An impact-resistant anode coating polymer adhesive, preparation method and application

Abstract

The application belongs to the technical field of adhesives, and particularly relates to an impact-resistant anode coating polymer adhesive, a preparation method and application. Alpha-lipoic acid monomers, methoxy polyethylene glycol acrylate monomers, an initiator and a chain transfer agent are dissolved in an organic solvent to obtain a mixture, a heating reaction is performed, then the reaction is terminated by immersing in liquid nitrogen, and a polymer adhesive precursor is obtained through solvent precipitation, and then mixed with a compound containing guanidino and carboxyl groups to obtain the polymer adhesive. Through molecular structure design and multi-component synergistic effect, the adhesive is endowed with excellent interfacial adhesion and high impact mechanical properties, and the functionalization of the lithium metal battery anode coating is realized.

Description

Technical Field

[0001] This invention belongs to the field of adhesive technology, specifically relating to an impact-resistant anodized polymer adhesive, its preparation method, and its application. Background Technology

[0002] Adhesion, a ubiquitous interfacial phenomenon in nature, is essential for life activities such as gecko crawling and mussel attachment. Inspired by nature, humans have used natural adhesives in production activities since ancient times. From the adhesive materials of the Stone Age to the synthetic adhesives widely used in modern industrial systems in electronics, medicine, construction, consumer goods, and aerospace, adhesives have become a key basic material supporting human social development and industrial progress.

[0003] Based on various supramolecular interactions such as hydrogen bonding, host-guest interaction, metal coordination, and ionic bonding, researchers have constructed a series of novel and high-performance supramolecular polymer adhesives. Among them, hydrogen bond-mediated supramolecular self-assembly is an important approach to achieving bottom-up construction and functionalization of materials. Introducing hydrogen bond interactions into the bonding system can not only effectively regulate the mechanical properties and adhesive characteristics of the material, but also endow the system with stimulus responsiveness and interfacial self-adaptation capabilities, expanding the application boundaries of supramolecular adhesive materials. However, current multi-hydrogen bonded adhesives still face many bottlenecks: some hydrogen bonded adhesives have weak hydrogen bond forces, making it difficult to balance cohesive-interfacial adhesion forces; some hydrogen bonded adhesives have complex synthesis and high application costs; and some hydrogen bonded adhesives lack sufficient functionality, making it difficult to meet the current industrial demand for multifunctional adhesives.

[0004] Addressing the application needs and existing challenges of multi-hydrogen-bonded supramolecular binders, designing and synthesizing multi-hydrogen-bonded units with high bonding strength, easy functionalization, and simple preparation has become the core of constructing high-performance binders. Developing multifunctional, responsive supramolecular binders based on novel synthetic methods has become an important development trend in this field. Summary of the Invention

[0005] The purpose of this invention is to provide an impact-resistant anode coating polymer adhesive, its preparation method, and its application. Through molecular structure design and the synergistic effect of multiple components, the adhesive is endowed with excellent interfacial adhesion properties and high impact mechanical properties, while realizing the functionalization of the lithium metal battery anode coating.

[0006] To achieve the above objectives, the first aspect of the present invention provides a polymer adhesive precursor, the structural formula of which is shown below:

[0007] Wherein, x and y are positive integers from 10 to 200, n is a positive integer from 3 to 50, and R1 and R2 are each independently one of hydrogen, amino, carboxyl, hydroxyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted piperidinyl, and substituted or unsubstituted imidazolyl, wherein the substituted group is amino, carboxyl, hydroxyl, or halogen.

[0008] Furthermore, R2 is an amino group, a carboxyl group, or an amino or carboxyl-substituted C1-C10 alkyl group, and R1 is a substituted or unsubstituted C1-C20 alkyl group.

[0009] Furthermore, the structural formula of the polymer adhesive precursor is shown below:

[0010] m is a positive integer from 1 to 12, and n is a positive integer from 3 to 30.

[0011] Furthermore, the structural formula of the polymer adhesive precursor is shown below:

[0012] Where x ranges from 28 to 136, and y ranges from 33 to 133.

