CN116375035A - Preparation method of three-dimensional porous silicon-carbon composite material and composite material thereof - Google Patents

Preparation method of three-dimensional porous silicon-carbon composite material and composite material thereof Download PDF

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CN116375035A
CN116375035A CN202310270626.3A CN202310270626A CN116375035A CN 116375035 A CN116375035 A CN 116375035A CN 202310270626 A CN202310270626 A CN 202310270626A CN 116375035 A CN116375035 A CN 116375035A
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carbon
porous silicon
composite material
silicon
carbon composite
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吴俊杰
李惠军
梁奇
袁媛
段传阳
孙慧云
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Hubei Snow New Material Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/023—Preparation by reduction of silica or free silica-containing material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to the technical field of battery silicon cathodes, in particular to a preparation method of a three-dimensional porous silicon-carbon composite material and the composite material thereof. The porous silicon-carbon anode material is synthesized by utilizing pore channels of porous silicon dioxide, a rich porous carbon conductive network is formed, the rich three-dimensional conductive network and a graded micro-mesoporous network inside the material provide effective guarantee for the conductivity, the circulation performance and the multiplying power performance of the porous silicon-carbon material, the low-temperature aluminothermic reaction and the CVD coating effectively control the size of silicon and strengthen the electrochemical activity of silicon nano particles in the process of preparing the three-dimensional porous silicon-carbon composite material, the preparation process is simple, the mass ratio and the size of carbon and silicon are controllable, the volume expansion of silicon can be effectively inhibited, and the conductivity, the circulation performance and the multiplying power of the silicon-carbon material are improved.

Description

Preparation method of three-dimensional porous silicon-carbon composite material and composite material thereof
Technical Field
The invention relates to the technical field of battery silicon cathodes, in particular to a preparation method of a three-dimensional porous silicon-carbon composite material and the composite material thereof.
Background
At present, the silicon-based negative electrode of the battery is mainly constructed in the following modes: (1) the nano-silicon is prepared and mixed and embedded into a carbon matrix to form a nano-microstructure, the requirements on equipment are very high when the nano-silicon is crushed to nano-size, and meanwhile, the crushed nano-silicon is easy to agglomerate, so that the requirements on dispersing equipment are very high; (2) the growth of the silicon nanowire requires a certain noble metal catalyst, and the production cost is high; (3) and preparing the silicon-carbon negative electrode by reducing mesoporous silicon through magnesian heat and then compositing the mesoporous silicon with a carbon material.
Among these methods, the magnesium thermal reduction (MRR) is still a viable process in the production of silicon materials, but the reaction temperature (600-700 ℃) of MRR is very low due to the exothermic nature of MRR and the limited mass transfer process, while the local temperature of silicon materials is up to 1700 ℃, resulting in byproducts including magnesium silicate (Mg 2SiO 4) and magnesium silicide (Mg 2 Si); secondly, the excessively high reaction temperature not only increases the energy consumption, but also increases the size of Si crystal grains along with the increase of the reaction time, so that the material has poor circulation stability, and the silicon size after the magnesia reduction is increased and agglomerated; finally, in the aspect of constructing a three-dimensional carbon conductive network in the pore canal, the specific surface area (300 m < 2 >. G < -1 >) and the pore volume of the reduced porous silicon material are much smaller than those of porous silicon dioxide (900 m < 2 >. G < -1 >), and the constructed three-dimensional conductive network is not abundant. Patent CN102208634B discloses the preparation of a porous silicon-carbon anode material, in which the silicon-carbon anode is a porous conductive network constructed after reduction of silicon dioxide into porous silicon, but the specific surface area of the reduced material is significantly reduced, which indicates that the growth of silicon particles and collapse of the porous structure at high temperature occur during the reduction of silicon dioxide.
Therefore, there is a need for a method for preparing a three-dimensional porous silicon-carbon composite material with good conductivity, cycle performance and rate capability, simple preparation process, and controllable mass ratio of carbon to silicon and size, and a composite material thereof.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a three-dimensional porous silicon-carbon composite material and the composite material thereof, and aims to solve the problem that the traditional three-dimensional porous silicon-carbon composite material is poor in conductivity, circulation performance and multiplying power performance.
