SiNSs@Cu@PANi nanosphere structure composite material and a preparation method thereof
By stimulating nanoscale silicon spheres with light to generate photogenerated electrons and holes, and combining this with copper ion etching, in-situ polyaniline coating of SiNSs@Cu@PANi nanosphere structures was achieved. This solved the problems of volume expansion and conductivity of silicon-based anode materials and improved the performance of lithium-ion batteries.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- ZHEJIANG UNIV
- Filing Date
- 2026-02-27
- Publication Date
- 2026-06-09
Smart Images
Figure CN122177781A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of inorganic nanocomposite materials, and particularly relates to a SiNSs@Cu@PANi nanosphere structure composite material and its preparation method. Background Technology
[0002] In recent years, with the rapid development of new energy electric vehicles and portable electronic devices, the demand for high-energy-density lithium-ion batteries has been increasing daily. While graphite, a traditional lithium-ion battery anode material, possesses excellent cycle stability, its theoretical specific capacity is only 372 mAh / g, making it increasingly difficult to meet future energy storage needs. In contrast, silicon anode materials have a specific capacity of 4200 mAh / g (Li... 4.4 The superior theoretical specific capacity of silicon (Si) represents an order of magnitude improvement over traditional graphite anodes, making it a research hotspot in the field of novel high-energy-density lithium-ion battery anode materials. Furthermore, silicon exhibits a V0.4 (vs. Li / Li) + The appropriate operating potential for silicon-based anode materials is a voltage platform that effectively avoids lithium dendrite formation while maintaining a high energy density advantage. Furthermore, as the second most abundant element in the Earth's crust, silicon possesses significant resource advantages and environmental benefits. However, silicon-based anode materials still face significant challenges in practical commercial applications. First, silicon exhibits a large volume expansion effect, undergoing significant volume changes during charging and discharging, leading to problems such as particle breakage, electrode structure collapse, and separation of active material from the current collector. This mechanical stress not only damages the integrity of the electrode but also continuously exposes fresh silicon surfaces, triggering continuous SEI film growth and electrolyte consumption, ultimately resulting in rapid capacity decay. Second, the SEI film on the silicon surface is difficult to maintain integrity during volume changes; repeated breakage and regeneration consume large amounts of lithium ions and electrolyte, reducing coulombic efficiency. Additionally, an uneven SEI film may lead to excessively high local current density, causing safety issues such as lithium dendrite growth. Third, silicon, as a semiconductor material, has a relatively low intrinsic conductivity (approximately 10⁻⁶). -3 The electron transport dynamics performance of silicon-based anode materials is limited by their electron transport ratio (S / cm), which is particularly pronounced at high rates, thus restricting their application in high-power devices.
[0003] In recent years, research on silicon-based anode materials using conductive polymers (such as polyaniline and polypyrrole) has attracted increasing attention. Conductive polymers possess strong structural toughness, which, as an outer coating layer, can significantly improve the structural and interfacial stability of silicon-based anode materials. They also exhibit high conductivity, which can significantly improve the electron transport dynamics of silicon materials. As a typical representative of conductive polymers, the synthesis of polyaniline follows an oxidative radical reaction mechanism, which includes three key steps: initiation, chain growth, and termination. In the traditional preparation process of silicon / polyaniline composites, the polymerization reaction is mainly initiated by adding external chemical oxidants (such as FeCl3, ammonium persulfate, and hydrogen peroxide). However, chemical oxidation may cause some aniline monomers to oxidize prematurely in solution, resulting in uneven coating of polyaniline on the silicon material surface, or even the formation of a free phase (separate precipitation).
[0004] This invention is based on the semiconductor photoelectric effect of silicon. It utilizes light to excite nanoscale silicon spheres, causing the separation of photogenerated electrons and holes. The strong oxidizing properties of these photogenerated holes then initiate an in-situ polymerization reaction of aniline monomers on the surface of the nanoscale silicon spheres, thereby achieving in-situ coating of the nanoscale silicon spheres with polyaniline. Simultaneously, this invention introduces copper ions into the reaction system. The introduction of copper ions allows for rapid recombination with photogenerated electrons. This not only inhibits the recombination of photogenerated electrons and holes to some extent, improving the utilization efficiency of the photocurrent, but also enables the deposition of metallic copper nanoparticles, further enhancing the electronic conductivity of the composite material. Summary of the Invention
[0005] To address the aforementioned problems, this invention provides a simple, efficient, and environmentally friendly SiNSs@Cu@PANi nanosphere composite material and its preparation method.