[0013] A second aspect of this invention provides a method for preparing the polymer adhesive precursor, comprising: dissolving α-lipoic acid monomer, methoxy polyethylene glycol acrylate monomer, initiator, and chain transfer agent in an organic solvent to obtain a mixture; heating the mixture to react; immersing the mixture in liquid nitrogen to terminate the reaction; and obtaining the polymer adhesive precursor by solvent precipitation; the structural formula of the methoxy polyethylene glycol acrylate monomer is shown below:

[0014] The structural formula of the chain transfer agent is shown below: .

[0015] Furthermore, the structural formula of the chain transfer agent is shown below: Preferably, the structural formula is as follows: .

[0016] Furthermore, the reaction temperature is 60-80℃.

[0017] The molar ratio of the α-lipoic acid monomer, the methoxy polyethylene glycol acrylate monomer, the initiator, and the chain transfer agent is (360-4200):(840-1800):1:10. And / or, the solvent used in the solvent precipitation is isopropyl ether.

[0018] A third aspect of the present invention provides a polymer adhesive, comprising the polymer adhesive precursor described above or the polymer adhesive precursor obtained by the preparation method described above, and a compound containing both guanidine and carboxyl groups; the structural formula of the compound containing both guanidine and carboxyl groups is shown below:

[0019] k is a positive integer from 0 to 10, and R is hydrogen, amino, carboxyl, hydroxyl, substituted or unsubstituted C1-C20 alkyl or alkoxy.

[0020] Furthermore, the structural formula of the compound containing both guanidine and carboxyl groups is shown below:

[0021] k is a positive integer from 1 to 6.

[0022] Furthermore, the compound containing both guanidine and carboxyl groups is L-arginine, and its structural formula is shown below: .

[0023] Furthermore, the molar ratio of the x and y content in the polymer adhesive precursor to the molar ratio of the compound containing both guanidine and carboxyl groups is (28.3-135.6):(33.0-132.6):(14.2-135.6).

[0024] Further, the polymer adhesive precursor is first dissolved in a mixed solvent of tetrahydrofuran and water, and the compound containing both guanidine and carboxyl groups is dissolved in water. Then, the two solutions are mixed evenly, and the solvent is removed to obtain the polymer adhesive. Preferably, the volume ratio of the tetrahydrofuran to water is 1:(2-5).

[0025] The molar ratio between the L-arginine and the α-lipoic acid component in the polymer adhesive precursor is (33-100):100.

[0026] A fourth aspect of the present invention provides an application of the aforementioned polymer adhesive for use in anode coatings, electrode bonding, and shock-resistant energy storage devices for lithium metal batteries.

[0027] In summary, compared with the prior art, the above-described technical solutions conceived by this invention mainly possess the following technical advantages: (1) The polymer adhesive precursor provided by the present invention contains carboxyl groups and ether bonds, which provides a guarantee for the multiple salt bridge hydrogen bonding effect of the adhesive, thereby ensuring the bonding strength.

[0028] (2) The present invention constructs a multi-salt bridge hydrogen bond structure in the adhesive molecular chain. Through the dynamic synergistic effect between carboxyl, amino and guanidine groups, the adhesive is endowed with excellent cohesive force and interfacial adhesion, which effectively ensures the integrity of the electrode structure during the charging and discharging process.

[0029] (3) The present invention uses reversible addition fracture chain transfer (RAFT) active controllable polymerization to prepare adhesives, which can precisely control the polymer chain structure, molecular weight and component ratio to achieve an efficient balance between adhesion performance and impact resistance mechanical properties. The preparation process is simple and controllable and the conditions are mild, which provides a guarantee for the industrial production and stable batch production of adhesives.

[0030] (4) The adhesive of the present invention has both mechanical and electrochemical response characteristics. When subjected to impact or volume deformation, it can absorb energy through dynamic recombination of hydrogen bonds, achieving strong impact resistance and deformation resistance. At the same time, the adhesive can be reduced in situ at the lithium metal battery interface to build a stable solid electrolyte interphase (SEI) film, thereby achieving interface impedance regulation and uniform lithium ion transport, significantly improving the stability of the battery interface.