In order to achieve the above object, the preparation method of the three-dimensional porous silicon-carbon composite material provided by the invention comprises the following steps:
preparing porous silicon dioxide, taking inorganic silicon as a silicon source, adding a micropore template agent and a mesoporous template agent into the silicon source, so that the silicon source is assembled into a porous structure, and applying high temperature to the porous structure in an air atmosphere to obtain a porous silicon dioxide material;
preparing a porous silicon dioxide/carbon composite material, dissolving monosaccharide/polysaccharide and a nitrogen-containing compound in a solvent, adding the porous silicon dioxide material, depositing carbon into pore channels of the porous silicon dioxide material, solidifying for 12-24 hours, and adding inert gas or NH 3 Carbonizing for 2h in atmosphere to obtain porous silicon dioxide/carbon composite material;
preparing porous silicon carbon, adding the porous silicon dioxide/carbon composite material into Al-AlCl 3 Solid phase mixing reaction is carried out for 3-5h, then acid solvent is added to remove byproduct AlOCl, and porous silicon carbon is obtained;
coating the mesoporous silicon-carbon composite material with carbon, flowing the porous silicon-carbon with Ar for 3h, and then carrying out C 2 H 2 and/Ar is coated for 0.5-1 h, so that the carbon coating of the mesoporous silicon-carbon composite material is realized.
Further, the step of carbon coating of the mesoporous silicon-carbon composite material can be as follows:
and (3) carbon coating of the mesoporous silicon-carbon composite material, namely mixing porous silicon-carbon with asphalt in proportion, and keeping the temperature at 650 ℃ for 3-5 hours to realize carbon coating of the mesoporous silicon-carbon composite material.
Further, the step of preparing the porous silica/carbon composite material further comprises the steps of:
weighing 0.5 g-1 g of sucrose, polysaccharide, organic matters and 0.1 g-0.2 g of nitrogen-containing element compound, dissolving in 25ml of ethanol or water, and fully and uniformly mixing;
adding 0.5 g-1 g of the porous silica material in the step 1, stirring for 2-6 h, depositing carbon into the pore canal by an impregnation method, and then solidifying for 12-24 h;
carbonizing the solidified porous silicon dioxide material for 2 hours at 600-700 ℃ under Ar/He/N2/NH3 gas atmosphere to finally obtain the porous silicon dioxide/carbon composite material.
Further, the microporous template agent and the mesoporous template agent comprise one or more of tetrapropylammonium hydroxide (TRAOH), cetyltrimethylammonium bromide (CTAB) and polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123).
Further, the acidic solution comprises at least one of dilute hydrochloric acid, dilute nitric acid and dilute acetic acid;
further, the nitrogen-containing compound comprises one or more of ethylenediamine, urea, ammonia water, diethylenetriamine and polyethyleneimine.
Further, in the step of preparing the porous silicon carbon, the mass ratio of the porous silicon dioxide/carbon composite material to the Al to the AlCl3 is as follows: porous silica/carbon composite: alCl3=2.5:1-3:5-10.
Further, the silicon source is one or more of tetraethyl orthosilicate, tetrapropoxysilane or sodium silicate.
Further, the porous silica material is of an ordered three-dimensional cubic pore canal structure, and can be one of a mesoporous molecular sieve KIT-6, a micro-mesoporous composite structure ZSM-5/KIT-6, ZSM-5/SBA-15, ZSM-5/MCM-41, ZSM-5/MCM-48, beta/KIT-6, beta/SBA-15 and Beta/MCM-41.
The invention also provides a three-dimensional porous silicon-carbon composite material, which comprises the following steps:
the three-dimensional porous silicon-carbon composite material is obtained by the preparation method of the three-dimensional porous silicon-carbon composite material according to any one of the technical schemes.
