Star-shaped polymers and their preparation methods, binders, electrode materials, electrodes and batteries

Abstract

This application discloses a star-shaped polymer and its preparation method, binder, electrode material, electrode sheet, and battery. The star-shaped polymer has the following structure: R1-(OCO-R2-R3-R4-R5). n The star-shaped polymer in this application is constructed from the core outwards as a rigid fluorocarbon segment, an ion-conducting segment, and an interfacial bonding / crosslinking segment, giving it a high degree of branching and excellent solution / melt rheological properties. After the star-shaped polymer is formed into a film, the physical entanglement between its star arms and the subsequent chemical crosslinking work together to form a denser and more stable mechanical network, thereby improving its structural strength and enabling it to simultaneously possess efficient lithium-ion transport channels and ultra-high interfacial adhesion capabilities.

Description

Technical Field

[0001] This application relates to the field of battery technology, specifically to a star-shaped polymer and its preparation method, binder, electrode material, electrode sheet and battery. Background Technology

[0002] With the explosive growth in demand for electric vehicles and large-scale energy storage, developing next-generation lithium-ion batteries with higher energy density, longer cycle life, and higher safety has become a global consensus. The application of high-capacity electrode materials such as silicon-based anodes, lithium metal anodes, and high-nickel cathodes has placed unprecedented demands on battery binders: on the one hand, binders must withstand the huge volume changes of electrode materials during charging and discharging, providing ultra-strong mechanical bonding force to maintain the integrity of the electrode structure; on the other hand, traditional binders such as polyvinylidene fluoride (PVDF) have extremely low ionic conductivity, which severely hinders ion transport and increases interfacial impedance.

[0003] To improve ionic conductivity, researchers have attempted to introduce highly ion-conducting segments such as polyethylene oxide (PEO) and polyionic liquids. However, these flexible segments typically lead to a sharp decrease in the material's mechanical strength, making it difficult to meet electrode bonding requirements. Conversely, attempts to enhance mechanical properties (such as increasing crosslinking or introducing rigid segments) severely hinder ion transport. This inherent contradiction between "bonding strength" and "ionic conductivity" has become a core bottleneck restricting the development of high-performance binders. Summary of the Invention

[0004] This application provides a star-shaped polymer and its preparation method, binder, electrode material, electrode sheet and battery, aiming to solve the inherent contradiction between the adhesive strength and ionic conductivity of the binder.

[0005] This application provides a star-shaped polymer having the following structure: R1-(OCO-R2-R3-R4-R5) n ; Wherein, R1 is an alkyl or ether group; The structural formula of R2 is -A m1 -B m2 - where A is a fluoroethyl group containing at least one fluorine atom, B is a fluoroethyl group containing a substituent, the substituent being an alkyl group, a fluoroalkyl group, a chlorine atom, an alkoxy group, or a fluoroalkoxy group, m1 is an integer greater than or equal to 50, and m2 is an integer greater than or equal to 2. The structural formula of R3 is: Among them, R6, R8, R 10 Each occurrence is independently selected from -H and -CH3, R7 is a polyol ether ester group, R9 is an ester group containing at least one of cycloalkyl, phenyl, and tert-butyl groups, R 11 It is an ester group; R4 includes and , where R 12 R 14 Each occurrence is independently selected from -H and -CH3, R 13 It is an ester group or an ether group, R 15 It is an amide group or an amide group containing substituents, wherein the substituents are at least one of carboxyl and hydroxyl groups; Each occurrence of R5 is independently selected from a halogen atom; n is an integer between 3 and 12, n1 is an integer greater than or equal to 1, n2 is an integer greater than or equal to 1, n3 is an integer greater than or equal to 1, n4 is an integer greater than or equal to 0, and n5 is an integer greater than or equal to 1. For connecting points.

[0006] Accordingly, this application also provides a method for preparing a star-shaped polymer, comprising: A polyol and an α-haloacylating agent are mixed in a first solvent to carry out a first acylation reaction, yielding an initiator; An initiator and symmetrical fluorinated olefins and amorphous fluorinated olefins are mixed in a second solvent to carry out an atom transfer radical addition reaction to obtain a reaction solution containing the first intermediate. Hydroxysulfonic acid and acylacrylic acid derivative are mixed in a third solvent to carry out a second acylation reaction to obtain acryloyloxysulfonate; Acryloyloxysulfonate was mixed with an alkaline lithium source in a fourth solvent and neutralized to obtain the first active monomer. The reaction solution containing the first intermediate is mixed with polyol ether acrylate, an acrylate monomer containing at least one of cycloalkyl, phenyl and tert-butyl groups, and a first active monomer, and subjected to an atom transfer radical polymerization reaction to obtain a reaction solution containing the second intermediate. A catecholamine compound and an acylacrylic acid derivative are mixed in a fifth solvent and subjected to an amidation reaction to obtain a second active monomer; The reaction solution containing the second intermediate and the second active monomer are mixed in the sixth solvent to carry out the third atom transfer radical polymerization reaction to obtain the star polymer; Among them, polyols contain at least 3 alcohol hydroxyl groups.

