphene nanoplatelets have a dimension of 10-200nm in a radial direction of the core body, and the first nano-silicon layer has a dimension of 8-180nm in the radial direction of the core body.
10. The carbon-silicon composite powder of claim 1, wherein a dimension of the second vertical graphene nanoplatelets along a radial direction of the core is greater than a dimension of the second nano-silicon layer along the radial direction of the core.
11. The carbon-silicon composite powder according to claim 10, wherein the second vertical graphene nanoplatelets have a dimension of 10-200nm in the radial direction of the core body, and the second nano-silicon layer has a dimension of 5-150nm in the radial direction of the core body.
12. The method for producing a carbon-silicon composite powder according to any one of claims 1 to 11, comprising: performing a first deposition reaction on the nuclear body in a first graphene reaction gas, and then performing a second deposition reaction in a first silicon reaction gas to prepare an intermediate; carrying out a third deposition reaction on the intermediate in a second graphene reaction gas, and then carrying out a fourth deposition reaction in a second silicon reaction gas;
the first graphene reaction gas comprises a first carbon source gas and a first hydrogen gas, and the second graphene reaction gas comprises a second carbon source gas and a second hydrogen gas; the volume ratio of the first carbon source gas to the first hydrogen gas and the volume ratio of the second carbon source gas to the second hydrogen gas are each independently (5:95) - (30:70);
the temperature of the first deposition reaction and the temperature of the third deposition reaction are each independently 1050-1150 ℃, and the time of the first deposition reaction and the time of the third deposition reaction are each independently 1-6h;
the temperature of the second deposition reaction and the temperature of the fourth deposition reaction are each independently 700-800 ℃, and the time of the second deposition reaction and the time of the fourth deposition reaction are each independently 0.5-3h.
13. The method for producing a carbon-silicon composite powder according to claim 12, wherein the first carbon source gas and the second carbon source gas are each independently selected from at least one of an alkane, an alkene, an alkyne, benzene, and a ketone.
14. The method for producing a carbon-silicon composite powder according to claim 13, wherein the first carbon source gas and the second carbon source gas are each independently selected from at least one of methane, ethane, propane, ethylene, propylene, acetylene, propyne, benzene, and acetone.
15. The method for producing a carbon-silicon composite powder according to claim 12, wherein the first silicon reaction gas comprises a first silicon source gas and the second silicon reaction gas comprises a second silicon source gas; the first silicon source gas and the second silicon source gas are each independently selected from at least one of silane, silicon tetrachloride, trichlorosilane, and dichlorosilane.
16. The method of producing a carbon-silicon composite powder according to claim 15, wherein the first silicon reaction gas further comprises a third hydrogen gas, and the volume ratio of the first silicon source gas to the third hydrogen gas is (5:95) - (30:70);
the second silicon reactant gas further comprises a fourth hydrogen gas, the volume ratio of the second silicon source gas to the fourth hydrogen gas being (5:95) - (30:70).
17. Use of the carbon-silicon composite powder according to any one of claims 1-11 for preparing a negative electrode material of a lithium ion battery.
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