Preparation of self-repairing adhesive of supramolecular network containing gradient hydrogen bonds and application of self-repairing adhesive in silicon-based lithium battery
By constructing a supramolecular network self-healing adhesive containing ureidopyrimidinone and citric acid, the problem of insufficient cycle life in silicon-based lithium batteries was solved, achieving efficient self-healing and strong adhesion, thus extending battery life.
Patent Information
- Application Number
- CN202511080829.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-04
- Publication Date
- 2025-11-21
AI Technical Summary
Existing self-healing binders cannot effectively improve the cycle life and performance of silicon-based lithium batteries, especially in terms of volume expansion and lithium-ion diffusion kinetics.
By preparing a supramolecular network self-healing adhesive containing four hydrogen bonds between ureidopyrimidinones and hydrogen bonds between acrylic acid and citric acid, a six-arm star-shaped block structure is constructed using free radical polymerization technology to form a multi-level dynamic hydrogen bond network, thereby enhancing the self-healing ability and adhesion strength of the adhesive, which is suitable for silicon-based lithium batteries.
It extends the cycle life of silicon-based lithium batteries, improves the structural integrity and self-healing performance of the batteries, effectively releases the internal stress of silicon particles, and maintains the stability of the electrodes.
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Figure CN120988620A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of silicon-based lithium batteries, and particularly relates to preparation of a self-repairing adhesive containing a gradient hydrogen bond supramolecular network and application thereof in silicon-based lithium batteries. BACKGROUND
[0002] With the continuous development of related industries, lithium ion batteries mainly using graphite (372 mAh·g -1 ) as the negative electrode gradually cannot meet the market demand. Therefore, a material with high specific capacity, low delithiation potential (<0.5 V) and abundant reserves is urgently needed to replace graphite as a new negative electrode material. Among a large number of graphite replacement materials, silicon (Si) is one of the most promising negative electrode materials. Its advantages are as follows: (1) silicon has extremely high weight specific capacity (4200 mAh·g -1 ) and volume specific capacity (9786 mAh·cm -3 ); (2) silicon shows a relatively low delithiation voltage (about 0.2-0.5 V) during charging and discharging; (3) silicon is abundant in the earth's crust, low in cost, environmentally friendly and non-toxic. These advantages make silicon one of the most popular negative electrode materials. Although silicon negative electrodes have many advantages, their commercial application still faces difficulties: (1) the lithium storage mechanism of silicon-based negative electrodes is alloying reaction, which will cause serious volume expansion during the cycle process, and then make the silicon-based material gradually fragment and powder and expose the silicon surface; (2) repeated formation of the solid electrolyte interface (SEI) will lead to irreversible loss of active Li + and rapid reduction of capacity; (3) silicon has relatively slow lithium ion diffusion kinetics and low electronic conductivity. These problems ultimately lead to reduced coulombic efficiency and cycle life of silicon-based lithium ion batteries. The current commercial adhesives such as polyacrylic acid (PAA), polyvinylidene fluoride (PVDF), sodium alginate (SA) and hydroxymethyl cellulose (CMC) cannot make the silicon lithium battery work for a long cycle due to their own defects.
[0003] In order to solve the cycle problem of silicon lithium batteries, self-repairing adhesives are widely used in silicon-based lithium ion batteries, which have the ability to repair the broken surface or crack through reversible dynamic interaction, and can maintain the firmness and integrity of the electrode. Chen et al. synthesized a new type of self-repairing poly(ether-thiourea) (SHPET) polymer, which has balanced rigidity and softness and is suitable for silicon anodes. The prepared silicon anode with self-repairing adhesive has excellent structural stability and excellent electrochemical performance, which can provide a discharge capacity of up to 3744 mAh g -1 at a current density of 420 mAg -1 , and can provide a discharge capacity of up to 3744 mAh g -185.6% after 250 cycles at a high current rate. Malik et al. designed a multifunctional adhesive that can self-heal and highly stretch: polydioxothiophene: polyacrylic acid: phytic acid (PEDOT: PAA: PA, PDPP), which provides self-healing and excellent structural integrity for silicon anodes. After 100 cycles, the silicon negative electrode still has a reversible capacity of 2312 mAh g -1 , the initial coulombic efficiency is as high as 94%, and the excellent rate performance provides 2084 mAh g -1 at a rate of 5C. The self-healing adhesive can significantly improve the performance of the silicon negative electrode, and therefore has broad application prospects in the field of silicon-based lithium batteries.