[0006] This invention discloses a method for synthesizing nanoscale silicon sphere / copper nanoparticle / polyaniline composite materials based on the semiconductor properties of silicon. It utilizes light to excite the nanoscale silicon spheres, generating a photoelectric effect that separates photogenerated electrons and holes. Then, the strong oxidizing properties of photogenerated holes and the strong reducing properties of photogenerated electrons are used to initiate an in-situ polymerization reaction of aniline monomers on the surface of the nanoscale silicon spheres and promote a metal-assisted chemical etching reaction of silicon by copper ions. This achieves in-situ coating of polyaniline and in-situ loading of copper nanoparticles. The introduction of copper nanoparticles has two positive implications for material preparation: firstly, it can control the valence band structure of semiconductor silicon; secondly, by promoting the synchronous consumption of photogenerated electrons, it suppresses electron-hole recombination, thereby significantly enhancing the photocatalytic activity. In particular, this method offers a novel, simple, and environmentally friendly approach for preparing core-shell structured nanoscale silicon sphere / copper nanoparticle / polyaniline composite materials.
[0007] The technical solution adopted in this invention is as follows: A SiNSs@Cu@PANi nanosphere structure composite material, wherein the composite material consists of nanospheres with a particle size of 50-200 nm, and the nanospheres are composed of a polyaniline coating layer and nanoscale silicon spheres modified with copper nanoparticles encapsulated in the coating layer.
[0008] A method for developing a SiNSs@Cu@PANi nanosphere composite material includes the following steps: (1) Nanoscale silicon spheres and ammonium fluoride were dissolved and dispersed in deionized water to obtain the first dispersion; (2) Dissolve aniline and phytic acid in the first dispersion, and transfer the resulting reaction solution to an ice-water bath and continue stirring to obtain a second dispersion; (3) Dissolve the copper salt in deionized water and stir until homogeneous, then add it dropwise to the second dispersion to obtain the third dispersion; (4) The third dispersion was placed under a xenon lamp light source and photoreaction was carried out in an ice bath. After the reaction was completed, the SiNSs@Cu@PANi nanosphere composite material was obtained by centrifugation, washing and separation.
[0009] Preferably, the mass ratio of the nanoscale silicon spheres to aniline is 1:1 to 20:1; and the mass ratio of aniline to phytic acid is 1:2.
[0010] Preferably, the concentration of ammonium fluoride in the first dispersion is 0.3 mol / L; and the concentration of copper salt in the reaction solution is 0.005~0.1 mol / L.
[0011] Preferably, the copper salt is one or more of copper sulfate, copper nitrate, and copper chloride.
[0012] Preferably, the stirring time in the ice-water bath in step (2) is at least 3 hours.
[0013] Preferably, the photoreaction time in step (4) is 6 hours.
[0014] Furthermore, during the photoreaction process, the nanoscale silicon spheres generate a photoelectric effect, achieving the separation of photogenerated electrons and photogenerated holes. Then, by utilizing the strong oxidizing properties of photogenerated holes and the strong reducing properties of photogenerated electrons, an in-situ polymerization reaction of aniline monomers is initiated on the surface of the nanoscale silicon spheres, and the metal-assisted chemical etching reaction of silicon by copper ions is promoted, thereby achieving in-situ coating of polyaniline and in-situ loading of copper nanoparticles.