[0031] (5) The adhesive prepared by the present invention has excellent lithium-ion conductivity and interface stability while ensuring high adhesion strength and high impact resistance. It can be directly used for lithium metal battery anode coating, effectively inhibiting lithium dendrite growth and alleviating volume expansion, which greatly broadens the application scenarios of traditional adhesives in high energy density and high safety energy storage devices. Attached Figure Description

[0032] Figure 1 For P(LA) 30.4 - co -PEG 67.4 1H NMR spectra and assignments of RAFT chain transfer agent, α-lipoic acid, and methoxy polyethylene glycol acrylate monomer.

[0033] Figure 2 For P(LA) 30.4 - co -PEG 67.4 ), P(LA 30.4 - co -PEG 67.4 ) / Arg 20.3 1H NMR spectrum and assignment of L-arginine.

[0034] Figure 3 For P(LA) 30.4 - co -PEG 67.4 ) / Arg 20.3 Frequency scan rheological curves.

[0035] Figure 4 For P(LA) 30.4 - co -PEG 67.4 ) / Arg 20.3 2×2 cm bonded as an adhesive 2 A diagram illustrating how a stainless steel plate can lift a 20.7 kg solvent tank.

[0036] Figure 5 For P(LA) 30.4 - co -PEG 67.4 ) / Arg 20.3 Long-cycle variation diagram of lithium-lithium symmetric cells assembled with anode coating and uncoated symmetric cells at constant current density.

[0037] Figure 6 For P(LA) 91.2 - co -PEG 108.4 ) / Arg 45.6 Frequency scan rheological curves.

[0038] Figure 7 This is a schematic diagram illustrating the principle of the polymer adhesive of the present invention in an impact-resistant anodized coating. Detailed Implementation

[0039] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. Furthermore, the technical features involved in the various embodiments of this invention described below can be combined with each other as long as they do not conflict with each other.

[0040] This invention relates to an impact-resistant anodized polymer adhesive comprising two compounds with the following structural formulas, which are bonded together by hydrogen bonds: ,

[0041] coThis indicates random copolymerization, not actual functional groups. It means the two polymer chains are directly connected by carbon-carbon bonds. x and y are positive integers greater than or equal to 10, n is a positive integer greater than or equal to 3, and k is a positive integer from 0 to 10. Preferably, x and y are positive integers from 10 to 200, n is a positive integer from 3 to 50, and R1 and R2 are each independently one of hydrogen, amino, carboxyl, hydroxyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted piperidinyl, and substituted or unsubstituted imidazolyl, wherein the substituted group is amino, carboxyl, hydroxyl, or halogen.

[0042] Preferably, the chemical structure of the material is shown in Formula I: ; Formula I The ratio of x, y, and z ranges from (28.3-135.6):(33.0-132.6):(14.2-135.6).

[0043] like Figure 7 A target polymer adhesive was prepared by combining reversible addition-fragmentation chain transfer polymerization (RAFT) with precise blending modification. This adhesive constructs a unique salt-bridged hydrogen bond structure. Relying on the hydrogen bond effect of the salt bridge, it not only imparts ultra-high cohesive strength to the adhesive but also significantly improves the material's impact toughness, effectively overcoming the defects of traditional lithium metal battery anode coatings, such as weak mechanical properties and easy detachment and cracking during cycling. Simultaneously, the polyethylene glycol side chains in the adhesive can efficiently conduct lithium ions, giving the material excellent lithium-ion conductivity. Furthermore, the lipoic acid and L-arginine components in the system can be reduced in situ on the lithium metal anode surface, self-assembling to form a stable and uniform solid electrolyte interphase (SEI) film rich in lithium nitride and lithium sulfide. Utilizing the controllable activity characteristics of RAFT polymerization, the impact mechanical properties and electrochemical properties of the material can be precisely controlled and balanced. This adhesive can inhibit lithium dendrite growth on lithium metal anodes by leveraging its excellent impact resistance, while simultaneously optimizing the anode interface composition and interfacial stability, making it widely applicable in the field of high-performance, stable lithium metal batteries.

