CN113193195A - Nitrogen-doped carbon-coated nano silicon composite material with adjustable nitrogen content and preparation method thereof - Google Patents
Nitrogen-doped carbon-coated nano silicon composite material with adjustable nitrogen content and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 76
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- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 52
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 49
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
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- GIOKUMNZQFCEPI-UHFFFAOYSA-N 3-[methyl-[2-[methyl-[3-(3,4,5-trimethoxybenzoyl)oxypropyl]amino]ethyl]amino]propyl 3,4,5-trimethoxybenzoate;dihydrochloride Chemical compound Cl.Cl.COC1=C(OC)C(OC)=CC(C(=O)OCCCN(C)CCN(C)CCCOC(=O)C=2C=C(OC)C(OC)=C(OC)C=2)=C1 GIOKUMNZQFCEPI-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention provides a nitrogen-doped carbon-coated nano-silicon composite material with adjustable nitrogen content and a preparation method thereof, and the preparation method comprises the following steps: the nano silicon and the tetraethoxysilane are subjected to hydrolysis reaction under the action of ammonia water as a catalyst to synthesize Si @ SiO2Particles; reacting Si @ SiO2Dispersing in hydrochloric acid solution containing aniline and o-phenylenediamine, adding ammonium persulfate solution to initiate polymerization reaction, drying the obtained product, and calcining at high temperature to form Si @ SiO2@NC；Si@SiO2And etching the @ NC with hydrofluoric acid to form an egg yolk structure Si @ void @ NC. The invention can control the monomerThe relative concentration of the aniline and the o-phenylenediamine realizes the adjustability of the doping amount of nitrogen elements, further improves the electrochemical performance of the material, has the advantages of mild reaction conditions, simple equipment, simplicity and convenience in operation, safety, reliability and the like, and has good charge-discharge cycle performance and rate capability when being used as a lithium/sodium ion battery cathode material.
Description
Technical Field
The invention relates to the technical field of battery cathode material manufacturing, in particular to a preparation method of a nitrogen-doped carbon-coated nano silicon composite material with adjustable nitrogen content.
Background
The lithium ion battery has the characteristics of safety, long service life, convenience and portability, so that the lithium ion battery is widely applied to the fields of numerous electronic products as a portable novel energy source. Currently, lithium ion batteries are developing towards lithium type battery materials with high specific capacity, high rate cycling performance and high safety performance.
The negative electrode material is a very important component of the lithium ion battery, and directly influences the energy density and the electrochemical performance of the lithium ion battery. The theoretical specific capacity of the traditional graphite cathode material is 372mAh/g, and the requirement of a high-specific-energy lithium ion battery cannot be met. Silicon is due to its high theoretical capacity (4200mAh/g), low intercalation potential (< 0.5Vvs. Li/Li)+) And the advantages of abundant reserves and the like are widely concerned. However, silicon as a negative electrode material has problems of poor conductivity, large volume expansion effect, unstable surface solid electrolyte membrane, and the like, and application thereof to a lithium ion battery is hindered. The carbon-coated silicon can inhibit the expansion of the silicon and increase the conductivity of the silicon so as to improve the electrochemical performance of the silicon cathode. Recently, it has been shown that doping the carbon layer with nitrogen can increase the conductivity of the material, provide additional active sites, and increase the reversible capacity of the composite material (Journal of Power Sources 2016,318: 184-191). Wangdan et al (CN 106941174A) disclose a method for preparing nitrogen-doped silicon-carbon composite negative electrode material by taking acrylamide as nitrogen source; bin et al (CN 109786666a) disclose a method for preparing a nitrogen-doped carbon-coated silicon nanoparticle composite material, in which dopamine is used as a nitrogen source; song also man et al (CN 111628148A) disclose a preparation method of a core-shell structure silicon-nitrogen doped carbon composite negative electrode material, which uses resorcinol and formaldehyde as carbon sources, and (C)cHdNeOk)nIs a nitrogen source. Although the composite material of nitrogen-doped carbon-coated silicon is successfully prepared by the technologies, the performance of the composite material is improved to a certain extent, in the methods, a single organic matter is selected as a nitrogen source, the doping proportion of nitrogen elements in a carbon layer is fixed, and the doping amount is low. Particularly, the conductivity of the carbon layer is affected by the nitrogen doping amount, and the wettability of the carbon-coated silicon composite materials with different nitrogen doping ratios in different electrolyte systems and the reaction activity difference of lithium ions are large.