The invention provides a preparation method of a three-dimensional porous silicon-carbon composite material and a composite material thereof, which aim to take a molecular sieve with a structure of abundant micro-mesopores and three-dimensional pore channels as a carrier, firstly deposit amorphous carbon in the pore channels to construct a rich three-dimensional conductive network, then prepare mesoporous silicon carbon by adopting a low-temperature thermit reduction reaction, ensure the yield of porous silicon dioxide on the basis of low energy consumption by adopting the thermit reduction reaction, and then coat a layer of amorphous carbon by adopting a CVD process, so that the reduced nano silicon particles are prevented from losing electrochemical activity due to agglomeration. The preparation process is simple, the mass ratio and the size of carbon and silicon are controllable, and the excellent three-dimensional conductive network and the hierarchical micro-mesoporous network inside the material ensure the characteristics of high capacity, long circulation and high multiplying power of the material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern of a three-dimensional porous silicon-carbon composite material prepared in accordance with an embodiment of the present invention;
FIG. 2 is an SEM image of KIT-6 made according to an embodiment of the invention;
FIG. 3 is an adsorption-desorption curve of a three-dimensional porous Si-C composite material N2 prepared according to an embodiment of the present invention;
FIG. 4 is a thermal gravimetric curve of a three-dimensional porous silicon-carbon composite made in accordance with one embodiment of the present invention;
FIG. 5 is a graph showing electrochemical performance testing of a three-dimensional porous silicon-carbon composite material prepared in accordance with one embodiment of the present invention;
FIG. 6 is a wide angle XRD pattern for ZSM-5/KIT-6 of the comparative example.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that all directional indicators (such as up, down, left, right, front, and rear … …) in the embodiments of the present invention are merely used to explain the relative positional relationship, movement, etc. between the components in a particular posture (as shown in the drawings), and if the particular posture is changed, the directional indicator is changed accordingly.
Furthermore, the description of "first," "second," etc. in this disclosure is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
In the present invention, P123 is a triblock copolymer, which is called polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, and has a molecular formula of PEO-PPO-PEO.
KIT-6 (porius Si), a porous silicon material with nanostructures.
ZSM-5/KIT-6 is a microporous-mesoporous composite molecular sieve.
It will be appreciated that the source of the inorganic silicon used in the present invention can be the finished inorganic silicon or the inorganic silicon extracted from coal ash, rice hulls.
The preparation method of the three-dimensional porous silicon-carbon composite material can comprise the following detailed steps:
s1: preparation of porous silica: 4.0g of P123 are weighed out and dissolved in 30g of distilled water and 120g of HCl (2M). After stirring to dissolve completely, 4.0g of n-butanol and 8.4g of tetraethyl orthosilicate were added. Then mixing for 24 hours at the water bath temperature of 35-40 ℃, and then carrying out hydrothermal reaction for 24 hours at the temperature of 100 ℃. The obtained silica is separated by filtration or centrifugation and a porous material is obtained at a high temperature under an air atmosphere.
S2: preparation of porous silica/carbon: weighing 0.5 g-1 g of sucrose/other monosaccharide polysaccharide/organic matters, dissolving 0.1 g-0.2 g of nitrogen element-containing compound (ethylenediamine, urea, ammonia water, diethylenetriamine, polyethyleneimine and other amine molecules) in 25ml of ethanol or water, fully mixing, adding 0.5 g-1 g of KIT-6 in the step 1, stirring for 2-6 h, solidifying for 12-24 h, and carbonizing for 2h (600-700 ℃) under Ar/He/N2/NH3 gas atmosphere to obtain the porous silicon-carbon material.
S3: preparing porous silicon carbon, namely preparing the porous silicon carbon material obtained in the step S2 according to the porous silicon material: al: alcl3=2.5: 1: 5-10, ar/He/N at 200-300 DEG C 2 Reacting for 3-5h under atmosphere.
S4: the porous silicon carbon material obtained in S3 was purified of by-products (AlOCl) in the reaction with diluted hydrochloric acid (1M) and diluted nitric acid (1M).
S5: and (3) flowing the material obtained in the step (S4) at 800 ℃ for 3 hours with 200ml/min of Ar, and then coating the material in C2H2/Ar (10%/90%, 200 ml/min) for 0.5 hour, so as to realize carbon coating of the mesoporous silicon-carbon composite material. Or mixing the material obtained in the step 4 with asphalt according to a certain proportion, and carrying out carbon coating at 650 ℃ for 3-5 hours to realize carbon coating of the mesoporous silicon-carbon composite material.