[0044] The composition includes: α-lipoic acid monomer (LA), methoxy polyethylene glycol acrylate monomer (PEG), (dodecyl trithiocarbonate)-2-methylpropionic acid (RAFT chain transfer agent) and azobisisobutyronitrile (AIBN, RAFT) initiator, and L-arginine (Arg).

[0045] The chemical name of the RAFT chain transfer agent is 2-(dodecyltrithiocarbonate)-2-methylpropionic acid, which has a well-defined structural formula as shown in Formula II.

[0046] ; Formula II The chemical name of the α-lipoic acid monomer is 5-(1,2-dithiocyclopentyl)valerate, which has a well-defined structural formula as shown in Formula III.

[0047] ; Formula III The aforementioned polyethylene glycol has a clearly defined acrylate-based polyethylene glycol monomethyl ether monomer, as shown in Formula IV.

[0048] ; Formula IV The chemical structure of the L-arginine is 2-amino-5-guanidinovalerate, which has a well-defined structural formula as shown in Formula III.

[0049] ; Formula V The initiator is chemically named azobisisobutyronitrile (AIBN), and it has a well-defined structural formula as shown in Formula VI.

[0050]

[0051] Style VI This invention provides a method for preparing an impact-resistant anodized polymer adhesive, comprising the following steps: Step 1: Preparation of polymer precursor P(LA) by reversible addition-fragmentation chain transfer polymerization x - co -PEG y ) Alpha-lipoic acid, methoxy polyethylene glycol acrylate, RAFT initiator, RAFT chain transfer agent, and organic solvent were placed in a Schlenk flask and bubbled for 30 min to remove air; then immersed in 70 °C water. o The reaction was carried out in a constant temperature oil bath for several hours, and then the polymerization was terminated by immersion in liquid nitrogen. The pure polymer precursor was obtained by solvent precipitation. Step 2: Impact-resistant salt-bridged hydrogen-bonded polymer adhesive P(LA) x - co -PEG y ) / Arg z Preparation (1) Take a round-bottom flask of appropriate size, dissolve the polymer precursor obtained in step one in an organic-water mixed solvent, and stir at room temperature for 30 mins until completely homogeneous; take another round-bottom flask of appropriate size, and dissolve L-arginine in an aqueous solution. Mix the solutions in the two round-bottom flasks and stir for 30 mins until completely homogeneous.

[0052] (2) The solvent in (1) is removed by high-temperature evaporation to obtain the impact-resistant salt-bridged hydrogen-bonded polymer adhesive P(LA). x - co -PEG y ) / Arg z .

[0053] Preferably, in step one, the organic solvent is a polar organic solvent, preferably one of N,N-dimethylformamide or tetrahydrofuran.

[0054] Preferably, in step two (1), the organic component in the organic-water solvent is a polar organic solvent that is miscible with water, preferably one or more of methanol, ethanol, N,N-dimethylformamide and dimethyl sulfoxide; the ratio of organic solvent to water does not exceed 1:3.

[0055] Preferably, in step two (1), the concentration of the organic-aqueous solvent and the aqueous solvent after dissolving the polymer precursor and L-arginine should not exceed 0.2 g / mL.

[0056] Preferably, in step two (2), the high-temperature evaporation temperature is 90-150°C. o C, with the preferred temperature being 100℃.

[0057] Example 1 P(LA 30.4 - co -PEG 67.4 ) polymer precursor, P(LA) 30.4 - co -PEG 67.4 ) / Arg 20.3 Preparation method of impact-resistant anodized polymer binder The preparation method mainly includes the following steps: Step 1: Preparation of polymer precursor P(LA) by reversible addition-fragmentation chain transfer polymerization 30.4 - co -PEG 67.4 ) α-Lipoic acid, methoxy polyethylene glycol acrylate, AIBN, RAFT chain transfer agent, and DMF were placed in a Schlenk flask and bubbled for 30 min to remove air. The mixture was then immersed in a 70°C oil bath for 6 hours to terminate polymerization, followed by precipitation with isopropyl ether to obtain a pure polymer precursor. P(LA) was then prepared. 30.4 - co -PEG 67.4 The molar amounts of the polymer precursors are shown in Table 1 below.