In order to solve the difference in the technologies, the invention provides a preparation technology of a carbon-coated silicon composite material with adjustable nitrogen doping amount, wherein the doping ratio of nitrogen to carbon in the technology can be adjusted in a wider range, so that the composite material has better compatibility in different electrolyte systems, and further shows excellent electrochemical performance.
Disclosure of Invention
The invention provides a nitrogen-doped carbon-coated nano silicon composite material with adjustable nitrogen content and a preparation method thereof, wherein An sacrificial silicon dioxide template is introduced between silicon and carbon to serve as a void layer, and a copolymer of aniline (An) and o-phenylenediamine (OPD) serves as a nitrogen-doped carbon shell protective layer to prepare the nano silicon @ nitrogen-doped carbon composite material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a nitrogen-doped carbon-coated nano silicon composite material with adjustable nitrogen content comprises the following steps:
(1) the nano silicon and the tetraethoxysilane are subjected to hydrolysis reaction under the action of ammonia water as a catalyst to synthesize Si @ SiO2Particles;
(2) reacting Si @ SiO2Dispersing in hydrochloric acid solution containing aniline and o-phenylenediamine, adding ammonium persulfate to initiate polymerization reaction, drying the obtained product, and calcining at high temperature to form Si @ SiO2@NC；
(3)Si@SiO2Hydrofluoric acid for @ NCAnd forming an egg yolk structure Si @ void @ NC after etching.
According to the scheme, the particle size of the nano silicon powder is 30-150 nm
According to the scheme, the reaction condition in the step (1) is that the magnetic stirring is carried out in a water bath at the temperature of 25-40 ℃ for 4-12 hours.
According to the scheme, the dispersion is dispersed by an ultrasonic device.
According to the scheme, the mass ratio of the tetraethoxysilane to the nano-silicon is 1: 1-15: 1.
According to the scheme, the total concentration of the aniline and the o-phenylenediamine is 0.04-0.2 mol// L, and the ratio of the amounts of the o-phenylenediamine and the aniline is 0-4. The thickness of the carbon layer in the present invention can be controlled by the concentration of the polymerized monomers (aniline and o-phenylenediamine), and the cycle stability is gradually enhanced as the concentration of the polymerized monomers is decreased. This phenomenon occurs because when the carbon layer is thick, the migration process of lithium ions from the electrolyte to the silicon core is affected, and the reduction of the monomer concentration can realize the reduction of the carbon layer thickness, thereby improving the cycle performance of the material.
According to the scheme, the polymerization condition is that the reaction is carried out for 4-12 hours under the temperature of 0-40 ℃ by magnetic stirring.
According to the scheme, the high-temperature calcination condition is that the temperature rise rate is 2-5 ℃/min, the carbonization temperature is 400-900 ℃, and the carbonization time is 0.5-4 h under the argon atmosphere.
According to the scheme, the mass fraction of the hydrofluoric acid solution is 5%, and the etching time is 0.5-2 h.