The invention has the following application examples:
example 1
4.0g of P123 are weighed out and dissolved in 30g of distilled water and 120g of HCl (2M). After stirring to dissolve completely, 4.0g of n-butanol and 8.4g of tetraethyl orthosilicate were added. Then mixed for 24 hours at a water bath temperature of 40 ℃ and then reacted for 24 hours at a hydrothermal temperature of 100 ℃. The obtained silicon dioxide (KIT-6) is centrifugally separated, and KIT-6 is obtained at a high temperature in an air atmosphere; 1g of sucrose is weighed and dissolved in 25ml of ethanol or water, after being fully and evenly mixed, 1g of KIT-6 is added and stirred for 6 hours, and is solidified for 12 hours, and then Ar/NH is carried out 3 Carbonizing for 2h (700 ℃) in gas atmosphere to obtain mesoporous SiO 2 Carbon material. According to porous silica/carbon: al: alCl 3 =2.5: 1:10 g is weighed and mixed to react for 5 hours in Ar atmosphere at 250 ℃, and then dilute hydrochloric acid (1M) is used for removing byproducts in the reaction; then flowing at 800 ℃ with 200ml/min Ar for 3 hours, then at C 2 H 2 And (3) coating Ar (10%/90%, 200 ml/min) for 0.5h to obtain the three-dimensional porous silicon-carbon composite material.
As shown in fig. 1, the 211 crystal plane of the small angle XRD curve indicates the formation of 3D cubic pore channels; as amorphous carbon is introduced into the mesoporous channel, the peak of the small angle XRD becomes small, indicating successful introduction of amorphous carbon; wide angle XRD showed successful amorphous carbon incorporation and reduction of silica to silicon.
As shown in FIG. 2, the prepared porous silica has a rock-like morphology and a particle size of 5-10 um.
FIG. 3 is a graph showing the three-dimensional porous silicon carbon composite material prepared in example 1 and the N of KIT-6 2 Adsorption and desorption curves show that the specific surface area of the material is reduced along with the introduction of the amorphous carbon, which indicates that the amorphous carbon is successfully filled into mesoporous channels.
As shown in fig. 4, fig. 4 is a thermal weight curve of the three-dimensional porous silicon-carbon composite material prepared in example 1, and it is understood that the mass ratio of silicon is about 40%.
As shown in fig. 5, fig. 5 is an electrochemical performance test curve of the three-dimensional porous silicon carbon composite material prepared in example 1, and the capacity of the material after circulation is maintained at 1300mah g -1 And the material has a unique three-dimensional conductive network and mesoporous structure, so that the material has good multiplying power performance.
Example 2
4.0g of P123 are weighed out and dissolved in 30g of distilled water and 120g of HCl (2M). After stirring to dissolve completely, 4.0g of n-butanol and 8.4g of tetraethyl orthosilicate were added. Then mixed for 24 hours at a water bath temperature of 40 ℃ and then reacted for 24 hours at a hydrothermal temperature of 100 ℃. The obtained silicon dioxide (KIT-6) is centrifugally separated, and KIT-6 is obtained at a high temperature in an air atmosphere; 1g of sucrose and 0.1g of ethylenediamine are weighed and dissolved in 25ml of ethanol or water, after being fully and evenly mixed, 1g of KIT-6 is added for stirring for 6 hours, solidification is carried out for 12 hours, and then mesoporous SiO is obtained by carbonization for 2 hours (700 ℃) under Ar gas atmosphere 2 Carbon material; according to porous silica/carbon: al: alcl3=2.5: 1:10 g is weighed and mixed to react for 5 hours in Ar atmosphere at 250 ℃, and then dilute hydrochloric acid (1M) is used for removing byproducts in the reaction; then flowing at 800 ℃ with 200ml/min Ar for 3 hours, then at C 2 H 2 And (3) coating Ar (10%/90%, 200 ml/min) for 0.5h to obtain the three-dimensional porous silicon-carbon composite material.