[0058] Table 1. Molar Feed Ratio

[0059] Step 2: Impact-resistant salt-bridged hydrogen-bonded polymer adhesive P(LA) 30.4 - co -PEG 67.4 ) / Arg 20.3 Preparation (1) Take a round-bottom flask of appropriate size, and put the polymer precursor P(LA) obtained in step one into the flask. 30.4 - co -PEG 67.4 Dissolve L-arginine in a THF-water mixture and stir at room temperature for 30 mins until completely homogeneous. Take another appropriately sized round-bottom flask and dissolve L-arginine in an aqueous solution in a ratio corresponding to that of α-lipoic acid in the polymer precursor. Mix the solutions from both round-bottom flasks and stir for 30 mins until completely homogeneous. The mass-volume ratio of dissolved substances in the solutions of polymer precursor and L-arginine is shown in Table 2 below.

[0060] Table 2. Mass-to-volume ratio of dissolved substances in solutions of polymer precursors and L-arginine.

[0061] At this point, the molar ratio of α-lipoic acid to L-arginine in the polymer precursor is 30.4:20.3.

[0062] (2) Pour the mixed solution from (1) into a polytetrafluoroethylene mold, place it in an oven at 100°C for high-temperature evaporation for 30 mins until the water and THF are completely evaporated, and finally obtain the impact-resistant salt-bridged hydrogen-bonded polymer adhesive P(LA). 30.4 - co -PEG 67.4 ) / Arg 20.3 .

[0063] For example P(LA) 30.4 - co -PEG 67.4 ) / Arg 20.3 Conduct the experiment.

[0064] 1. Testing the polymer precursor P(LA) 30.4 - co -PEG 67.4 ), impact-resistant salt-bridged hydrogen-bonded polymer adhesive P(LA) 30.4 - co -PEG 67.4 ) / Arg 20.3 Its chemical structure.

[0065] To ensure the accuracy of the subsequent addition of L-arginine and to verify the successful preparation of the impact-resistant salt-bridged hydrogen-bonded polymer adhesive, the chemical structure of the polymer precursor needs to be tested first, using P(LA) as an example. 30.4 - co -PEG 67.4 For example, by using nuclear magnetic resonance testing and assigning characteristic hydrogen (such as...) Figure 1 As shown), RAFT polymerization raw materials and polymer precursor P(LA) are used. 30.4 - co -PEG 67.4 By comparing the characteristic hydrogens of the monomers (methoxy polyethylene glycol acrylate characteristic hydrogen 5, α-lipoic acid characteristic hydrogen 8) with the characteristic hydrogen 1 of the RAFT chain transfer agent, the success of the polymer precursor synthesis can be clearly characterized and the content of α-lipoic acid in the polymer can be obtained. 30.4 - co -PEG 67.4 Each polymer molecule in the product consists on average 30.4 α-lipoic acid monomers and 67.4 methoxy polyethylene glycol acrylates.

[0066] To verify the successful preparation of the impact-resistant salt-bridged hydrogen-bonded polymer adhesive, its structure needs to be tested, specifically P(LA) 30.4 - co -PEG 67.4 ) / Arg 20.3 For example, through nuclear magnetic resonance testing (such as...) Figure 2 As shown), P(LA) 30.4 - co -PEG 67.4 ) / Arg 20.3 With polymer precursor P(LA) 30.4 - co -PEG 67.4By comparing the characteristic hydrogens of P(LA) and L-arginine, characteristic hydrogen 1 shifted from approximately 12 ppm in the polymer precursor to approximately 9 ppm, characteristic hydrogen 2 shifted from 2.4 ppm to 2.2 ppm, and characteristic hydrogen 3 shifted from 7.7 ppm to 8.1 ppm. This ultimately confirmed the presence of impact-type salt-bridged hydrogen-bonded polymer adhesive P(LA) 30.4 - co -PEG 67.4 ) / Arg 20.3 The synthesis was successful.