In detail, the preparation method of the nitrogen-doped carbon-coated nano silicon composite material with adjustable nitrogen content comprises the following steps:
(1) weighing nano silicon, dispersing the nano silicon into deionized water containing ethanol, ultrasonically dispersing, slowly dripping ammonia water, and continuously stirring; slowly dripping 3-aminopropyltriethoxysilane, and continuously stirring; finally, slowly dripping ethyl orthosilicate and continuously stirring; the solid was separated off, washed and dried, and the sample obtained was designated as Si @ SiO2；
(2) Adding a certain amount of Si @ SiO2Dispersing in ethanol, slowly adding hydrochloric acid dropwise under stirring, and adding benzeneAdding amine and o-phenylenediamine monomers into the dispersion liquid, and continuously stirring; slowly dropwise adding an ammonium persulfate aqueous solution, reacting for 4-12 h, washing and drying. Annealing the obtained sample at a high temperature of 400-900 ℃ for 0.5-4 h at a heating rate of 2-5 ℃/min under the protection of argon atmosphere gas to obtain Si @ SiO2@NC；
(3) Reacting Si @ SiO2And dispersing the @ NC into an HF acid solution, continuously stirring, finally centrifugally washing with deionized water and ethanol, drying at the temperature of 40-60 ℃ for 6-10 h, and marking the obtained sample as Si @ void @ NC.
The nitrogen-doped carbon-coated nano-silicon composite material with adjustable nitrogen content is of a yolk shell type structure: si @ void @ NC, wherein Si is used as a core, the N-doped carbon layer NC is used as a shell, and a gap layer is arranged between the Si core and the NC shell.
A nitrogen-doped carbon-coated nano-silicon composite material-based half battery comprises a nitrogen-doped carbon-coated nano-silicon composite material, conductive carbon black and polyvinylidene fluoride, wherein N-methyl pyrrolidone is used as a solvent, battery slurry is prepared and coated on copper foil, a counter electrode is made of lithium metal, and a button battery is assembled to obtain the half battery.
According to the nitrogen-doped carbon-coated nano-silicon composite material-based half battery, the composite material, conductive carbon black and polyvinylidene fluoride (PVDF) are mixed into battery slurry by taking N-methyl pyrrolidone (NMP) as a solvent according to the mass ratio of 8:1:1, the battery slurry is coated on copper foil, and metal lithium is taken as a counter electrode to assemble a CR2032 type button battery, so that the half battery used for testing is obtained. The binder plays a main role in the electrode preparation process to bind the active material and the conductive agent together while adhering to the current collector. Adhesion is a key property of the adhesive to battery performance. In the prior art, carboxymethyl cellulose (CMC) is often used as a binder, the CMC can generate stronger bonding capacity with the silicon surface to form a relatively stable electrode structure, and the pulverization of silicon during multiple volume changes is inhibited, but the reversibility of silicon during lithium intercalation/lithium deintercalation is influenced by the too strong bonding force of a covalent bond, and finally the electrode fails. Compared with CMC, PVDF is more widely applied, has more excellent viscosity and electrochemical stability, and is beneficial to improving the mechanical stability and the cycle life of the silicon cathode.
Compared with the prior art, the invention has the following remarkable advantages:
(1) the nitrogen-doped carbon-coated nano silicon composite material with adjustable nitrogen content is of a yolk shell structure, and a gap layer between silicon and carbon provides a space for volume change generated in the process of removing/embedding lithium ions by silicon; the common core-shell type is that a carbon layer is coated outside a silicon core, and the yolk type core-shell structure is that a clearance layer is arranged between the silicon core and the carbon layer, and is similar to an egg structure, and the clearance layer is egg white. The volume change of the silicon in the lithium ion elimination/insertion process reaches four times of the volume change of the silicon, the introduction of the void layer can lead the silicon to freely expand/contract in the lithium ion elimination/insertion process so as to avoid the damage of an outer carbon shell, and the outer carbon shell can be used as a protective layer so as to avoid the exposure of an inner silicon core in electrolyte.
(2) According to the nitrogen-doped carbon-coated nano silicon composite material with adjustable nitrogen content, the aniline and o-phenylenediamine copolymer is used as the nitrogen-doped carbon layer, so that the conductivity of the material can be effectively improved, and a stable SEI film is formed. Meanwhile, nitrogen is doped, and defects can be caused around the nitrogen, and the defects can provide additional lithium storage capacity; by controlling An: the quantity ratio of OPD substances realizes the regulation and control of the doping quantity and the doping proportion of nitrogen elements, realizes the adjustability of nitrogen relative to carbon, and can effectively improve the electrochemical performance.