[0015] This invention uses nanoscale silicon spheres, aniline, and copper salts as raw materials, ammonium fluoride as an etchant, phytic acid as a polyaniline dopant, and deionized water as a reaction solvent to prepare nanoscale silicon sphere / polyaniline composite materials via photoinitiation. The preparation process can be divided into the following stages: 1. Pre-etching treatment of nanoscale silicon spheres Before preparing the nanoscale silicon sphere / copper nanoparticle / polyaniline composite material, the nanoscale silicon sphere raw material is first pretreated. When the nanoscale silicon spheres are dispersed in a mixed solution containing ammonium fluoride, the ammonium fluoride will react with the oxides (SiO₂) formed on the surface of the nanoscale silicon spheres due to natural oxidation. x Thin film etching removes the precipitate. On one hand, the etching effect of ammonium fluoride causes the surface of the nanospheres to transition from hydrophilic SiO₂. x The surface transforms into a hydrophobic silicon surface, which is more conducive to the accumulation of aniline on the surface of nanoscale silicon spheres, thus promoting photoinitiated polymerization. On the other hand, SiO₂ acts as a light filtering layer. x Removing the coating enhances the photoactivation ability of the nanoscale silicon spheres and increases the photocurrent intensity during the reaction process.
[0016] 2. Photo-initiated in-situ polymerization of aniline By adding aniline and phytic acid to the reaction dispersion after etching of nanoscale silicon spheres and then irradiating it in an ice bath, a one-step photo-initiated nanoscale silicon sphere / polyaniline composite material can be prepared. During the polymerization reaction, phytic acid acts as a dopant and crosslinking agent, promoting the formation of a three-dimensional interconnected conductive network in polyaniline, thereby improving the overall electronic conductivity of the conductive polymer. Under illumination, the nanoscale silicon spheres, as semiconductor materials, exhibit a photoelectric effect, resulting in the separation of photogenerated electrons and holes. The aniline monomers aggregated on the surface of the nanoscale silicon spheres are oxidized by the highly oxidizing photogenerated holes, thereby initiating a free radical polymerization reaction of the aniline monomers, achieving in-situ growth of polyaniline on the surface of the nanoscale silicon spheres, thus obtaining the photo-initiated nanoscale silicon sphere / polyaniline composite material.
[0017] 3. Illumination-promoted copper ion metal-assisted chemical etching reaction During the photo-initiated in-situ polymerization of aniline, photogenerated electrons from photoexcited semiconductor nanoscale silicon spheres can simultaneously drive copper ion metal-assisted chemical etching, thereby achieving in-situ loading of copper nanoparticles on the silicon sphere surface. The introduction of copper nanoparticles is beneficial for further improving the electronic conductivity of the composite material. Furthermore, the introduction of copper nanoparticles has two positive implications for material preparation: firstly, it can regulate the valence band structure of semiconductor silicon; secondly, by promoting the synchronous consumption of photogenerated electrons, it suppresses electron-hole recombination, thus significantly enhancing the photocatalytic activity.
[0018] The structure, morphology, and properties of the polyaniline-coated copper nanoparticle-modified nanoscale silicon sphere (SiNSs@Cu@PANi) composite material synthesized by one-step photodeposition using the present invention were characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), thermogravimetric analysis (TG), and X-ray photoelectron spectroscopy (XPS). The characterization revealed that the material is a core-shell structured nanosphere with a particle size of 50–200 nm, consisting of an outer polyaniline coating layer and an inner copper nanoparticle-modified nanoscale silicon sphere core.
[0019] Compared with the prior art, the beneficial effects of the present invention are: (1) This invention uses nanoscale silicon spheres as raw materials and utilizes the photoelectric effect of silicon to generate photogenerated holes and photogenerated electrons in situ on the surface of the nanoscale silicon spheres by irradiation. This, in turn, initiates the polymerization of aniline monomers in situ on the surface of the nanoscale silicon spheres and simultaneously promotes the metal-assisted chemical etching reaction of copper ions. After the photoreaction, copper nanoparticles can be loaded and polyaniline coating can be applied. Compared with the traditional chemical oxidation to introduce a conductive polymer coating layer, the preparation concept of this invention is innovative, simple to operate, and environmentally friendly. At the same time, the introduction of copper nanoparticles can, on the one hand, regulate the valence band structure of semiconductor silicon, and on the other hand, suppress electron-hole recombination by promoting the synchronous consumption of photogenerated electrons, thereby significantly enhancing the photocatalytic reaction activity.
