A surface elastomer coating of silicon-containing particles of an organic-inorganic interpenetrating network structure and a method for preparing the same

Abstract

The application discloses a kind of organic-inorganic interpenetrating network structure's silicon-containing particle surface elastomer coating and its preparation method, the preparation method disperses carbon nanotube in polymer A solution, silicon-containing particle is added to further disperse composite, then after spray drying, polymer B solution is added, flocculation precipitate is formed, and the final product is obtained after collecting precipitate and spray drying again.The application uses a variety of polymers to gradually modify single-walled carbon nanotubes, and inorganic silicon-containing active particles are added simultaneously to form an interpenetrating network structure, which has good electronic and ionic conductivity, excellent viscoelasticity and adhesion, can adhere to the surface of silicon-containing particles continuously and tightly during the volume expansion and contraction of silicon-containing particles during electrochemical charging and discharging, maintain stable electronic and ionic transmission at the micro and macro levels, and maintain the surface of negative electrode plate flat, sufficiently reduce the overpotential on the surface of silicon-containing particles, effectively inhibit the rapid growth of SEI film, and achieve high electrochemical charging and discharging stability and extremely high coulomb efficiency.

Description

Technical Field

[0001] This invention belongs to the field of lithium-ion battery technology, specifically relating to an organic-inorganic interpenetrating network structure of a silicon-containing particle surface elastomer coating layer and its preparation method. Background Technology

[0002] Lithium-ion batteries consist of five parts: positive electrode material, negative electrode material, electrolyte, separator, and casing. Currently, graphite is the primary negative electrode material used in lithium-ion batteries, holding a market share of over 90%. However, its low specific capacity (theoretically 372 mAh / g) hinders further development. Silicon / silicon suboxide has a specific capacity exceeding that of graphite by 10 times / 5 times, making it a promising direction for the development of negative electrode materials for lithium-ion batteries. However, the volume expansion and contraction of silicon (>300%) and silicon suboxide (>200%) during charge-discharge cycles severely affect the stable operation of lithium-ion batteries. Furthermore, silicon repeatedly forms unstable SEI films in lithium-ion batteries, accelerating electrode damage.

[0003] To overcome the problems of low coulombic efficiency and high expansion rate of silicon, many research groups at home and abroad have made considerable efforts. Among the many materials, single-walled carbon nanotubes have been confirmed to effectively improve the stability of silicon / silicon suboxide during battery cycling. The main reasons are based on the following two aspects: (1) Single-walled carbon nanotubes have excellent conductivity. Silicon / silicon suboxide, as a semiconductor, has the defect of poor conductivity when used in lithium-ion batteries. In the poor conductivity battery environment, the lithium insertion and delithiation of silicon / silicon suboxide are extremely uneven, resulting in polarization and reducing the cycle life of the battery. Single-walled carbon nanotubes themselves have good conductivity. At the same time, the nanoscale carbon nanotubes can form effective electrical contact sites with silicon, which ensures the conductivity of silicon / silicon suboxide anode materials while improving electron transport efficiency and improving the overall electrochemical performance. (2) Single-walled carbon nanotubes have the characteristics of both rigidity and flexibility. Flexible single-walled carbon nanotubes (SHUs) are similar to "segments" of polymer molecules, exhibiting localized movement without overall displacement. This effectively mitigates the volume expansion of silicon / silicon suboxide during the charging and discharging process of lithium-ion batteries. The flexibility of SHUs is also reflected in their resilience; when silicon / silicon suboxide particles shrink, the SHUs maintain good contact with them, reducing the growth of malignant SEI (silicon-embedded interphase). The rigidity of SHUs is manifested in their high mechanical strength, ensuring that the electrode surface does not crack during cycling and promoting tight bonding among the components.