(3) The hydrolysis of TEOS and APTES is utilized, and Si @ SiO is obtained after the hydrolysis of APTES2The surface of the material is provided with amino (-NH)2) The silicon dioxide nano-silica-based polymer carbon material can be used as an initiation site of subsequent polymerization to form a uniform coating layer, a smooth silicon dioxide template can be formed on the surface of a nano-silicon, the smooth silicon dioxide layer is beneficial to subsequent coating of a polymer carbon material, and APTES mainly promotes TEOS to form the uniform silicon dioxide coating layer on the surface of the nano-silicon. The carbon layer enhances the conductivity of the material on the one hand and acts as a protective layer to reduce the exposure of the silicon to the electrolyte on the other hand. The volume expansion effect of silicon is mainly buffered by the void layer and partly by the carbon layer. When the coating effect of the carbon layer is poor, the silicon is repeatedly inserted/removed with lithium to crack the uneven carbon layer, and the failure of the carbon layer causes the silicon to be exposed in the electrolyte, which shows that the specific capacity of the electrode isRapid decrease and poor cycle stability. The carbon layer cladding of this application is even, can effectively avoid above problem. Compared with the homopolymerization reaction of aniline, the copolymer formed by o-phenylenediamine and aniline can be uniformly coated with Si @ SiO2The particles and the coating layer formed at the same time are thinner, so that the Si @ void @ NC composite material with a relatively thinner carbon layer can be obtained, and the cycle stability and the first discharge specific capacity of the silicon electrode can be improved.
(4) The preparation method of the nitrogen-doped carbon-coated nano silicon composite material with adjustable nitrogen content has the advantages that the reaction conditions are easy to control, no special requirements are required on equipment, and the operation is simple and convenient; compared with the traditional chemical deposition method, the synthetic route is simple and the cost is low; compared with a ball milling method and a solvothermal method, the synthesized silicon-carbon composite material is high in structural strength and good in cycling stability.
Drawings
FIG. 1 is a transmission electron micrograph of a product of example 1 of the present invention;
FIG. 2 is an X-ray photoelectron spectrum of the product of example 1 of the present invention;
FIG. 3 is a graph of discharge cycle performance for the product of example 1 and the comparative product made with different An to OPD ratios according to the present invention.
Detailed Description
Example 1:
the invention provides a preparation method of a nitrogen-doped carbon-coated nano silicon composite material with adjustable nitrogen content, which comprises the following steps:
(1) weighing 250mg of nano silicon powder, dispersing into a flask containing 280mL of ethanol and 70mL of deionized water, performing ultrasonic dispersion for 15-30 minutes, then placing the flask into a water bath kettle, and keeping magnetic stirring at 25 ℃.4mL of aqueous ammonia (14.5 mol/L) was slowly added dropwise with stirring for 60 minutes. Then, 0.4mL of 3-Aminopropyltriethoxysilane (APTES) was slowly added dropwise thereto, and the mixture was stirred for 30 minutes. Finally, 3g of tetraethyl orthosilicate (TEOS) were slowly added dropwise, and stirring was maintained for 12 hours. And finally, centrifugally washing the sample for 3-4 times by using deionized water and ethanol, and drying the washed sample for 8 hours in vacuum at the temperature of 50 ℃, wherein the obtained sample is marked as Si @ SiO2；
(2) 1.2g of synthesized Si @ SiO2Ultrasonically dispersing in 100mL of ethanol, and slowly dripping 8335mL of hydrochloric acid solution (12mol/L) is continuously stirred for 10-20 minutes. And then adding aniline and o-phenylenediamine monomer into the dispersion according to the mass ratio of 5:5 (the total mass is 0.01mol), carrying out ultrasonic treatment for 20-30 minutes, and continuously stirring in a water bath kettle at 25 ℃. Finally, 10mL of ammonium persulfate aqueous solution (2.85 g of ammonium persulfate dissolved in 10mL of deionized water) is slowly dropped to react for 4 hours, and the reaction solution is washed and dried. Annealing the obtained sample at 800 ℃ for 2 hours at the heating rate of 2 ℃/min under the protection of argon atmosphere gas to obtain Si @ SiO2@NC；
(3) Weighing 1.0g of Si @ SiO2@ NC was dispersed in a 5% by mass HF acid solution and stirred continuously for 1 hour. And finally, centrifugally washing the sample by using deionized water and ethanol for 3-4 times, and drying the sample at the temperature of 50 ℃ for 8 hours to obtain the sample marked as Si @ void @ NC.