[0004] However, the existing self-healing binder needs to be further improved in terms of improving the cycle life and other performances of the silicon-based lithium battery, and therefore, how to construct a self-healing adhesive containing a gradient hydrogen bond supramolecular network to further improve the cycle life and other performances of the silicon-based lithium battery is a technical problem to be solved by the present application. SUMMARY
[0005] In order to overcome the shortcomings of the prior art, the present application provides a preparation method of a self-healing adhesive containing a gradient hydrogen bond supramolecular network and its application in a silicon-based lithium battery. The self-healing adhesive has high-efficiency self-healing performance due to the dynamic interaction between the four hydrogen bonds between the urea-based pyrimidone and the hydrogen bonds between the acrylic acid and the citric acid, is suitable for a silicon-based lithium battery, can prolong the cycle life of the silicon lithium battery, and is expected to be widely used in the field of silicon-based lithium batteries.
[0006] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is:
[0007] The first aspect of the present application provides a preparation method of a self-healing adhesive containing a gradient hydrogen bond supramolecular network, and the preparation method comprises the following steps:
[0008] (1) reacting a monomer containing a mercapto group, carbon disulfide and bromobenzene in tetrahydrofuran to prepare a linear RAFT reagent BTPA;
[0009] (2) adding the linear RAFT reagent BTPA, dipentaerythritol, N,N-dicyclohexyl carbodiimide, 4-dimethylaminopyridine into tetrahydrofuran, and preparing a six-armed star-shaped RAFT reagent through esterification reaction;
[0010] (3) adding the six-arm star RAFT reagent, tert-butyl acrylate monomer and initiator azobisisobutyronitrile into tetrahydrofuran and 1,4-dioxane to obtain a six-arm star self-repairing adhesive A through a RAFT polymerization reaction, and then adding the six-arm star self-repairing adhesive A, pyrimidinone monomer and initiator azobisisobutyronitrile into tetrahydrofuran and 1,4-dioxane to obtain a six-arm star block self-repairing adhesive B through a RAFT polymerization again;
[0011] (4) blending the six-arm star block self-repairing adhesive B with a monomer containing a hydroxyl group to obtain a self-repairing adhesive containing a gradient hydrogen-bonded supramolecular network.
[0012] The urea-based pyrimidinone monomer and the acrylate monomer are subjected to free radical polymerization through the six-arm star RAFT reagent, and the multistage dynamic hydrogen-bonded network endows the adhesive with excellent self-healing ability, improves the surface crack of lithium pieces in the cycle process, and has strong adhesion between the adhesive and SiNPs, can withstand large volume expansion and release the internal stress of SiNPs in the repeated lithiation / delithiation process, and prolongs the service life of the battery.
[0013] Preferably, the monomer containing a mercapto group is at least one of the following compounds:
[0014]
[0015] Preferably, the pyrimidinone monomer is at least one of the following compounds:
[0016]
[0017] Preferably, the monomer containing a hydroxyl group is at least one of the following compounds:
[0018]
[0019] More preferably, the monomer containing a hydroxyl group is a compound with the following structure:
[0020]
[0021] Preferably, in step (1), the reaction temperature is 0°C, the reaction time is 12-14h, and after the reaction, extraction, drying and rotary evaporation treatment are performed.
[0022] Preferably, in step (2), the reaction temperature is 0°C, the reaction time is 24h, and after the reaction, the mixture is separated and purified by column chromatography, and then dried.
[0023] Preferably, in step (3), the reaction temperature is 70°C, the reaction time is 12-24h, and after the reaction, the product is precipitated with deionized water and dried.
[0024] The second aspect of the present application provides a self-healing adhesive containing a gradient hydrogen-bonded supramolecular network prepared by the above preparation method.
[0025] The third aspect of the present application provides an application of the self-healing adhesive containing a gradient hydrogen-bonded supramolecular network in a silicon-based lithium battery.
[0026] Preferably, the assembly method of the silicon-based lithium battery is as follows: adding nanosilicon, the self-healing adhesive containing a gradient hydrogen-bonded supramolecular network and acetylene black (SP) into deionized water, ball-milling, coating on a copper foil, drying, cutting into an electrode sheet, and assembling a Li||Si battery.
[0027] Preferably, the diameter of the electrode sheet is 14 mm.