[0004] Early research on the application of single-walled carbon nanotubes (SUCs) in lithium-ion batteries mainly focused on methods for preparing SUC and silicon composite materials. For example, reference 10.1021 / jp1063403 (J.Phys.Chem.C2010,114,15862–15867) describes using pulsed laser deposition (PLD) to deposit silicon onto SUC paper to obtain Si / SWCNT flexible paper. Electrochemical measurements showed that under charge-discharge conditions of 25 mA / g, the 2.2% Si / SWCNT composite material exhibited a capacity of 163 mA h g⁻¹ after 50 cycles, representing a capacity increase of over 60% compared to the original SUCs. Later, with the deepening research on silicon as a negative electrode material for lithium-ion batteries, the silicon-single-walled carbon nanotube composite system no longer only included the two mentioned above. Metals, carbon materials, and other organic / inorganic materials were successively introduced into this system. For example, in reference 10.1016 / j.nanoen.2012.09.007, silicon was added to a germanium nanoparticle-single-walled carbon nanotube (Ge-NP:SWCNT) hybrid electrode, which improved the electrochemical performance of a high-capacity independent anode in lithium-ion batteries. Electrochemical tests showed that the charging capacity of the Si-Ge-NP:SWCNT independent anode exceeded 1200 mAh / g, with an initial coulombic efficiency of 85%. In addition, the team led by Wei Fei at Tsinghua University combined high aspect ratio single-walled carbon nanotubes with SiO2... X A SiOx@C|SWCNT composite material was successfully prepared, achieving an initial coulombic efficiency of 81.52%, which to some extent solves the problem of low initial coulombic efficiency in silicon oxide. After 200 cycles, the capacity still remained at 915.89 mAh / g. Even under tensile stress as high as 6.2 GPa, SWCNTs maintained good contact with SiOx@C. However, it should be noted that large-scale production of high aspect ratio single-walled carbon nanotubes still faces challenges, and the high cost also limits its application in silicon / silicon suboxide anode materials. In conclusion, the high cost of single-walled carbon nanotubes greatly restricts their use in the field of composite material preparation.

[0005] Besides the aforementioned composite approaches, another promising approach is the incorporation of single-walled carbon nanotubes (SWCNTs) into binders for use in lithium-ion batteries. For example, reference 10.1007 / s11581-019-03391-w describes how adding a small amount of SWCNTs as a conductive additive to the SiO / C anode improves electrochemical performance, achieving a capacity retention of 90.30% after 600 cycles at 1C. The blend of SWCNTs and organic binders can significantly buffer the volume expansion of silicon-based materials, effectively suppressing electrode structural damage. Furthermore, Professor Wang Jiaping's research group at Tsinghua University proposed a "dispersion-anchoring" strategy to improve the uniformity of nano-silicon electrodes, thereby reducing the loss of active material and promoting cycle stability. Their initial coulombic efficiency exceeded 89%, and after 200 cycles, they still maintained a capacity of 1164.5 mAh / g, demonstrating better cycle stability. For example, Chinese invention patent CN112331831B uses a specific composite process involving a silicon anode sheet, porous copper foil, and single-walled carbon nanotubes. This allows silicon particles in the silicon anode undercoat to enter the pores of the porous copper foil, reserving space for silicon particle expansion. Simultaneously, the single-walled carbon nanotubes form a conductive network, and their rigidity inhibits silicon expansion and growth, resulting in a volumetric energy density exceeding 800 Wh / L. Another example is Chinese invention patent CN115954458A, where the inventors use a novel binder that combines commonly used silicon-based anode binders with single-walled carbon nanotubes. Electrochemical tests on the silicon-based anode showed a capacity retention rate exceeding 80% after 400 cycles, with an electrode expansion rate of approximately 60%.

[0006] However, most of the above studies involve mechanically mixing single-walled carbon nanotubes and binders. Such binders have poor bonding with silicon-containing particles and have significant limitations in practical applications. For example, it is difficult to solve the problem of dispersibility of single-walled carbon nanotubes in aqueous systems and the depolymerization of polymers and single-walled carbon nanotubes after deep cycling, which affects battery life.

[0007] Therefore, a silicon-containing particle surface elastomer coating layer with an organic-inorganic interpenetrating network structure and its preparation method are urgently needed. Summary of the Invention

[0008] To address the shortcomings of existing technologies, this invention provides an organic-inorganic interpenetrating network structure for coating silicon-containing particles with an elastomer coating layer and a method for preparing the same.