Comparative example: under the same other conditions, the nitrogen-doped carbon-coated nano silicon composite material with adjustable nitrogen content is prepared by changing the proportion of the aniline and the o-phenylenediamine.
The prepared material is analyzed by a transmission electron microscope, the figure 1 can clearly distinguish the void layer of the composite material between the silicon core and the carbon shell, and the carbon layer is uniformly coated with the nano silicon. The prepared material is subjected to X-ray photoelectron spectroscopy analysis, the result is shown in figure 2, and the sample contains four elements of silicon, carbon, nitrogen and oxygen which are shown in figure 2, so that the successful doping of the nitrogen element is proved. The product of example 1 is made into a lithium ion battery negative pole piece, and a charge-discharge performance test is carried out on the lithium ion battery negative pole piece, and the result is shown in fig. 3, when the mass ratio of the aniline to the o-phenylenediamine is 5:5, the cycling stability of the material is better, and the capacity is kept above 600mAh/g after 30 cycles at the current density of 0.1A/g. The improved cycling stability is attributed to the coating of nitrogen-doped carbon, which blocks the attack of the electrolyte on the silicon core, and the nitrogen doping improves the conductivity of the material and provides lithium storage capability. The relative concentration of polymeric monomer aniline and o-phenylenediamine is simply controlled, so that the doping amount of nitrogen in the carbon layer can be regulated and controlled, and the electrochemical performance is effectively improved. The preparation method of the nitrogen-doped carbon-coated nano-silicon composite material with adjustable nitrogen content provided by the invention is simple and convenient to operate, and the prepared material has good electrochemical performance and wide commercialization prospect.
TABLE 1 Nitrogen-doped carbon-coated nano-silicon prepared by different An: OPD ratios has relative nitrogen content. As can be seen from Table 1, the nitrogen content relative to the carbon content of the prepared nitrogen-doped carbon-coated nano silicon composite material is changed along with the difference of An and OPD, so that the nitrogen content relative to the carbon content can be adjusted.
Example 2:
the invention provides a preparation method of a nitrogen-doped carbon-coated nano silicon composite material with adjustable nitrogen content, which comprises the following steps:
(1) weighing 250mg of nano silicon powder, dispersing into a flask containing 280mL of ethanol and 70mL of deionized water, performing ultrasonic dispersion for 15-30 minutes, then placing the flask into a water bath kettle, and keeping magnetic stirring at 30 ℃.4mL of aqueous ammonia (14.5 mol/L) was slowly added dropwise with stirring for 60 minutes. Then, 0.4mL of APTES was slowly added dropwise with stirring for 30 minutes. Finally, 2.4g of tetraethyl orthosilicate (TEOS) were slowly added dropwise, and stirring was maintained for 4 hours. And finally, centrifugally washing the sample for 3-4 times by using deionized water and ethanol, and drying the washed sample for 8 hours in vacuum at the temperature of 50 ℃, wherein the obtained sample is marked as Si @ SiO2；
(2) 1.2g of synthesized Si @ SiO2Ultrasonically dispersing the mixture in 100mL of ethanol, slowly and dropwise adding 8.335mL of hydrochloric acid solution (12mol/L), and continuously stirring for 10-20 minutes. And then adding aniline and o-phenylenediamine monomer into the dispersion according to the mass ratio of 8:2 (the total mass is 0.02mol), carrying out ultrasonic treatment for 20-30 minutes, and continuously stirring in a water bath kettle at 30 ℃. Finally, 10mL of ammonium persulfate aqueous solution (2.85 g of ammonium persulfate dissolved in 10mL of deionized water) is slowly dropped and reacted for 12 hours, and then the reaction solution is washed and dried. Annealing the obtained sample at the high temperature of 500 ℃ for 4 hours at the heating rate of 5 ℃/min under the protection of argon atmosphere gas to obtain Si @ SiO2@NC；
(3) Weighing 1.0gSi @ SiO2@ NC was dispersed in a 5% by mass HF acid solution and stirred continuously for 1 hour. And finally, centrifugally washing the sample by using deionized water and ethanol for 3-4 times, and drying the sample at the temperature of 40 ℃ for 10 hours to obtain the sample marked as Si @ void @ NC.