[0020] (2) This invention synthesizes a polyaniline-coated copper nanoparticle-modified nanoscale silicon sphere composite material through one-step photodeposition. The nanoscale silicon spheres have a particle size of approximately 50–100 nm, exhibiting a typical core-shell structure. The external polyaniline coating acts as a protective layer to buffer the significant volume expansion of silicon materials during cycling and stabilize the SEI film. Simultaneously, as a conductive polymer with excellent conductivity, it significantly improves the electronic conductivity of the silicon nanoscale spheres. The internal structure consists of copper nanoparticle-modified nanoscale silicon spheres, and the introduction of copper nanoparticles further enhances the electronic conductivity of the composite material.
[0021] According to the method of the present invention, a one-step photodeposition synthesis of polyaniline-coated copper nanoparticle-modified nanoscale silicon sphere composite material can be efficiently and rapidly prepared, and the prepared material does not require subsequent processing. Therefore, the present invention provides a method for rapidly preparing a one-step photodeposition synthesis of polyaniline-coated copper nanoparticle-modified nanoscale silicon sphere composite material. The polyaniline-coated copper nanoparticle-modified nanoscale silicon sphere composite material synthesized by the present invention in a one-step photodeposition process has great application potential in the field of silicon-based lithium-ion battery anode materials. Attached Figure Description
[0022] Figure 1 These are the infrared (FT-IR) spectra of Embodiment 1 and Comparative Examples 1 to 3 of the present invention.
[0023] Figure 2 These are scanning electron microscope (SEM) images of Embodiment 1 and Comparative Examples 1-3 of the present invention.
[0024] Figure 3 This is the XPS spectrum of Embodiment 1 of the present invention.
[0025] Figure 4 These are the (TG) diagrams of Embodiment 1 and Comparative Examples 1-3 of the present invention in an argon atmosphere. Detailed Implementation
[0026] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but the present invention is not limited to the following examples.
[0027] Example 1 (1) Weigh 0.1 g of nano-sized silica spheres and 0.333 g of ammonium fluoride, disperse and dissolve them in 30 mL of deionized water, stir for 24 h to obtain a pale yellow first dispersion; (2) Measure 100 μL of aniline and 280 μL of 50% phytic acid aqueous solution, dissolve them in the first dispersion, and stir in an ice bath for 3 h to obtain the second dispersion; (3) Weigh 0.075 g of copper sulfate pentahydrate and dissolve it in the second dispersion to obtain the third dispersion; (4) The third dispersion was placed under a xenon lamp light source and subjected to photoreaction in an ice bath for 6 hours; (5) After the reaction was completed, the SiNSs@Cu@PANi nanosphere composite material was obtained by centrifugation at 6000 r / min, followed by repeated washing with deionized water and anhydrous ethanol, and then drying.
[0028] Example 2 (1) Weigh 0.1 g of nano-sized silica spheres and 0.333 g of ammonium fluoride, disperse and dissolve them in 30 mL of deionized water, stir for 24 h to obtain a pale yellow first dispersion; (2) Measure 50 μL of aniline and 140 μL of 50% phytic acid aqueous solution, dissolve them in the first dispersion, and stir in an ice bath for 3 h to obtain the second dispersion; (3) Weigh 0.075 g of copper sulfate pentahydrate and dissolve it in the second dispersion to obtain the third dispersion; (4) The third dispersion was placed under a xenon lamp light source and subjected to photoreaction in an ice bath for 6 hours; (5) After the reaction was completed, the SiNSs@Cu@PANi nanosphere composite material was obtained by centrifugation at 6000 r / min, followed by repeated washing with deionized water and anhydrous ethanol, and then drying.
[0029] Example 3 (1) Weigh 0.1 g of nano-sized silica spheres and 0.333 g of ammonium fluoride, disperse and dissolve them in 30 mL of deionized water, stir for 24 h to obtain a pale yellow first dispersion; (2) Measure 25 μL of aniline and 70 μL of 50% phytic acid aqueous solution, dissolve them in the first dispersion, and stir in an ice bath for 3 h to obtain the second dispersion; (3) Weigh 0.075 g of copper sulfate pentahydrate and dissolve it in the second dispersion to obtain the third dispersion; (4) The third dispersion was placed under a xenon lamp light source and subjected to photoreaction in an ice bath for 6 hours; (5) After the reaction was completed, the SiNSs@Cu@PANi nanosphere composite material was obtained by centrifugation at 6000 r / min, followed by repeated washing with deionized water and anhydrous ethanol, and then drying.