[0009] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0010] The first objective of this invention is to provide an organic-inorganic interpenetrating network structure for a silicon-containing particle surface elastomeric coating layer. The elastomeric coating layer includes a grafted 3D network structure and a fabric-like structure formed by inorganic and organic components. The inorganic components include carbon nanotubes and silicon-containing particles, and the organic components include polymer A and polymer B. The grafted 3D network structure is used to provide a tough-rigid skeleton, and the fabric-like structure is used to increase the viscoelasticity and adhesion of the system.

[0011] Preferably, the carbon nanotube is one of single-walled carbon nanotube and multi-walled single-walled carbon nanotube; the polymer A and polymer B are one of polyacrylic acid, sodium carboxymethyl cellulose, chitosan, guar gum, sodium alginate, gellan gum, and pectin, and the polymer A and polymer B use different components.

[0012] The second objective of this invention is to provide a method for preparing an elastomeric coating layer on the surface of silicon-containing particles with an organic-inorganic interpenetrating network structure, comprising the following steps: dispersing carbon nanotubes in a polymer A solution, adding silicon-containing particles therein for further dispersion and composite, then spray drying the mixture and adding it to a polymer B solution to form a flocculated precipitate, collecting the precipitate and spray drying it again to obtain the final product.

[0013] Preferably, it includes the following steps:

[0014] S1. Dispersion of carbon nanotubes in polymer A: Dissolve polymer A in water and stir vigorously until a homogeneous solution is formed. Then add carbon nanotubes and sonicate to obtain a dispersion CNTs / Pol-1@Liq; where polymer A is not explicitly referred to as Pol-1.

[0015] S2, Composite of silicon-containing particles and dispersion CNTs / Pol-1@Liq: Add silicon-containing particles to the dispersion CNTs / Pol-1@Liq prepared in step S1, sonicate to form a uniform dispersion, and then spray dry to obtain dry powder SiOx / CNTs / Pol-1 (0≤x≤1);

[0016] S3. Preparation of the final product: The dry powder SiOx / CNTs / Pol-1 (0≤x≤1) prepared in step S2 is mixed evenly with polymer B in water. The precipitate is collected and then spray-dried to obtain dry powder Pol-2 / SiOx / CNTs / Pol-1 (0≤x≤1); where polymer B is not explicitly referred to as Pol-2.

[0017] Preferably, the carbon nanotube is one of single-walled carbon nanotube or multi-walled single-walled carbon nanotube.

[0018] Preferably, polymer A and polymer B are one of polyacrylic acid, sodium carboxymethyl cellulose, chitosan, guar gum, sodium alginate, gellan gum, and pectin, and polymer A and polymer B are prepared using different components.

[0019] Preferably, the mass ratio of the carbon nanotubes to polymer A is 1:(0.5-2).

[0020] Preferably, the mass ratio of the silicon-containing particles to the carbon nanotubes is 8:(0.5-1).

[0021] Preferably, the mass ratio of the dry powder SiOx / CNTs / Pol-1 (0≤x≤1) to polymer B is (8~10):(0.5~1).

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] In this invention, the polymer forms a tight coating layer on the surface of silicon-containing particles, which, together with the single-walled carbon nanotube framework embedded in the coating layer, inhibits the excessively rapid growth of the SEI film. The fabric-like structure formed on the surface of the battery electrode is resistant to the repeated volume expansion and contraction of the active silicon-containing particles during charging and discharging, maintaining good contact on the electrode surface without detachment. This invention provides excellent viscoelasticity and adhesion to constrain the silicon-containing particles and conductive components in a fixed position, so that the silicon / silicon suboxide particles do not lose electrical contact during charging and discharging expansion. The synergistic effect between the various components leads to the high initial coulombic efficiency of the nano-silicon / silicon suboxide anode.