Example 3:
the invention provides a preparation method of a nitrogen-doped carbon-coated nano silicon composite material with adjustable nitrogen content, which comprises the following steps:
(1) weighing 250mg of nano silicon powder, dispersing into a flask containing 280mL of ethanol and 70mL of deionized water, performing ultrasonic dispersion for 15-30 minutes, then placing the flask into a water bath kettle, and keeping magnetic stirring at 35 ℃.4mL of aqueous ammonia (14.5 mol/L) was slowly added dropwise with stirring for 60 minutes. Then, 0.4mL of APTES was slowly added dropwise with stirring for 30 minutes. Finally, 1.4g of tetraethyl orthosilicate (TEOS) was slowly added dropwise, and stirring was maintained for 18 hours. And finally, centrifugally washing the sample for 3-4 times by using deionized water and ethanol, and drying the washed sample for 8 hours in vacuum at the temperature of 50 ℃, wherein the obtained sample is marked as Si @ SiO2；
(2) 1.2g of synthesized Si @ SiO2Ultrasonically dispersing the mixture in 100mL of ethanol, slowly and dropwise adding 8.335mL of hydrochloric acid solution (12mol/L), and continuously stirring for 10-20 minutes. And then adding aniline and o-phenylenediamine monomer into the dispersion according to the mass ratio of 10:0 (the total mass is 0.01mol), carrying out ultrasonic treatment for 20-30 minutes, and continuously stirring in a water bath kettle at 35 ℃. Finally, 10mL of ammonium persulfate aqueous solution (2.85 g of ammonium persulfate dissolved in 10mL of deionized water) is slowly dropped and reacted for 8 hours, and then the reaction solution is washed and dried. Annealing the obtained sample at the high temperature of 700 ℃ for 1 hour at the heating rate of 3 ℃/min under the protection of argon atmosphere gas to obtain Si @ SiO2@NC；
(3) Weighing 1.0g of Si @ SiO2@ NC was dispersed in a 5% by mass HF acid solution and stirred continuously for 1 hour. And finally, centrifugally washing the sample by using deionized water and ethanol for 3-4 times, and drying the sample at the temperature of 60 ℃ for 6 hours to obtain the sample marked as Si @ void @ NC.