[0028] Compared with the prior art, the present application has the following beneficial effects:
[0029] The present application discloses a preparation method of a self-healing adhesive containing a gradient hydrogen-bonded supramolecular network. Firstly, a linear RAFT reagent is prepared from a monomer containing a mercapto group, carbon disulfide and bromobenzyl. Then, a six-arm star RAFT reagent is prepared from the linear RAFT reagent and dipentaerythritol through esterification. Subsequently, a six-arm star block self-healing adhesive is prepared by radical polymerization. Finally, the six-arm star block self-healing adhesive is copolymerized with citric acid to obtain the self-healing adhesive containing a gradient hydrogen-bonded supramolecular network. The prepared adhesive has high self-repairing efficiency due to the multistage hydrogen bond network itself. When the adhesive is applied to a silicon lithium battery, the internal stress of SiNP can be released, and the cycle life of the battery is prolonged. Specifically, the present application has the following advantages:
[0030] (1) The urea-based-pyrimidinone unit in the adhesive forms a more stable quadruple hydrogen bond, has a super-high association constant and excellent bond energy, and makes the adhesive have the advantages of a simultaneously self-healing polymer network and strong binding between the polymer and silicon;
[0031] (2) The weak hydrogen bond formed between acrylic acid and citric acid is introduced into the quadruple hydrogen bond polymer network, and the rigid-flexible network made by gradient hydrogen bonds provides energy dissipation capacity to maintain the structural integrity of the silicon electrode during the cycle process. BRIEF DESCRIPTION OF DRAWINGS
[0032] Figure 1 It is a gradient hydrogen bond mechanism diagram of the adhesive in Example 1.
[0033] Figure 2 It is a reaction flow chart in Example 1.
[0034] Figure 3 It is a nuclear magnetic resonance hydrogen spectrum diagram of the 6-ARM-RAFT reagent in Example 1.
[0035] Figure 4 FT-IR spectrum of 6-ARM-RAFT reagent in Example 1.
[0036] Figure 5 FT-IR spectra of 6-ARM-PAA-UPy-CA in Example 1 at different temperatures.
[0037] Figure 6 Cycle performance of Li||Si assembled with PAA, 6-ARM-PAA in Comparative Example 1, 6-ARM-PAA-UPy in Comparative Example 2, 6-ARM-PAA-UPy-CA in Example 1 as binder.
[0038] Figure 7 Rate performance of Li||Si assembled with PAA, 6-ARM-PAA in Comparative Example 1, 6-ARM-PAA-UPy in Comparative Example 2, 6-ARM-PAA-UPy-CA in Example 1 as binder. DETAILED DESCRIPTION
[0039] The specific embodiments of the present application will be further described below. It should be noted that the description of these embodiments is used to help understand the present application, but does not constitute a limitation on the present application. In addition, the technical features involved in each embodiment of the present application described below can be combined with each other as long as they do not conflict with each other.
[0040] The experimental methods in the following examples are all conventional methods unless otherwise specified, and the experimental materials used in the following examples are all commercially available unless otherwise specified.
[0041] Example 1: Preparation of a supramolecular network self-healing adhesive containing gradient hydrogen bonds and lithium battery using the adhesive
[0042] 1. Preparation of a supramolecular network self-healing adhesive containing gradient hydrogen bonds
[0043] The preparation process of the adhesive is as shown in Figure 2 The preparation method thereof comprises the following steps:
[0044] (1) Preparation of linear RAFT reagent BTPA:
[0045] To a stirred suspension of 5.36 g K3PO4 in dry tetrahydrofuran was added 2.00 mL of 3-mercaptopropionic acid and stirred for 10 min. To this solution was added 4.14 mL of CS2 dropwise at 0 °C. After stirring for 2 h, 2.73 g of benzyl bromide was added. The reaction mixture was stirred overnight, the suspension was filtered and the filter cake was washed. After drying the organic extract with MgSO4, the solvent was removed by rotary evaporation and dried in an oven to give linear RAFT agent BTPA.