Example 3
4.0g of P123 are weighed out and dissolved in 30g of distilled water and 120g of HCl (2M). After stirring to dissolve completely, 4.0g of n-butanol and 8.4g of tetraethyl orthosilicate were added. Then mixed for 24 hours at a water bath temperature of 40 ℃ and then reacted for 24 hours at a hydrothermal temperature of 100 ℃. The obtained silicon dioxide (KIT-6) is centrifugally separated, and KIT-6 is obtained at a high temperature in an air atmosphere; 1g of sucrose and 0.2g of ethylenediamine are weighed and dissolved in 25ml of ethanol or water, after being fully and evenly mixed, 1g of KIT-6 is added for stirring for 6 hours, solidification is carried out for 12 hours, and then mesoporous SiO is obtained by carbonization for 2 hours (700 ℃) under Ar gas atmosphere 2 Carbon material; according to porous silica/carbon: al: alCl 3 =2.5: 1:10 g is weighed and mixed to react for 5 hours in Ar atmosphere at 250 ℃, and then dilute hydrochloric acid (1M) is used for removing byproducts in the reaction; then flowing at 800 ℃ with 200ml/min Ar for 3 hours, then at C 2 H 2 /Ar(10％And/90 percent, 200 ml/min) for 0.5 hour to obtain the three-dimensional porous silicon-carbon composite material.
Example 4
4.0g of P123 are weighed out and dissolved in 30g of distilled water and 120g of HCl (2M). After stirring to dissolve completely, 4.0g of n-butanol and 8.4g of tetraethyl orthosilicate were added. Then mixed for 24 hours at a water bath temperature of 40 ℃ and then reacted for 24 hours at a hydrothermal temperature of 100 ℃. The obtained silicon dioxide (KIT-6) is centrifugally separated, and KIT-6 is obtained at a high temperature in an air atmosphere; 1g of sucrose and 0.1g of polyethyleneimine are weighed and dissolved in 25ml of ethanol or water, after being fully and evenly mixed, 1g of KIT-6 is added for stirring for 6 hours, the mixture is solidified for 12 hours, and then the mixture is carbonized for 2 hours (700 ℃) under Ar gas atmosphere to obtain mesoporous SiO 2 Carbon material; according to porous silica/carbon: al: alCl 3 =2.5: 1:10 g is weighed and mixed to react for 5 hours in Ar atmosphere at 250 ℃, and then dilute hydrochloric acid (1M) is used for removing byproducts in the reaction; then flowing at 800 ℃ with 200ml/min Ar for 3 hours, then at C 2 H 2 And (3) coating Ar (10%/90%, 200 ml/min) for 0.5h to obtain the three-dimensional porous silicon-carbon composite material.
Example 5
4.0g of P123 are weighed out and dissolved in 30g of distilled water and 120g of HCl (2M). After stirring to dissolve completely, 4.0g of n-butanol and 8.4g of tetraethyl orthosilicate were added. Then mixed for 24 hours at a water bath temperature of 40 ℃ and then reacted for 24 hours at a hydrothermal temperature of 100 ℃. The obtained silicon dioxide (KIT-6) is centrifugally separated, and KIT-6 is obtained at a high temperature in an air atmosphere; 1g of sucrose and 0.2g of polyethyleneimine are weighed and dissolved in 25ml of ethanol or water, after being fully and evenly mixed, 1g of KIT-6 is added for stirring for 6 hours, the mixture is solidified for 12 hours, and then the mixture is carbonized for 2 hours (700 ℃) under Ar gas atmosphere to obtain mesoporous SiO 2 Carbon material; according to porous silica/carbon: al: alCl 3 =2.5: 1:10 g is weighed and mixed to react for 5 hours in Ar atmosphere at 250 ℃, and then dilute hydrochloric acid (1M) is used for removing byproducts in the reaction; then flowing at 800 ℃ with 200ml/min Ar for 3 hours, then at C 2 H 2 And (3) coating Ar (10%/90%, 200 ml/min) for 0.5h to obtain the three-dimensional porous silicon-carbon composite material.