[0030] Example 4 (1) Weigh 0.1 g of nano-sized silica spheres and 0.333 g of ammonium fluoride, disperse and dissolve them in 30 mL of deionized water, stir for 24 h to obtain a pale yellow first dispersion; (2) Measure 10 μL of aniline and 28 μL of phytic acid aqueous solution with a mass fraction of 50%, dissolve them in the first dispersion, and stir in an ice bath for 3 h to obtain the second dispersion; (3) Weigh 0.075 g of copper sulfate pentahydrate and dissolve it in the second dispersion to obtain the third dispersion; (4) The third dispersion was placed under a xenon lamp light source and subjected to photoreaction in an ice bath for 6 hours; (5) After the reaction was completed, the SiNSs@Cu@PANi nanosphere composite material was obtained by centrifugation at 6000 r / min, followed by repeated washing with deionized water and anhydrous ethanol, and then drying.
[0031] Example 5 (1) Weigh 0.1 g of nano-sized silica spheres and 0.333 g of ammonium fluoride, disperse and dissolve them in 30 mL of deionized water, stir for 24 h to obtain a pale yellow first dispersion; (2) Measure 5 μL of aniline and 14 μL of 50% phytic acid aqueous solution, dissolve them in the above dispersion, and stir in an ice bath for 3 h to obtain a second dispersion; (3) Weigh 0.075 g of copper sulfate pentahydrate and dissolve it in the second dispersion to obtain the third dispersion; (4) The third dispersion was placed under a xenon lamp light source and subjected to photoreaction in an ice bath for 6 hours; (5) After the reaction was completed, the SiNSs@Cu@PANi nanosphere composite material was obtained by centrifugation at 6000 r / min, followed by repeated washing with deionized water and anhydrous ethanol, and then drying.
[0032] Example 6 (1) Weigh 0.1 g of nano-sized silica spheres and 0.333 g of ammonium fluoride, disperse and dissolve them in 30 mL of deionized water, stir for 24 h to obtain a pale yellow first dispersion; (2) Measure 100 μL of aniline and 280 μL of 50% phytic acid aqueous solution, dissolve them in the above dispersion, and stir in an ice bath for 3 h to obtain a second dispersion; (3) Weigh 0.75 g of copper sulfate pentahydrate and dissolve it in the second dispersion to obtain the third dispersion; (4) The third dispersion was placed under a xenon lamp light source and subjected to photoreaction in an ice bath for 6 hours; (5) After the reaction was completed, the SiNSs@Cu@PANi nanosphere composite material was obtained by centrifugation at 6000 r / min, followed by repeated washing with deionized water and anhydrous ethanol, and then drying.
[0033] Example 7 (1) Weigh 0.1 g of nano-sized silica spheres and 0.333 g of ammonium fluoride, disperse and dissolve them in 30 mL of deionized water, stir for 24 h to obtain a pale yellow first dispersion; (2) Measure 100 μL of aniline and 280 μL of 50% phytic acid aqueous solution, dissolve them in the above dispersion, and stir in an ice bath for 3 h to obtain a second dispersion; (3) Weigh 0.038 g of copper sulfate pentahydrate and dissolve it in the second dispersion to obtain the third dispersion; (4) The third dispersion was placed under a xenon lamp light source and subjected to photoreaction in an ice bath for 6 hours; (5) After the reaction was completed, the SiNSs@Cu@PANi nanosphere composite material was obtained by centrifugation at 6000 r / min, followed by repeated washing with deionized water and anhydrous ethanol, and then drying.
[0034] Example 8 (1) Weigh 0.1 g of nano-sized silica spheres and 0.333 g of ammonium fluoride, disperse and dissolve them in 30 mL of deionized water, stir for 24 h to obtain a pale yellow first dispersion; (2) Measure 100 μL of aniline and 280 μL of 50% phytic acid aqueous solution, dissolve them in the above dispersion, and stir in an ice bath for 3 h to obtain a second dispersion; (3) Weigh 0.041 g of copper chloride and dissolve it in the second dispersion to obtain the third dispersion; (4) The third dispersion was placed under a xenon lamp light source and subjected to photoreaction in an ice bath for 6 hours; (5) After the reaction was completed, the SiNSs@Cu@PANi nanosphere composite material was obtained by centrifugation at 6000 r / min, followed by repeated washing with deionized water and anhydrous ethanol, and then drying.