[0024] This invention employs a variety of polymers to progressively modify single-walled carbon nanotubes, while simultaneously incorporating inorganic silicon-containing active particles to form an interpenetrating network structure. This structure exhibits excellent electronic and ionic conductivity, superior viscoelasticity, and adhesion. It can continuously and tightly adhere to the surface of silicon-containing particles during the electrochemical charge-discharge volume expansion and contraction process, maintaining stable electron and ion transport at both the micro and macro levels and ensuring the flatness of the negative electrode surface. This effectively reduces the overpotential on the surface of silicon-containing particles, suppresses excessively rapid SEI film growth, and achieves high electrochemical charge-discharge stability and extremely high coulombic efficiency. Attached Figure Description

[0025] Figure 1 This is a reference figure showing the relative motion mechanism between the additive and silicon-based particles during the charging and discharging process of this invention;

[0026] Figure 2 This is a schematic diagram showing the fragmentation of silicon particles before and after charging and discharging according to the present invention.

[0027] Figure 3 This is a SEM image of the surface of the negative electrode sheet prepared in Example 1 of this invention;

[0028] Figure 4This is a SEM image (another region) of the surface of the negative electrode sheet prepared in Example 1 of the present invention;

[0029] Figure 5 This is a charge-discharge curve of the negative electrode sheet prepared in Example 1 of the present invention;

[0030] Figure 6 These are the electrochemical impedance spectra of the negative electrode sheets prepared in Example 1 and Comparative Example 3 of this invention after 50 cycles. Detailed Implementation

[0031] The preferred embodiments of the present invention will be described below with reference to the accompanying drawings. It should be understood that the preferred embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0032] Example 1

[0033] This embodiment provides an organic-inorganic interpenetrating network structure for a silicon-containing particle surface elastomeric coating layer. The elastomeric coating layer includes a grafted 3D network structure and a fabric-like structure formed by inorganic and organic components. The inorganic components include carbon nanotubes and silicon-containing particles, and the organic components include polymer A and polymer B. The grafted 3D network structure is used to provide a tough-rigid skeleton, and the fabric-like structure is used to increase the viscoelasticity and adhesion of the system.

[0034] This embodiment also provides a method for preparing an elastomer coating layer on the surface of silicon-containing particles with an organic-inorganic interpenetrating network structure. First, carbon nanotubes are dispersed in a polymer solution A. Then, silicon-containing particles are added to the solution for further dispersion and composite formation. After spray drying, the mixture is added to a polymer solution B to form a flocculated precipitate. The precipitate is collected and spray-dried again to obtain the final product. Specifically, the preparation steps are as follows:

[0035] (1) Dispersion of single-walled carbon nanotubes in polymer A: 2g of sodium carboxymethyl cellulose was dissolved in 198g of water and stirred vigorously until a uniform and transparent solution was formed. 1g of single-walled carbon nanotubes was added to the solution and ultrasonically dispersed evenly with an ultrasonic gun to obtain a dispersion of CNTs / CMC@Liq. The ultrasonic conditions were 40-50W for 1h.

[0036] (2) Composite of silicon particles and CNTs / Pol-1@Liq: 8g of Si particles were weighed and added to 100ml of CNTs / CMC@Liq. After ultrasonication to form a uniform dispersion, the mixture was spray-dried to obtain dry Si / CNTs / CMC powder. The ultrasonication conditions were: 40-50W for 1h. The spray drying conditions were: inlet air temperature: 220℃, outlet temperature: 100℃, and feed rate: 5ml / min.

[0037] (3) Preparation of the final product: The dry powder Si / CNTs / CMC in step (2) is mixed evenly with 0.5g of polyacrylic acid in 200ml of water, and then spray-dried to obtain dry powder PAA / Si / CNTs / CMC (0.5:8:0.5:1).

[0038] Example 2

[0039] The preparation method of Example 1 is different from that of Example 1 in that: the polymer B is selected as chitosan, and the final dry powder CTS / Si / CNTs / CMC (0.5:8:0.5:1) is obtained.

[0040] Example 3

[0041] The preparation method of Example 1 is different from that of Example 1 in that: the polymer B is sodium alginate, and the final dry powder SA / Si / CNTs / CMC (0.5:8:0.5:1) is obtained.

[0042] Example 4

[0043] The preparation method of Example 1 is different from that of Example 1 in that: polymer A is selected as gellan gum, and the final powder is named CTS / Si / CNTs / GG (0.5:8:0.5:1).

[0044] Example 5

[0045] The preparation method of Example 1 is different from that of Example 1 in that: polymer A is selected as pectin, and the final dry powder CTS / Si / CNTs / PT (0.5:8:0.5:1) is obtained.