[0067] 2. Test P(LA) 30.4 - co -PEG 67.4 ) / Arg 20.3 Its impact resistance.

[0068] The impact resistance was tested by a rheometer in a constant temperature and humidity indoor environment. The rheological test mode was oscillation mode, with a constant oscillation test temperature of 25℃, a constant oscillation strain of 0.1%, and an oscillation frequency from 0.1 Hz to 100 Hz. 25 data points were taken in logarithmic mode.

[0069] Through testing, P(LA) 30.4 - co -PEG 67.4 ) / Arg 20.3 It exhibits excellent impact resistance (as shown in the attached diagram in the instruction manual). Figure 3 (As shown). Its storage modulus increases rapidly with increasing frequency, rising from 3000 Pa at an initial frequency of 0.1 Hz to approximately 10 Pa at 100 Hz. 6 The modulus increased by 538 times, and the intersection of its storage modulus and loss modulus was less than 10 Hz, demonstrating excellent shock resistance. This can be attributed to the salt bridge hydrogen bond formed between α-lipoic acid and L-arginine, which is highly directional and responds quickly to impact due to the high entropy penalty.

[0070] 3. Test P(LA) 30.4 - co -PEG 67.4 ) / Arg 20.3 Adhesion properties.

[0071] (1) Sample preparation Before characterizing the adhesion properties, the sample was prepared. First, the polymer sample was heated to 90°C. After the polymer softened, it was coated onto the surface of different substrates. Then, another substrate plate was pressed onto the bonding surface and a pressure of 5 kg was applied for 30 min. Finally, it was cooled to 25°C to complete the preparation.

[0072] (2) Shear strength The shear test was conducted continuously in a constant temperature and humidity environment using a universal testing machine. The tensile rate was 10 mm / min. Each test parameter had to be measured repeatedly at least 5 times and the average value was taken.

[0073] Through testing, P(LA) 30.4 - co -PEG 67.4 ) / Arg 20.3 It exhibits good mechanical properties under different substrates, and its shear strength is shown in Table 3 below. It can be seen that P(LA) 30.4 - co -PEG 67.4 ) / Arg 20.3 The adhesive exhibited excellent adhesion to both hydrophilic and hydrophobic substrates. Materials tested for adhesion included stainless steel, glass, aluminum, copper, polymethyl methacrylate, polypropylene, polyethylene terephthalate, polystyrene, and polytetrafluoroethylene. 30.4 - co -PEG 67.4 ) / Arg 20.3 The maximum viscous shear strength to stainless steel substrates reached 2.6 MPa, the maximum viscous shear strength to glass substrates reached 2.4 MPa, and the viscous shear strength to polypropylene reached 0.5 MPa, demonstrating excellent adhesive properties.

[0074] Table 3 P(LA) 30.4 - co -PEG 67.4 ) / Arg 20.3 Adhesion performance on different substrates

[0075] (3) Application scenarios Through P(LA) 30.4 - co -PEG 67.4 ) / Arg 20.3 The two bonded stainless steel sheets can lift approximately 60 kg, with a bonding area of ​​400 mm². 2 This indicates that the polymer has high adhesion to different surfaces. Meanwhile, through P(LA) 30.4 - co -PEG 67.4 ) / Arg 20.3 The prepared sample can easily lift a 20.7 kg solvent container (as shown in the attached diagram in the instruction manual). Figure 4As shown in the figure, its high adhesion strength and stability make it applicable in various fields. In the field of anode coatings, this means that it can adhere firmly to lithium metal anodes, avoiding detachment due to volume changes during charging and discharging.

[0076] 4. Test P(LA) 30.4 - co -PEG 67.4 ) / Arg 20.3 Battery performance when used as an anodic coating P(LA 30.4 - co -PEG 67.4 ) / Arg 20.3 As an anode coating for lithium metal batteries, it can adhere firmly to the lithium metal surface, and its impact resistance can suppress lithium dendrite growth, ultimately achieving long-cycle stability of lithium metal batteries. The application of this anode coating was verified by assembling lithium-lithium symmetric coin cells and conducting constant current long-cycle tests.