Example 6
4.0g of P123 are weighed out and dissolved in 30g of distilled water and 120g of HCl (2M).After stirring to dissolve completely, 4.0g of n-butanol and 8.4g of tetraethyl orthosilicate were added. Then mixed for 24 hours at a water bath temperature of 40 ℃ and then reacted for 24 hours at a hydrothermal temperature of 100 ℃. The obtained silicon dioxide (KIT-6) is centrifugally separated, and KIT-6 is obtained at a high temperature in an air atmosphere; 1g of sucrose and 0.1g of ethylenediamine are weighed and dissolved in 25ml of ethanol or water, after being fully and evenly mixed, 1g of KIT-6 is added and stirred for 6 hours, and the mixture is solidified for 12 hours, and then NH is carried out 3 Carbonizing for 2h (700 ℃) in a gas atmosphere to obtain a mesoporous SiO 2/carbon material; according to porous silica/carbon: al: alCl 3 =2.5: 1:10 g is weighed and mixed to react for 5 hours in Ar atmosphere at 250 ℃, and then dilute hydrochloric acid (1M) is used for removing byproducts in the reaction; then flowing at 800 ℃ with 200ml/min Ar for 3 hours, then at C 2 H 2 And (3) coating Ar (10%/90%, 200 ml/min) for 0.5h to obtain the three-dimensional porous silicon-carbon composite material.
Example 7
4.0g of P123 are weighed out and dissolved in 30g of distilled water and 120g of HCl (2M). After stirring to dissolve completely, 4.0g of n-butanol and 8.4g of tetraethyl orthosilicate were added. Then mixed for 24 hours at a water bath temperature of 40 ℃ and then reacted for 24 hours at a hydrothermal temperature of 100 ℃. The obtained silicon dioxide (KIT-6) is centrifugally separated, and KIT-6 is obtained at a high temperature in an air atmosphere; 1g of sucrose and 0.2g of ethylenediamine are weighed and dissolved in 25ml of ethanol or water, after being fully and evenly mixed, 1g of KIT-6 is added and stirred for 6 hours, and the mixture is solidified for 12 hours, and then NH is carried out 3 Carbonizing for 2h (700 ℃) in gas atmosphere to obtain mesoporous SiO 2 Carbon material; according to porous silica/carbon: al: alCl 3 =2.5: 1:10 g is weighed and mixed to react for 5 hours in Ar atmosphere at 250 ℃, and then dilute hydrochloric acid (1M) is used for removing byproducts in the reaction; then flowing at 800 ℃ with 200ml/min Ar for 3 hours, then at C 2 H 2 And (3) coating Ar (10%/90%, 200 ml/min) for 0.5h to obtain the three-dimensional porous silicon-carbon composite material.
Example 8
4.0g of P123 are weighed out and dissolved in 30g of distilled water and 120g of HCl (2M). After stirring to dissolve completely, 4.0g of n-butanol and 8.4g of tetraethyl orthosilicate were added. Then mixed for 24 hours at a water bath temperature of 40 ℃ and then reacted for 24 hours at a hydrothermal temperature of 100 ℃. The resulting silica (KIT-6) was separated by centrifugation and dried in airObtaining KIT-6 at high temperature under atmosphere; 1g of sucrose and 0.1g of polyethyleneimine are weighed and dissolved in 25ml of ethanol or water, after being fully and evenly mixed, 1g of KIT-6 is added, the mixture is stirred for 6 hours, solidified for 12 hours, and then NH is carried out 3 Carbonizing for 2h (700 ℃) in gas atmosphere to obtain mesoporous SiO 2 Carbon material; according to porous silica/carbon: al: alCl 3 =2.5: 1:10 g is weighed and mixed to react for 5 hours in Ar atmosphere at 250 ℃, and then dilute hydrochloric acid (1M) is used for removing byproducts in the reaction; then flowing at 800 ℃ with 200ml/min Ar for 3 hours, then at C 2 H 2 And (3) coating Ar (10%/90%, 200 ml/min) for 0.5h to obtain the three-dimensional porous silicon-carbon composite material.