[0046] Example 6

[0047] The preparation method according to Example 1 differs from that in Example 1 in that the mass ratio of single-walled carbon nanotubes and sodium carboxymethyl cellulose in step (1) is 1:1, and the final dry powder PAA / Si / CNTs / CMC (0.5:8:0.5:0.5) is obtained.

[0048] Example 7

[0049] The preparation method according to Example 1 differs from that in Example 1 in that the mass ratio of single-walled carbon nanotubes and sodium carboxymethyl cellulose in step (1) is 1:0.5, and the final dry powder PAA / Si / CNTs / CMC (0.5:8:0.5:0.25) is obtained.

[0050] Example 8

[0051] The preparation method according to Example 1 differs from that in Example 1 in that the mass ratio of silicon particles to single-walled carbon nanotubes in step (2) is 8:1, and the final dry powder PAA / Si / CNTs / CMC (0.5:8:1:2) is obtained.

[0052] Example 9

[0053] The preparation method according to Example 1 differs from that in Example 1 in that the mass ratio of silicon particles to single-walled carbon nanotubes in step (2) is 9:1, and the final dry powder PAA / Si / CNTs / CMC (1:8:0.33:0.67) is obtained.

[0054] Example 10

[0055] The preparation method according to Example 1 differs from that in Example 1 in that the silicon-containing particles in step (2) are selected as SiO, and the final dry powder PAA / SiO / CNTs / CMC (0.5:8:0.5:1) is obtained.

[0056] Example 11

[0057] The preparation method according to Example 1 differs from that in Example 1 in that: in step (2), the silicon-containing particles are selected as a mixture of SiO and Si with a mass ratio of 1:1, and finally dry powder PAA / SiO@Si / CNTs / CMC (0.5:8:0.5:1) is obtained.

[0058] Comparative Example 1

[0059] The preparation method according to Example 1 differs from that in Example 1 in that 0.1g of single-walled carbon nanotubes are used in step (1).

[0060] Comparative Example 2

[0061] The preparation method according to Example 1 differs from that in Example 1 in that step (3) is omitted.

[0062] Comparative Example 3

[0063] The preparation method according to Example 1 differs from that in Example 1 in that: single-walled carbon nanotubes are not added in step (1).

[0064] Performance testing

[0065] Figure 1 , 2 The relative motion changes of each component in the system during the lithium insertion-delithiation process and the working principle of the elastic coating layer on the surface of silicon-containing particles were demonstrated.

[0066] (1) The structure and morphology of the negative electrode sheet are characterized as follows:

[0067] The negative electrode sheet prepared in Example 1 was characterized by scanning electron microscopy (SEM), such as... Figure 2 , 3 As shown, a woven-like structure with single-walled carbon nanotubes as the framework was observed on the surface of the negative electrode material, especially... Figure 3 "Well" and "o" shaped surfaces were observed.

[0068] The first-cycle charge-discharge performance of the negative electrode sheet prepared in Example 1 was characterized using the following method: After standing for 12 hours, under a charge-discharge rate of 0.1C, the electrode was first discharged to 0.001V to obtain the discharge curve, and then charged to 2V to obtain the charging curve. Figure 4 As shown, the first-cycle charge and discharge capacities of the composite material are 3295.0 mAh / g and 3631.8 mAh / g, respectively, corresponding to a first-cycle coulombic efficiency of 87.2%.

[0069] The cyclic performance of the elastic coating / silicon-containing particle composite material prepared in Example 1 was characterized by the following method: under a charge-discharge rate of 0.2C, the discharge capacity was obtained by first discharging to 0.001V and then charging to 2V to obtain the charge capacity. The discharge-charge ratio capacity was obtained by mass normalization.

[0070] (2) Mass fraction and lithium storage performance of silicon / silicon suboxide-based materials:

[0071] The silicon / silicon suboxide-based composite material prepared in the examples was subjected to electrochemical performance testing. All electrochemical performance tests were conducted by assembling CR2032 type button half-cells. The specific assembly method was as follows:

[0072] A lithium metal sheet with a thickness of 1 mm and a diameter of 16 mm was used as the counter electrode; 1 mol / L LiPF6 / EC:DEC:DMC (1:1:1) was used as the electrolyte; a polypropylene microporous membrane was used as the separator; and the battery was assembled in a glove box filled with Ar gas.