Example 4:
the invention provides a preparation method of a nitrogen-doped carbon-coated nano silicon composite material with adjustable nitrogen content, which comprises the following steps:
(1) weighing 250mg of nano silicon powder, dispersing into a flask containing 280mL of ethanol and 70mL of deionized water, performing ultrasonic dispersion for 15-30 minutes, then placing the flask into a water bath kettle, and keeping magnetic stirring at 40 ℃.4mL of aqueous ammonia (14.5 mol/L) was slowly added dropwise with stirring for 60 minutes. Then 0.4mL of APTES is slowly added dropwise, and the mixture is continuously stirred for 30 minutesA clock. Finally, 1.2g of tetraethyl orthosilicate (TEOS) was slowly added dropwise, and stirring was maintained for 24 hours. And finally, centrifugally washing the sample for 3-4 times by using deionized water and ethanol, and drying the washed sample for 8 hours in vacuum at the temperature of 50 ℃, wherein the obtained sample is marked as Si @ SiO2；
(2) 1.2g of synthesized Si @ SiO2Ultrasonically dispersing the mixture in 100mL of ethanol, slowly and dropwise adding 8.335mL of hydrochloric acid solution (12mol/L), and continuously stirring for 10-20 minutes. Then, mixing aniline and o-phenylenediamine monomer according to the mass ratio of 2: 8 (the total substance amount is 0.004mol), adding the dispersion into the dispersion, performing ultrasonic treatment for 20-30 minutes, and continuously stirring the mixture in a water bath kettle at 40 ℃. Finally, 10mL of ammonium persulfate aqueous solution (2.85 g of ammonium persulfate dissolved in 10mL of deionized water) is slowly dropped and reacted for 12 hours, and then the reaction solution is washed and dried. Annealing the obtained sample at 800 ℃ for 2 hours at the heating rate of 2 ℃/min under the protection of argon atmosphere gas to obtain Si @ SiO2@NC；
(3) Weighing 1.0g of Si @ SiO2And @ NC is dispersed into 5 percent HF acid solution by mass fraction and continuously stirred for 30 min. And finally, centrifugally washing the sample by using deionized water and ethanol for 3-4 times, and drying the sample at the temperature of 50 ℃ for 8 hours to obtain the sample marked as Si @ void @ NC.
TABLE 1 Nitrogen relative content of N-doped carbon-coated nano-silicon composite materials prepared by different An: OPD ratios
Claims (10)
1. The preparation method of the nitrogen-doped carbon-coated nano silicon composite material with adjustable nitrogen content is characterized by comprising the following steps of:
(1) the nano silicon and the tetraethoxysilane are subjected to hydrolysis reaction under the action of ammonia water as a catalyst to synthesize Si @ SiO2Particles;
(2) the above Si @ SiO2Dispersing in mixed hydrochloric acid solution of aniline and o-phenylenediamine, adding oxidant to initiate polymerization reaction, drying the obtained product, and calcining at high temperature to form Si @ SiO2@NC；
(3) The above-mentioned Si @ SiO2@NAnd C, etching by using hydrofluoric acid to form the Si @ void @ NC composite material.
2. The method for preparing the nitrogen-doped carbon-coated nano-silicon composite material with adjustable nitrogen content according to claim 1, wherein the particle size of the nano-silicon powder is 30-150 nm.
3. The preparation method of the nitrogen-doped carbon-coated nano-silicon composite material with adjustable nitrogen content as claimed in claim 1, wherein the reaction condition in the step (1) is water bath magnetic stirring at 25-40 ℃ for 4-12 h.
4. The preparation method of the nitrogen-doped carbon-coated nano-silicon composite material with adjustable nitrogen content according to claim 1, wherein the mass ratio of the tetraethoxysilane to the nano-silicon is 1: 1-15: 1.
5. The method for preparing the nitrogen-doped carbon-coated nano silicon composite material with adjustable nitrogen content according to claim 1, wherein the total concentration of the aniline and the o-phenylenediamine is 0.04 to 0.2mol/L, and the ratio of the amounts of the o-phenylenediamine and the aniline is 0 to 4.
6. The method for preparing nitrogen-doped carbon-coated nano-silicon composite material with adjustable nitrogen content as claimed in claim 1, wherein the polymerization condition is 0-40 ℃ and the reaction time is 4-12 h.
7. The method for preparing the nitrogen-doped carbon-coated nano-silicon composite material with adjustable nitrogen content according to claim 1, wherein the high-temperature calcination condition is an argon atmosphere, the temperature rise rate is 2-5 ℃/min, the carbonization temperature is 400-900 ℃, and the carbonization time is 0.5-4 h.
8. The method for preparing the nitrogen-doped carbon-coated nano-silicon composite material with adjustable nitrogen content according to claim 1, wherein the hydrofluoric acid solution is 5% by mass and the etching time is 0.5-2 h.
9. The nitrogen-doped carbon-coated nano-silicon composite material with adjustable nitrogen content is characterized in that the nitrogen-doped carbon-coated nano-silicon is of a yolk shell type structure: si @ void @ NC, wherein Si is used as a core, the N-doped carbon layer NC is used as a shell, and a gap layer is arranged between the Si core and the NC shell.