[0046] (2) Preparation of six-arm star-shaped RAFT agent:
[0047] To a dry flask containing 1.51 g dipentaerythritol was added 9.73 g of BTPA in 40 mL of dry tetrahydrofuran, followed by the dropwise addition of 7.37 g of N,N-dicyclohexylcarbodiimide and 0.437 g of 4-dimethylaminopyridine in 10 mL of dry tetrahydrofuran (THF) to the reaction mixture at 0 °C. The mixture was stirred at room temperature for 24 h. The crude product was isolated and purified by column chromatography, dried, to give the six-arm star-shaped RAFT agent. Its1H NMR spectrum is shown in Figure 3 Figure 4 and FT-IR spectrum is shown in
[0048] (3) Synthesis of six-arm star-shaped block self-healing adhesive:
[0049] A certain amount of THF and 1,4-dioxane was added to a 250 mL reaction flask containing 0.089 g of six-arm star-shaped RAFT agent, 38.45 g of monomer t-butyl acrylate (tBA), and 0.0024 g of initiator AIBN. After thorough mixing, the reaction flask was sealed with a rubber stopper. The mixture was subjected to freeze-thaw cycles three times, the reaction flask was filled with argon, and then the reaction flask was placed in a 70 °C oil bath for 24 h. After the polymerization was completed, the reaction flask was exposed to air, precipitated in deionized water, and the dissolution-precipitation operation was repeated three times. The obtained solid precipitate was dried in a vacuum oven overnight to give six-arm star-shaped self-healing adhesive A. The above procedure was repeated with 39.54 g of six-arm star-shaped self-healing adhesive A, 0.84 g of pyrimidone monomer, and 0.0024 g of initiator AIBN in a 250 mL reaction flask to give six-arm star-shaped block self-healing adhesive B.
[0050] (4) Synthesis of supramolecular network self-healing adhesive containing gradient hydrogen bonds:
[0051] The 0.077 g six-arm star block self-healing binder is dissolved in N,N-dimethylformamide, 0.02 g CA is dissolved in deionized water, the above solutions are mixed, magnetically stirred at room temperature for 2 h, and dried in a 60°C air oven to obtain a gradient hydrogen bond-containing supramolecular network self-healing adhesive 6-ARM-PAA-UPy-CA. The mechanism diagram of the gradient hydrogen bond of the obtained adhesive 6-ARM-PAA-UPy-CA is shown in Figure 1 .
[0052] The FT-IR spectrum of 6-ARM-PAA-UPy-CA at different temperatures is shown in Figure 5 . With the increase of temperature, the intensity of the carbonyl peak attributed to CA increases, representing the partial dissociation of the hydrogen bonds formed between CA and PAA, which can prove that the gradient hydrogen bond-containing supramolecular network self-healing adhesive has been successfully synthesized.
[0053] 2. Preparation of lithium battery
[0054] The above obtained adhesive is mixed with nano Si:acetylene black SP:6-ARM-PAA-UPy-CA in a mass ratio of 7:2:1, a certain volume of H2O is added to make the total volume 8 ml, and after ball milling for 12 h, it is coated on a copper foil, dried and cut into a pole piece with a diameter of 14 mm, and assembled into a Li||Si battery.
[0055] Example 2: Preparation of a gradient hydrogen bond-containing supramolecular network self-healing adhesive and lithium battery using the adhesive
[0056] 1. Preparation of a gradient hydrogen bond-containing supramolecular network self-healing adhesive
[0057] (1) Preparation of linear RAFT reagent BTPA:
[0058] The same as step (1) of example 1
[0059] (2) Preparation of six-arm star RAFT reagent:
[0060] The same as step (2) of example 1
[0061] (3) Synthesis of six-arm star block self-healing binder:
[0062] The same as step (3) of example 1
[0063] (4) Synthesis of gradient hydrogen bond-containing supramolecular network self-healing adhesive
[0064] A 0.077 g six-arm star block self-healing adhesive was dissolved in N,N- dimethylformamide, 0.038 g citric acid was dissolved in deionized water, the above solutions were mixed, and magnetic stirring was carried out at room temperature for 2 h, and drying was carried out in a 60 °C air oven to obtain a gradient hydrogen bond-containing supramolecular network self-healing adhesive 6-ARM-5PAA-UPy-CA.
[0065] 2. Preparation of a lithium battery
[0066] The same as Example 1
[0067] Example 3: Preparation of a gradient hydrogen bond-containing supramolecular network self-healing adhesive and a lithium battery using the adhesive
[0068] 1. Preparation of a gradient hydrogen bond-containing supramolecular network self-healing adhesive
[0069] (1) Preparation of linear RAFT reagent BTPA:
[0070] The same as step (1) of Example 1
[0071] (2) Preparation of six-arm star RAFT reagent:
[0072] The same as step (2) of Example 1
[0073] (3) Synthesis of six-arm star block self-healing adhesive:
[0074] The same as step (3) of Example 1
[0075] (4) Synthesis of gradient hydrogen bond-containing supramolecular network self-healing adhesive
[0076] A 0.077 g six-arm star block self-healing adhesive was dissolved in N,N- dimethylformamide, 0.038 g citric acid was dissolved in deionized water, the above solutions were mixed, and magnetic stirring was carried out at room temperature for 2 h, and drying was carried out in a 60 °C air oven to obtain a gradient hydrogen bond-containing supramolecular network self-healing adhesive 6-ARM-5PAA-UPy-CA.