[0073] The battery testing system is model LAND CT3002A, with a voltage range of 0.001 to 2V.

[0074] The lithium storage performance test results of the prepared electrode sheets are as follows (Table 1):

[0075]

[0076] As can be seen from the data in Table 1, the prepared elastomer coating layer on the surface of silicon particles with an organic-inorganic interpenetrating network structure improves the initial coulombic efficiency and cycle stability of the silicon particle negative electrode sheet.

[0077] The comparison of test results from Examples 1-5 shows that sodium carboxymethyl cellulose and polyacrylic acid are more suitable for polymers A and B. For polymer A, gellan gum and pectin are not well-suited for dispersing single-walled carbon nanotubes (SUVs), resulting in SUVs being difficult to disperse uniformly in the system. When SUVs are ultrasonically dispersed in carboxymethyl cellulose, polymer A can adhere to the SUVs, thus achieving good dispersion. For polymer B, polyacrylic acid provides stronger adhesion and tack. Although sodium alginate and chitosan have higher mechanical strength and inhibit the expansion of silicon-containing particles, their brittleness is greater than that of polyacrylic acid, causing the silicon-containing particles to break and pulverize, making it difficult for them to continue to act as binders.

[0078] Examples 1, 6-9 illustrate the effect of the component content on the electrochemical performance of the half-cell. The appropriate use of single-walled carbon nanotubes provides better protection for the electrode surface. An organic-inorganic interpenetrating network formed with single-walled carbon nanotubes as the 3D framework creates a dense coating layer on the surface of the silicon-containing particles. (Refer to electron microscopy). Figure 3 , 4 In Example 1, the best electrochemical performance was obtained, with a total single-walled carbon nanotube content of 5 wt%. Furthermore, the ratio of polymers A and B directly affects the electrochemical lithium storage performance of the silicon-containing particles; the optimal ratio of polymers A and B is 1:1. In Comparative Example 1, the amount of single-walled carbon nanotubes added is extremely low, making it difficult to meet the requirements for preparing an organic-inorganic interpenetrating network elastomer coating layer. Therefore, the resulting negative electrode has poor cycle performance. In Comparative Example 2, using only one polymer makes it difficult to obtain good electrochemical performance because its binding properties are concentrated on one polymer, without any additional performance enhancement.

[0079] Examples 1, 10, and 11 demonstrate that the elastomeric coating layer on the surface of silicon-containing particles with an organic-inorganic interpenetrating network structure prepared in this invention is beneficial for improving the initial coulombic efficiency and more stable cycling performance of silicon-containing particles (SiOx, 0≤x≤1). In particular, the initial coulombic efficiency of SiO is difficult to exceed 60%, but in this example, it reaches 78.8%, which is attributed to the modification of SiO particles by the organic-inorganic interpenetrating network elastomeric coating layer. A comparison between Example 1 and Comparative Example 3 shows that single-walled carbon nanotubes play a crucial role in the organic-inorganic interpenetrating network. Electrochemical performance shows that single-walled carbon nanotubes not only improve the initial coulombic efficiency of pure silicon particles but also significantly enhance cycling performance. Furthermore, Figure 6 The electrochemical impedance spectroscopy (EIS) spectra of Example 1 and Comparative Example 3 after 50 cycles are shown. The sample in Example 1 exhibits a lower electron transfer resistance (≈47 Ω) and a larger Warburg slope, while the sample in Comparative Example 3 has an electron transfer resistance much greater than 47 Ω. Figure 6This demonstrates the necessity of single-walled carbon nanotubes, which enhance the electron and ion transport efficiency in the battery and can still function normally after the silicon-containing particles expand and break apart.