10. A nitrogen-doped carbon-coated nano-silicon composite material-based half battery is characterized by comprising a nitrogen-doped carbon-coated nano-silicon composite material, conductive carbon black and polyvinylidene fluoride, wherein N-methyl pyrrolidone is used as a solvent, battery slurry is prepared and coated on copper foil, a counter electrode is made of lithium metal, and a button battery is assembled to obtain the half battery.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114420910A (en) * | 2022-01-19 | 2022-04-29 | 山东能源集团有限公司 | Nitrogen-doped silicon-carbon composite material with core-shell structure and preparation method thereof |
| CN114551882A (en) * | 2022-01-12 | 2022-05-27 | 华南师范大学 | Ferric fluoride cathode material and preparation method and application thereof |
| CN114804070A (en) * | 2022-04-06 | 2022-07-29 | 北京化工大学 | Preparation method of carbon nano hemispherical particles |
| WO2023133814A1 (en) * | 2022-01-14 | 2023-07-20 | 宁德时代新能源科技股份有限公司 | Composite material in yolk/core-shell structure, preparation method, and secondary battery containing composite material in yolk/core-shell structure |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012005180A1 (en) * | 2010-07-05 | 2012-01-12 | 独立行政法人産業技術総合研究所 | Electrode material, electrode containing same, battery, method for producing electrode material precursor, and method for producing electrode material using the method for producing electrode material precursor |
| CN106450251A (en) * | 2016-12-23 | 2017-02-22 | 合肥工业大学 | Anode material for Li-ion batteries and preparation method thereof |
| WO2019005411A1 (en) * | 2017-06-29 | 2019-01-03 | Powermers Inc. | An electrode for an electrochemical power source and an electrochemical power source comprising said electrode |
| CN110600718A (en) * | 2019-08-16 | 2019-12-20 | 南京理工大学 | Yolk double-carbon-shell structure silicon-based lithium ion battery cathode material and preparation method thereof |
-
2021
- 2021-04-25 CN CN202110448749.2A patent/CN113193195A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012005180A1 (en) * | 2010-07-05 | 2012-01-12 | 独立行政法人産業技術総合研究所 | Electrode material, electrode containing same, battery, method for producing electrode material precursor, and method for producing electrode material using the method for producing electrode material precursor |
| CN106450251A (en) * | 2016-12-23 | 2017-02-22 | 合肥工业大学 | Anode material for Li-ion batteries and preparation method thereof |
| WO2019005411A1 (en) * | 2017-06-29 | 2019-01-03 | Powermers Inc. | An electrode for an electrochemical power source and an electrochemical power source comprising said electrode |
| CN110600718A (en) * | 2019-08-16 | 2019-12-20 | 南京理工大学 | Yolk double-carbon-shell structure silicon-based lithium ion battery cathode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 黄仁忠: "锂离子电池纳米硅基负极的制备及电化学性能研究", 《中国硕士学位论文全文数据库工程科技I辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114551882A (en) * | 2022-01-12 | 2022-05-27 | 华南师范大学 | Ferric fluoride cathode material and preparation method and application thereof |
| WO2023133814A1 (en) * | 2022-01-14 | 2023-07-20 | 宁德时代新能源科技股份有限公司 | Composite material in yolk/core-shell structure, preparation method, and secondary battery containing composite material in yolk/core-shell structure |
| CN114420910A (en) * | 2022-01-19 | 2022-04-29 | 山东能源集团有限公司 | Nitrogen-doped silicon-carbon composite material with core-shell structure and preparation method thereof |
| CN114420910B (en) * | 2022-01-19 | 2023-12-01 | 山东能源集团有限公司 | Nitrogen-doped silicon-carbon composite material with core-shell structure and preparation method thereof |
| CN114804070A (en) * | 2022-04-06 | 2022-07-29 | 北京化工大学 | Preparation method of carbon nano hemispherical particles |
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