Example 9
4.0g of P123 are weighed out and dissolved in 30g of distilled water and 120g of HCl (2M). After stirring to dissolve completely, 4.0g of n-butanol and 8.4g of tetraethyl orthosilicate were added. Then mixed for 24 hours at a water bath temperature of 40 ℃ and then reacted for 24 hours at a hydrothermal temperature of 100 ℃. The obtained silicon dioxide (KIT-6) is centrifugally separated, and KIT-6 is obtained at a high temperature in an air atmosphere; 1g of sucrose and 0.2g of polyethyleneimine are weighed and dissolved in 25ml of ethanol or water, after being fully and evenly mixed, 1g of KIT-6 is added, stirred for 6 hours, solidified for 12 hours, and then treated by NH 3 Carbonizing for 2h (700 ℃) in a gas atmosphere to obtain a mesoporous SiO 2/carbon material; according to porous silica/carbon: al: alCl 3 =2.5: 1:10 g is weighed and mixed to react for 5 hours in Ar atmosphere at 250 ℃, and then dilute hydrochloric acid (1M) is used for removing byproducts in the reaction; then flowing at 800 ℃ with 200ml/min Ar for 3 hours, then at C 2 H 2 And (3) coating Ar (10%/90%, 200 ml/min) for 0.5h to obtain the three-dimensional porous silicon-carbon composite material.
Example 10
4.0g of P123 are weighed out and dissolved in 30g of distilled water and 120g of HCl (2M). After stirring to dissolve completely, 4.0g of n-butanol and 8.4g of tetraethyl orthosilicate were added. Then mixed for 24 hours at a water bath temperature of 40 ℃ and then reacted for 24 hours at a hydrothermal temperature of 100 ℃. The obtained silicon dioxide (KIT-6) is centrifugally separated, and KIT-6 is obtained at a high temperature in an air atmosphere; 1g of sucrose is weighed and dissolved in 25ml of ethanol or water, after being fully and evenly mixed, 1g of KIT-6 is added and stirred for 6 hours, and the mixture is solidified for 12 hours and then is treated by NH 3 Carbonizing for 2h (700 ℃) in gas atmosphere to obtain mesoporous SiO 2 Carbon material; according to porous silica/carbon: al: alCl 3 =2.5: 1:10 g is weighed and mixed to react for 5 hours in Ar atmosphere at 250 ℃, and then dilute hydrochloric acid (1M) is used for removing byproducts in the reaction; then flowing at 800 ℃ with 200ml/min Ar for 3 hours, then at C 2 H 2 And (3) coating Ar (10%/90%, 200 ml/min) for 0.5h to obtain the three-dimensional porous silicon-carbon composite material.
In all embodiments, with the introduction of nitrogen element in the carbon layer, the conductivity of the material is reduced, so that the rate performance of the material is obviously improved, and the optimal rate performance is 900mAh g -1 (5A/g), the invention adds molten salt Al-AlCl 3 The reaction temperature can be at 250 ℃, which is different from the prior art that no molten salt is added, so that AlCl is generated by the reaction 3 The thermit reaction is hindered, so that the prior art needs higher reaction temperature (1100 ℃), the preparation process is simple, the mass ratio and the size of carbon and silicon are controllable, the volume expansion of silicon can be effectively inhibited, and the conductivity, the circularity and the doubling performance of the silicon-carbon material are improved.
In combination with all the above embodiments, the present invention provides a preparation method of a three-dimensional porous silicon-carbon composite material and a composite material thereof, which aims to take a molecular sieve with a structure of abundant micro-mesopores and three-dimensional pore channels as a carrier, firstly deposit amorphous carbon in the pore channels to construct a abundant three-dimensional conductive network, then prepare mesoporous silicon carbon by adopting a low-temperature aluminothermic reduction reaction, ensure the yield of porous silicon dioxide on the basis of low energy consumption by adopting the aluminothermic reduction reaction, and then coat a layer of amorphous carbon by adopting a CVD process, so that the reduced nano silicon particles avoid losing electrochemical activity due to agglomeration. The preparation process is simple, the mass ratio and the size of carbon and silicon are controllable, and the excellent three-dimensional conductive network and the hierarchical micro-mesoporous network inside the material ensure the characteristics of high capacity, long circulation and high multiplying power of the material.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structural changes made by the description of the present invention and the accompanying drawings or direct/indirect application in other related technical fields are included in the scope of the invention.