[0080] In summary, the interpenetrating network structure of this invention exhibits excellent electronic and ionic conductivity, superior viscoelasticity, and adhesion. It can continuously and tightly adhere to the surface of silicon-containing particles during the electrochemical charge-discharge volume expansion and contraction process, maintaining stable electron and ion transport at both the micro and macro levels and ensuring the flatness of the negative electrode surface. This effectively reduces the overpotential on the surface of silicon-containing particles, suppresses excessively rapid SEI film growth, and achieves high electrochemical charge-discharge stability and extremely high coulombic efficiency.

[0081] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. An organic-inorganic interpenetrating network structure with a silicon-containing particle surface elastomer coating layer, characterized in that, The elastomeric encapsulation layer comprises a grafted 3D network structure and a fabric-like structure formed from inorganic and organic components. The inorganic components include carbon nanotubes and silicon-containing particles, and the organic components include polymer A and polymer B. The grafted 3D network structure provides a tough-rigid skeleton, and the fabric-like structure increases the viscoelasticity and adhesion of the system.

2. The silicon-containing particle surface elastomer coating layer of the organic-inorganic interpenetrating network structure according to claim 1, characterized in that, The carbon nanotubes are one of single-walled carbon nanotubes and multi-walled single-walled carbon nanotubes; the polymer A and polymer B are one of polyacrylic acid, sodium carboxymethyl cellulose, chitosan, guar gum, sodium alginate, gellan gum, and pectin, and polymer A and polymer B use different components.

3. A method for preparing an elastomeric coating layer on the surface of silicon-containing particles with an organic-inorganic interpenetrating network structure as described in claim 1, characterized in that, Includes the following steps: Carbon nanotubes are dispersed in polymer A solution, and silicon-containing particles are added to further disperse and composite them. After spray drying, they are added to polymer B solution to form flocculation and precipitation. The precipitate is collected and spray dried again to obtain the final product.

4. The method for preparing the elastomeric coating layer on the surface of silicon-containing particles with an organic-inorganic interpenetrating network structure according to claim 3, characterized in that, Specifically, the following steps are included: S1. Dispersion of carbon nanotubes in polymer A: Dissolve polymer A in water and stir vigorously until a homogeneous solution is formed. Then add carbon nanotubes and sonicate to obtain a dispersion of CNTs / Pol-1@Liq. S2, Composite of silicon-containing particles and dispersion CNTs / Pol-1@Liq: Add silicon-containing particles to the dispersion CNTs / Pol-1@Liq prepared in step S1, sonicate to form a uniform dispersion, and then spray dry to obtain dry powder SiOx / CNTs / Pol-1, 0≤x≤1; S3. Preparation of the final product: The dry powder SiOx / CNTs / Pol-1, 0≤x≤1 prepared in step S2 is mixed evenly with polymer B in water, the precipitate is collected and then spray-dried to obtain dry powder Pol-2 / SiOx / CNTs / Pol-1, 0≤x≤1.

5. The method for preparing the elastomeric coating layer on the surface of silicon-containing particles with an organic-inorganic interpenetrating network structure according to claim 4, characterized in that, The carbon nanotubes are one type of single-walled carbon nanotubes or multi-walled single-walled carbon nanotubes.

6. The method for preparing the elastomeric coating layer on the surface of silicon-containing particles with an organic-inorganic interpenetrating network structure according to claim 4, characterized in that, The polymer A and polymer B are one of polyacrylic acid, sodium carboxymethyl cellulose, chitosan, guar gum, sodium alginate, gellan gum, and pectin, and different components are used in the preparation of polymer A and polymer B.

7. The method for preparing the elastomeric coating layer on the surface of silicon-containing particles with an organic-inorganic interpenetrating network structure according to claim 4, characterized in that, The mass ratio of the carbon nanotubes to polymer A is 1:(0.5~2).

8. The method for preparing the elastomeric coating layer on the surface of silicon-containing particles with an organic-inorganic interpenetrating network structure according to claim 4, characterized in that, The mass ratio of the silicon-containing particles to carbon nanotubes is 8. : (0.5~1).

9. The method for preparing the elastomeric coating layer on the surface of silicon-containing particles with an organic-inorganic interpenetrating network structure according to claim 4, characterized in that, The mass ratio of the dry powder SiOx / CNTs / Pol-1 to polymer B is (8~10):(0.5~1), where 0≤x≤1.

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