[0077] The coin cell assembly was carried out in a temperature- and pressure-controlled glove box with water and oxygen content both less than 0.01 ppm. Using 15 mm diameter lithium metal sheets as electrodes, P(LA) was... 30.4 - co -PEG 67.4 ) / Arg 20.3 Dissolved in THF to prepare a 3% (w / w) solution, 40 μL was uniformly drop-coated onto a lithium metal sheet and left to stand for 12 h until the THF had completely evaporated. 20 μL of electrolyte was added to the coated lithium metal sheet, and a 17 mm diameter PP membrane was used. After adding another 20 μL of electrolyte, a lithium-lithium symmetric coin cell was assembled using another coated lithium metal sheet. Simultaneously, as a comparison, a lithium-lithium symmetric coin cell was assembled using an uncoated lithium metal sheet (bare lithium, BareLi). At 1 mA / cm²... 2 1 mAh / cm 2 Constant current cycling tests were performed at a current density of [value missing].

[0078] Through testing, P(LA) was applied. 30.4 - co -PEG 67.4 ) / Arg 20.3 The constant current cycling stability time of lithium-lithium symmetric batteries is significantly improved (e.g. Figure 5 As shown in the figure, compared to uncoated bare lithium, its stability time was extended by 8.5 times. This indicates that the material can serve as an excellent anode coating, significantly improving the stability of lithium metal batteries.

[0079] Example 2 P(LA 91.2 -co -PEG 108.4 ) polymer precursor, P(LA) 91.2 - co -PEG 108.4 ) / Arg 45.6 A method for preparing an impact-resistant anodized polymer binder, the method mainly includes the following steps: Step 1: The experimental method is similar to that of Example 1, except that the reaction time is 8 hours. The feed ratio for preparing the polymer precursor is shown in Table 4 below: Table 4. Feed ratio of polymer precursors

[0080] Step 2: Impact-resistant salt-bridged hydrogen-bonded polymer adhesive P(LA) 91.2 - co -PEG 108.4 ) / Arg 45.6 Preparation (1) The experimental method is similar to that in Example 1. The difference is that the mass-volume ratio of the dissolved substances in the preparation of the polymer precursor and L-arginine solution is shown in Table 5 below.

[0081] Table 5. Mass-volume ratio of dissolved substances in solutions of polymer precursors and L-arginine.

[0082] At this point, the molar ratio of lipoic acid to L-arginine in the polymer precursor is 2:1. (2) Pour the mixed solution from (1) into a polytetrafluoroethylene mold and place it at 120°C. o After high-temperature evaporation in oven C for 30 minutes until water and THF are completely evaporated, the impact-resistant salt-bridged hydrogen-bonded polymer adhesive P(LA) is finally obtained. 91.2 - co -PEG 108.4 ) / Arg 45.6 .

[0083] For example P(LA) 91.2 - co -PEG 108.4 ) / Arg 45.6 Conduct the experiment.

[0084] Test P(LA) 91.2 - co -PEG 108.4 ) / Arg 45.6 Its impact resistance.

[0085] The testing method is the same as in Example 1. Through testing, P(LA)91.2 - co -PEG 108.4 ) / Arg 45.6 It exhibited certain impact resistance (e.g.) Figure 6 (As shown). Its storage modulus increases rapidly with frequency, rising from 300 Pa at an initial frequency of 0.1 Hz to approximately 5 * 10 Pa at 100 Hz. 5 Pa, the modulus increased by 178 times, and the intersection of its storage modulus and loss modulus is greater than 10 Hz, compared to P(LA) in Example 1. 30.4 - co -PEG 67.4 ) / Arg 20.3 It has a certain degree of impact resistance.