Claims (10)

1. The preparation method of the three-dimensional porous silicon-carbon composite material is characterized by comprising the following steps of:
preparing porous silicon dioxide, taking inorganic silicon as a silicon source, adding a micropore template agent and a mesoporous template agent into the silicon source, so that the silicon source is assembled into a porous structure, and applying high temperature to the porous structure in an air atmosphere to obtain a porous silicon dioxide material;
preparing a porous silicon dioxide/carbon composite material, dissolving monosaccharide/polysaccharide and a nitrogen-containing compound in a solvent, adding the porous silicon dioxide material, depositing carbon into pore channels of the porous silicon dioxide material, solidifying for 12-24 hours, and adding inert gas or NH 3 Carbonizing for 2h in atmosphere to obtain porous silicon dioxide/carbon composite material;
preparing porous silicon carbon, adding the porous silicon dioxide/carbon composite material into Al-AlCl 3 Solid phase mixing and reacting for 3-5h, then adding an acid solvent to remove byproduct AlOCl to obtain porous silicon carbon;
coating the mesoporous silicon-carbon composite material with carbon, flowing the porous silicon-carbon with Ar for 3h, and then carrying out C 2 H 2 and/Ar is coated for 0.5-1 h, so that the carbon coating of the mesoporous silicon-carbon composite material is realized.
2. The method of preparing a three-dimensional porous silicon-carbon composite according to claim 1, wherein the step of carbon coating the mesoporous silicon-carbon composite further comprises:
and (3) carbon coating of the mesoporous silicon-carbon composite material, namely mixing porous silicon-carbon with asphalt in proportion, and keeping the temperature at 650 ℃ for 3-5 hours to realize carbon coating of the mesoporous silicon-carbon composite material.
3. The method of preparing a three-dimensional porous silicon-carbon composite according to claim 2, wherein the step of preparing a porous silica/carbon composite further comprises the steps of:
weighing 0.5 g-1 g of sucrose, polysaccharide, organic matters and 0.1 g-0.2 g of nitrogen-containing element compound, dissolving in 25ml of ethanol or water, and fully and uniformly mixing;
adding 0.5 g-1 g of the porous silica material in the step 1, stirring for 2-6 h, depositing carbon into the pore canal by an impregnation method, and then solidifying for 12-24 h;
carbonizing the solidified porous silicon dioxide material for 2 hours at 600-700 ℃ under Ar/He/N2/NH3 gas atmosphere to finally obtain the porous silicon dioxide/carbon composite material.
4. The method for preparing a three-dimensional porous silicon-carbon composite material according to claim 1, wherein the microporous template agent and the mesoporous template agent comprise one or more of tetrapropylammonium hydroxide (trail), cetyltrimethylammonium bromide (CTAB) and polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123).
5. The method for preparing a three-dimensional porous silicon-carbon composite material according to claim 1, wherein the acidic solution comprises at least one solution of dilute hydrochloric acid, dilute nitric acid and dilute acetic acid.
6. The method for preparing a three-dimensional porous silicon-carbon composite material according to claim 1, wherein the nitrogen-containing compound comprises one or more of ethylenediamine, urea, ammonia, diethylenetriamine and polyethyleneimine.
7. The method for preparing a three-dimensional porous silicon-carbon composite material according to claim 1, wherein in the step of preparing porous silicon-carbon, the mass ratio of porous silicon dioxide/carbon composite material, al and AlCl3 is: porous silica/carbon composite: alCl3=2.5:1-3:5-10.
8. The method for preparing a three-dimensional porous silicon-carbon composite material according to claim 7, wherein the silicon source is one or more of tetraethyl orthosilicate, tetrapropoxysilane, or sodium silicate.
9. The method for preparing a three-dimensional porous silicon-carbon composite material according to claim 8, wherein the porous silicon dioxide material has an ordered three-dimensional cubic pore structure and can be one of a mesoporous molecular sieve KIT-6, a micro mesoporous composite structure ZSM-5/KIT-6, ZSM-5/SBA-15, ZSM-5/MCM-41, ZSM-5/MCM-48, beta/KIT-6, beta/SBA-15 and Beta/MCM-41.
10. A three-dimensional porous silicon-carbon composite material, characterized in that the three-dimensional porous silicon-carbon composite material is obtained by the method for preparing the three-dimensional porous silicon-carbon composite material according to any one of claims 1 to 9.
CN202310270626.3A 2023-03-15 2023-03-15 Preparation method of three-dimensional porous silicon-carbon composite material and composite material thereof Pending CN116375035A (en)

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