[0035] Example 9 (1) Weigh 0.1 g of nano-sized silica spheres and 0.333 g of ammonium fluoride, disperse and dissolve them in 30 mL of deionized water, stir for 24 h to obtain a pale yellow first dispersion; (2) Measure 100 μL of aniline and 280 μL of 50% phytic acid aqueous solution, dissolve them in the above dispersion, and stir in an ice bath for 3 h to obtain a second dispersion; (3) Weigh 0.056 g of copper nitrate and dissolve it in the second dispersion to obtain the third dispersion; (4) The third dispersion was placed under a xenon lamp light source and subjected to photoreaction in an ice bath for 6 hours; (5) After the reaction was completed, the SiNSs@Cu@PANi nanosphere composite material was obtained by centrifugation at 6000 r / min, followed by repeated washing with deionized water and anhydrous ethanol, and then drying.
[0036] Comparative Example 1 Weigh 0.1 g of nanoscale silicon spheres and 0.333 g of ammonium fluoride, disperse and dissolve them in 30 mL of deionized water, and stir for 24 h. Then, centrifuge at 6000 r / min, wash repeatedly with deionized water and anhydrous ethanol, and dry to obtain nanoscale silicon sphere material.
[0037] Comparative Example 2 (1) Measure 100 μL of aniline and 280 μL of 50% phytic acid aqueous solution, dissolve them in deionized water, and stir in an ice bath for 3 h; (2) Add 50 μL of 20% hydrogen peroxide aqueous solution to the above solution and react for 6 h; (3) After the reaction is completed, centrifuge at 6000 r / min, then wash repeatedly with deionized water and anhydrous ethanol, and dry to obtain polyaniline material.
[0038] Comparative Example 3 (1) Weigh 0.1 g of nano-sized silicon spheres and 0.333 g of ammonium fluoride, and disperse and dissolve them in 30 mL of deionized water, stirring for 24 h; (2) Measure 100 μL of aniline and 280 μL of 50% phytic acid aqueous solution, dissolve them in the above dispersion, and stir in an ice bath for 3 h; (3) Place the above reaction solution under a xenon lamp light source and carry out the photoreaction in an ice bath for 6 hours; (4) After the reaction was completed, the mixture was centrifuged at 6000 r / min, then washed repeatedly with deionized water and anhydrous ethanol, and dried to obtain the polyaniline-coated nanoscale silicon sphere composite material prepared by photoinitiation.
[0039] Figure 1 The following are the infrared (FT-IR) spectra of SiNSs@Cu@PANi nanosphere composite material synthesized by one-step photodeposition (Example 1) and Comparative Examples 1-3: It can be seen that both Example 1 and Comparative Example 3 successfully introduced polyaniline coating layers, proving that photoinitiation to achieve in-situ coating of semiconductor silicon with polyaniline is feasible.
[0040] Figure 2The following are scanning electron microscope (SEM) images of the SiNSs@Cu@PANi nanosphere composite material synthesized by one-step photodeposition (Example 1) and Comparative Examples 1 and 3 (where a is Example 1, b is Comparative Example 3, and c is Comparative Example 1): It can be seen that compared with Comparative Example 1 (etched nanoscale silicon spheres), the surfaces of Examples 1 and 3 are rougher, further demonstrating that photoinitiation can achieve in-situ coating of polyaniline on the surface of nanoscale silicon spheres. Meanwhile, compared with Comparative Example 3, the introduction of copper ions can promote in-situ coating of polyaniline, resulting in a thicker polyaniline coating layer on the surface.
[0041] Figure 3 XPS spectra of the SiNSs@Cu@PANi nanosphere composite material synthesized by one-step photodeposition (Example 1): Figure 3 The XPS spectrum in (a) clearly demonstrates the successful introduction of polyaniline, and the presence of copper further confirms the successful introduction of copper nanoparticles. From... Figure 3 The presence of Si-OC chemical bonds can be found in the Si 2p spectrum of (b), which indicates that a certain chemical interaction is formed between the polyaniline coating layer introduced by photodeposition and the nanoscale silicon spheres, which is beneficial to further improve the structural stability of the composite material.