[0086] In summary, addressing the technical problems of existing adhesives such as insufficient hydrogen bonding strength, poor molecular structure tunability, cumbersome synthesis steps, limited functionality, and difficulty in simultaneously achieving adhesive, mechanical, and electrochemical performance, this invention employs a reversible addition-fragmentation chain transfer (RAFT) active controlled polymerization method. Using α-lipoic acid monomer and methoxy polyethylene glycol acrylate monomer as core copolymer units, and introducing L-arginine component through aqueous solution blending, a novel impact-resistant anode coating polymer adhesive is prepared after solvent evaporation. This invention aims to endow the adhesive with excellent interfacial adhesion and high impact resistance through molecular structure design and multi-component synergistic effects, while simultaneously functionalizing the anode coating of lithium metal batteries, achieving the goals of stabilizing the electrode structure, inhibiting lithium dendrite growth, and optimizing interfacial transport.

[0087] Those skilled in the art will readily understand that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A polymer adhesive precursor, characterized in that, Its structural formula is shown below: Wherein, x and y are positive integers from 10 to 200, n is a positive integer from 3 to 50, and R1 and R2 are each independently one of hydrogen, amino, carboxyl, hydroxyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted piperidinyl, and substituted or unsubstituted imidazolyl, wherein the substituted group is amino, carboxyl, hydroxyl, or halogen.

2. The polymer adhesive precursor according to claim 1, characterized in that, The structural formula of the polymer adhesive precursor is shown below: m is a positive integer from 1 to 12, and n is a positive integer from 3 to 30.

3. The polymer adhesive precursor according to claim 2, characterized in that, The structural formula of the polymer adhesive precursor is shown below: Where x ranges from 28 to 136, and y ranges from 33 to 133.

4. A method for preparing the polymer adhesive precursor according to any one of claims 1-3, characterized in that, include: An α-lipoic acid monomer, a methoxy polyethylene glycol acrylate monomer, an initiator, and a chain transfer agent were dissolved in an organic solvent to obtain a mixture. The mixture was then heated to react, and the reaction was terminated by immersion in liquid nitrogen. The polymer adhesive precursor was obtained by solvent precipitation. The structural formula of the methoxy polyethylene glycol acrylate monomer is shown below: The structural formula of the chain transfer agent is shown below: 。 5. The method for preparing the polymer adhesive precursor according to claim 4, characterized in that, The reaction temperature is 60-80℃; And / or, the molar ratio of the α-lipoic acid monomer, the methoxy polyethylene glycol acrylate monomer, the initiator and the chain transfer agent is (360-4200):(840-1800):1:10; And / or, the solvent used in the solvent precipitation is isopropyl ether.

6. A polymer adhesive, characterized in that, The polymeric adhesive precursor includes the polymeric adhesive precursor according to any one of claims 1-3 or the polymeric adhesive precursor obtained by the preparation method according to any one of claims 4-5, and a compound containing both guanidine and carboxyl groups; the structural formula of the compound containing both guanidine and carboxyl groups is shown below: k is a positive integer from 0 to 10, and R is hydrogen, amino, carboxyl, hydroxyl, substituted or unsubstituted C1-C20 alkyl or alkoxy.

7. The polymer adhesive according to claim 6, characterized in that, The structural formula of the compound containing both guanidine and carboxyl groups is shown below: k is a positive integer from 1 to 6.

8. The polymer adhesive according to claim 6, characterized in that, The molar ratio of the x and y content in the polymer adhesive precursor to the molar ratio of the compound containing both guanidine and carboxyl groups is (28.3-135.6):(33.0-132.6):(14.2-135.6).

9. The polymer adhesive according to claim 6, characterized in that, First, the polymer adhesive precursor is dissolved in a mixed solvent of tetrahydrofuran and water. Then, the compound containing both guanidine and carboxyl groups is dissolved in water. The two solutions are then mixed evenly, and the solvent is removed to obtain the polymer adhesive. Preferably, the volume ratio of the tetrahydrofuran to water is 1:(2-5); And / or, the molar ratio between the compound containing both guanidine and carboxyl groups and the α-lipoic acid component in the polymer adhesive precursor is (33-100):

100.

10. The application of the polymer adhesive according to any one of claims 6-9, characterized in that, Anode coatings, electrode bonding, and shock-resistant energy storage devices for lithium metal batteries.

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