[0077] 2. Preparation of a lithium battery
[0078] The same as Example 1
[0079] Comparative Example 1: Preparation of a six-arm star self-healing adhesive and a lithium battery using the adhesive
[0080] 1. Preparation of a six-arm star self-healing adhesive
[0081] (1) Preparation of linear RAFT reagent BTPA:
[0082] The same as step (1) of Example 1
[0083] (2) Preparation of the six-arm star-shaped RAFT agent:
[0084] The same as step (2) of Example 1
[0085] (3) Synthesis of the six-arm star-shaped self-healing adhesive A:
[0086] 0.089 g of the six-arm star-shaped RAFT agent, 38.45 g of the monomer t-butyl acrylate tBA and 0.0024 g of the initiator AIBN were dissolved in a 250 mL reaction bottle with a certain amount of THF and 1,4-dioxane. After mixing thoroughly, the reaction bottle was sealed with a rubber plug. The above mixture was subjected to freeze-thaw cycle for 3 times, the reaction bottle was filled with argon, and then the reaction bottle was placed in a 70°C oil bath for 24 h. After the polymerization was completed, the reaction bottle was exposed to air, precipitated in deionized water, and the dissolution-precipitation operation was repeated three times. The obtained solid precipitate was vacuum dried overnight to obtain the six-arm star-shaped self-healing adhesive 6-ARM-PAA.
[0087] 2. Preparation of lithium battery
[0088] The above obtained adhesive was mixed with nano Si:acetylene black SP:6-ARM-PAA at a mass ratio of 7:2:1, a certain volume of H2O was added to make the total volume 8 ml, and then ball-milled for 12 h. The mixture was coated on a copper foil, dried and cut into a pole piece with a diameter of 14 mm. The Li||Si battery was assembled and used.
[0089] As shown in Figure 6 , the battery using PAA as the adhesive has a specific capacity of 0 mAh / g after 200 cycles at a current density of 1C, while the battery using 6-ARM-PAA as the adhesive has a specific capacity of 543 mAh / g, indicating that the six-arm star-shaped structure is beneficial to form a tight network and thus improve the performance of the adhesive.
[0090] Preparation of a six-arm star-shaped self-healing adhesive and lithium battery using the same
[0091] 1. Preparation of a six-arm star-shaped self-healing adhesive
[0092] (1) Preparation of the linear RAFT agent BTPA:
[0093] The same as step (1) of Example 1
[0094] (2) Preparation of the six-arm star-shaped RAFT agent:
[0095] The same as step (2) of Example 1
[0096] (3) Synthesis of the six-arm star-shaped self-healing adhesive:
[0097] A 250 mL reaction bottle was charged with 0.089 g of six-arm star-shaped RAFT reagent, 38.45 g of monomer tert-butyl acrylate tBA, and 0.0024 g of initiator AIBN, and a certain amount of THF and 1,4-dioxane was added to dissolve. After mixing thoroughly, the reaction bottle was sealed with a rubber plug. The above mixture was subjected to freeze-thaw cycle for 3 times, the reaction bottle was filled with argon, and then the reaction bottle was placed in a 70°C oil bath for 24 h. After the polymerization was completed, the reaction bottle was exposed to air, precipitated in deionized water, and repeated the dissolution-precipitation operation three times. The obtained solid precipitate was vacuum dried overnight to obtain six-arm star-shaped self-healing adhesive A. A 250 mL reaction bottle was charged with 39.54 g of six-arm star-shaped self-healing adhesive A, 0.84 g of pyrimidone monomer, and 0.0024 g of initiator AIBN, and the above steps were repeated to obtain six-arm star-shaped block self-healing adhesive 6-ARM-PAA-UPy.
[0098] 2. Preparation of lithium battery
[0099] The above obtained adhesive, nano Si:acetylene black SP:6-ARM-PAA-UPy were mixed in a mass ratio of 7:2:1, a certain volume of H2O was added to make the total volume 8 ml, and then ball milled for 12 h. The mixture was coated on a copper foil, dried, and cut into a diameter of 14 mm to assemble a Li||Si battery.