[0042] Figure 4 The following are the (TG) graphs of the SiNSs@Cu@PANi nanosphere composite material synthesized by one-step photodeposition (Example 1) and Comparative Examples 1-3 in an argon atmosphere: It can be seen that, with other reaction conditions unchanged, the introduction of copper ions can greatly promote the in-situ polymerization reaction of polyaniline on the surface of nanoscale silicon spheres. This is mainly because the introduction of copper ions into the reaction system can, on the one hand, achieve the loading of copper nanoparticles, thereby regulating the valence band structure of semiconductor silicon; on the other hand, by promoting the synchronous consumption of photogenerated electrons, it suppresses electron-hole recombination, thus significantly enhancing the photocatalytic reaction activity. Finally, the mass percentages of the polyaniline coating in Example 1 and Comparative Example 3 were 29.67 wt% and 13.46 wt%, respectively.
[0043] The above description is merely a preferred embodiment of the present invention. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make many possible variations and modifications to the technical solutions of the present invention using the methods and techniques disclosed above, or modify them into equivalent embodiments with equivalent changes, without departing from the scope of the technical solutions of the present invention. Therefore, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solutions of the present invention shall still fall within the protection scope of the technical solutions of the present invention.
Claims
1. A SiNSs@Cu@PANi nanosphere structured composite material, characterized in that, The composite material consists of nanospheres with a particle size of 50–200 nm, which are composed of a polyaniline coating layer and nanoscale silicon spheres modified with copper nanoparticles encapsulated in the coating layer.
2. A method for developing a SiNSs@Cu@PANi nanosphere composite material, characterized in that, Includes the following steps: (1) Nanoscale silicon spheres and ammonium fluoride were dissolved and dispersed in deionized water to obtain the first dispersion; (2) Dissolve aniline and phytic acid in the first dispersion, and transfer the resulting reaction solution to an ice-water bath and continue stirring to obtain a second dispersion; (3) Dissolve the copper salt and add it to the second dispersion to obtain the third dispersion; (4) The third dispersion was placed under a xenon lamp light source and photoreaction was carried out in an ice bath. After the reaction was completed, the SiNSs@Cu@PANi nanosphere composite material was obtained by centrifugation, washing and separation.
3. The method for preparing the SiNSs@Cu@PANi nanosphere composite material according to claim 2, characterized in that, The mass ratio of the nanoscale silicon spheres to aniline is 1:1 to 20:1; the mass ratio of aniline to phytic acid is 1:
2.
4. The method for preparing the SiNSs@Cu@PANi nanosphere composite material according to claim 2, characterized in that, In the first dispersion, the concentration of ammonium fluoride is 0.3 mol / L; in the third dispersion, the concentration of copper salt is 0.005~0.1 mol / L.
5. The method for preparing the SiNSs@Cu@PANi nanosphere composite material according to claim 2, characterized in that, The copper salt is one or more of copper sulfate, copper nitrate, and copper chloride.
6. The method for preparing the SiNSs@Cu@PANi nanosphere structure composite material according to claim 2, characterized in that, The stirring time in the ice-water bath in step (2) is at least 3 hours.
7. The method for preparing the SiNSs@Cu@PANi nanosphere structure composite material according to claim 2, characterized in that, The photoreaction time in step (4) is 6 hours.
8. The method for preparing the SiNSs@Cu@PANi nanosphere composite material according to claim 2, characterized in that, During the photoreaction process, the nanoscale silicon spheres generate a photoelectric effect, achieving the separation of photogenerated electrons and photogenerated holes. Then, by utilizing the strong oxidizing properties of photogenerated holes and the strong reducing properties of photogenerated electrons, an in-situ polymerization reaction of aniline monomers is initiated on the surface of the nanoscale silicon spheres, and the metal-assisted chemical etching reaction of silicon by copper ions is promoted, thereby achieving in-situ coating of polyaniline and in-situ loading of copper nanoparticles.