[0100] In Figure 6 , the battery using 6-ARM-PAA as the adhesive had a specific capacity of 543 mAh g -1 after 200 cycles at a current density of 1C, while the specific capacity of 6-ARM-PAA-UPy was 1000 mAh g -1 , indicating that the addition of UPy formed a quadruple hydrogen bond network inside the adhesive, improving the performance of the adhesive; the specific capacity of the adhesive 6-ARM-PAA-UPy-CA with the addition of citric acid was 1481 mAh g -1 after 200 cycles, which was significantly better than 6-ARM-PAA-Upy, 6-ARM-PAA, and PAA, as shown in Figure 7 , in the rate test, the performance of 6-ARM-PAA-UPy-CA was also significantly better than 6-ARM-PAA-Upy, 6-ARM-PAA, and PAA, which proved that the addition of citric acid formed a supramolecular crosslinking network inside the adhesive, thereby improving the self-healing performance and mechanical properties of the material and prolonging the service life of the battery.
[0101] The embodiments of the present application are described in detail above, but the present application is not limited to the described embodiments. For those skilled in the art, various changes, modifications, replacements, and variations of the embodiments can be made without departing from the principles and spirits of the present application, and still fall within the protection scope of the present application.
Claims
1. A method for preparing a self-healing adhesive with a supramolecular network containing gradient hydrogen bonds, characterized in that, The preparation method includes the following steps: (1) The linear RAFT reagent BTPA is prepared by reacting a monomer containing a mercapto group, carbon disulfide, and benzyl bromide in tetrahydrofuran. (2) Linear RAFT reagent BTPA, bispentaerythritol, N,N-dicyclohexylcarbodiimide and 4-dimethylaminopyridine were added to tetrahydrofuran and esterified to prepare a six-armed star-shaped RAFT reagent. (3) A six-armed star-shaped RAFT reagent, tert-butyl acrylate monomer and initiator azobisisobutyronitrile were added to tetrahydrofuran and 1,4-dioxane, and a six-armed star-shaped self-healing adhesive A was obtained by RAFT polymerization. Then, the six-armed star-shaped self-healing adhesive A, pyrimidinone monomer and initiator azobisisobutyronitrile were added to tetrahydrofuran and 1,4-dioxane, and a six-armed star-shaped block self-healing adhesive B was obtained by RAFT polymerization again. (4) The six-armed star-shaped block self-healing adhesive B was blended with a monomer containing hydroxyl groups to obtain a supramolecular network containing gradient hydrogen bonds.
2. The method for preparing a self-healing adhesive with a supramolecular network containing gradient hydrogen bonds according to claim 1, characterized in that, The monomer containing a thiol group is at least one of the following compounds:
3. The method for preparing a self-healing adhesive with a supramolecular network containing gradient hydrogen bonds according to claim 1, characterized in that, The pyrimidinone monomer is at least one of the following compounds:
4. The method for preparing a self-healing adhesive with a supramolecular network containing gradient hydrogen bonds according to claim 1, characterized in that, The monomer containing a hydroxyl group is at least one of the following compounds:
5. The method for preparing a self-healing adhesive with a supramolecular network containing gradient hydrogen bonds according to claim 4, characterized in that, The monomer containing hydroxyl groups is a compound with the following structure:
6. The method for preparing a self-healing adhesive with a supramolecular network containing gradient hydrogen bonds according to claim 1, characterized in that, In step (1), the reaction temperature is 0℃, the reaction time is 12-14h, and after the reaction, extraction, drying and rotary evaporation are performed.
7. The method for preparing a self-healing adhesive with a supramolecular network containing gradient hydrogen bonds according to claim 1, characterized in that, In step (2), the reaction temperature is 0°C and the reaction time is 24h. After the reaction, the mixture is separated and purified by column chromatography and then dried.
8. The method for preparing a self-healing adhesive with a supramolecular network containing gradient hydrogen bonds according to claim 1, characterized in that, In step (3), the reaction temperature is 70℃, the reaction time is 12-24h, and the product is precipitated with deionized water and dried after the reaction.
9. A self-healing adhesive for a supramolecular network containing gradient hydrogen bonds prepared by the preparation method according to any one of claims 1-8.
10. The application of a self-healing adhesive with a supramolecular network containing gradient hydrogen bonds as described in claim 9 in silicon-based lithium batteries, characterized in that, The assembly method of the silicon-based lithium battery is as follows: nano-silicon, the self-healing adhesive of the supramolecular network containing gradient hydrogen bonds as described in claim 8, and acetylene black are added to deionized water, ball-milled, coated on copper foil, dried, and cut into electrode sheets to assemble Li||Si batteries.