[0007] In addition, this application also provides an adhesive comprising the star polymer described above, or a star polymer prepared by the method described above.

[0008] In addition, this application also provides an electrode material, including a positive active material and the above-mentioned binder, or a negative active material and the above-mentioned binder.

[0009] In addition, this application also provides an electrode sheet, including an active layer formed by curing the above-mentioned electrode material.

[0010] In addition, this application also provides a battery including the aforementioned electrode.

[0011] The star polymer in this application is constructed from the core (R1) outwards as a rigid fluorocarbon segment (R2), an ion-conducting segment (R3), and an interfacial bonding / crosslinking segment (R4), giving it a high degree of branching and excellent solution / melt rheological properties. After the star polymer is formed into a film, the physical entanglement between its star arms and the subsequent chemical crosslinking work together to form a denser and more stable mechanical network, thereby improving its structural strength and enabling it to simultaneously possess efficient lithium-ion transport channels and ultra-high interfacial adhesion. Detailed Implementation

[0012] The technical solutions in the embodiments of this application will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0013] To reconcile the inherent contradiction between "bonding strength" and "ionic conductivity," numerous attempts have been made in related technologies, but most have yielded limited results and failed to achieve a fundamental breakthrough: 1) Random copolymerization strategy: For example, random copolymerization of monomers containing ion-conducting groups with monomers containing rigid structures can introduce both functions simultaneously. However, due to the random and disordered distribution of functional groups on the molecular chain, efficient continuous ion transport channels cannot be formed, and the rigid and flexible units interfere with each other, resulting in the material's performance being only a compromise average of the two, failing to achieve synergistic enhancement. 2) Simple physical blending strategy: Physically mixing polymers with ion-conducting functions with polymers with bonding functions. However, due to the thermodynamic incompatibility of the two components, macroscopic phase separation easily occurs, leading to a sharp increase in interfacial impedance, and unsatisfactory ionic conductivity and mechanical stability. 3) Functionalized linear block copolymers: Linear amphiphilic block copolymers are designed in an attempt to construct ion channels through microphase separation. However, the topological limitations of linear structures lead to insufficient network stability under stress, and the spatial distribution of functional segments is difficult to control precisely. The interfacial bonding function and the bulk conduction function often restrict each other, resulting in limited improvement in overall performance.

[0014] This application provides a star-shaped polymer and its preparation method, an adhesive, an electrode material, an electrode sheet, and a battery. These are described in detail below. It should be noted that the order of description of the following embodiments is not intended to limit the preferred order of the embodiments. Furthermore, in the description of this application, the term "comprising" means "including but not limited to". The terms first, second, third, etc., are used merely as illustrative and do not impose numerical requirements or establish an order. Various embodiments of the present invention may exist in a range format; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the invention; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within that range. For example, it should be considered that a range description from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Additionally, whenever a numerical range is indicated herein, it means including any referenced number (fraction or integer) within the indicated range.

[0015] This application provides a star-shaped polymer with the following structure: R1-(OCO-R2-R3-R4-R5) n ; Wherein, R1 is an alkyl or ether group; The structural formula of R2 is -A m1 -B m2 - where A is a fluoroethyl group containing at least one fluorine atom, B is a fluoroethyl group containing a substituent, the substituent being an alkyl group, a fluoroalkyl group, a chlorine atom, an alkoxy group, or a fluoroalkoxy group, m1 is an integer greater than or equal to 50, preferably 80 to 150, for example, 80, 90, 100, 110, 120, 130, 140, 150, etc., and m2 is an integer greater than or equal to 2, preferably 5 to 20, for example, 5, 6, 8, 10, 12, 15, 17, 19, 20, etc.; The structural formula of R3 is: Among them, R6, R8, R 10 Each occurrence is independently selected from -H and -CH3, R7 is a polyol ether ester group, R9 is an ester group containing at least one of cycloalkyl, phenyl, and tert-butyl groups, R 11 It is an ester group; R4 includes and , where R 12 R 14 Each occurrence is independently selected from -H and -CH3, R 13 It is an ester group or an ether group, R 15 It is an amide group or an amide group containing substituents, wherein the substituents are at least one of carboxyl and hydroxyl groups; Each occurrence of R5 is independently selected from a halogen atom; n is an integer between 3 and 12, for example, it can be 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.; n1 is an integer greater than or equal to 1, for example, it can be 1, 2, 3, 4, 5, 6, 7, etc.; n2 is an integer greater than or equal to 1, for example, it can be 1, 2, 3, 4, 5, 6, 7, etc.; n3 is an integer greater than or equal to 1, for example, it can be 1, 2, 3, 4, 5, 6, 7, etc.; n4 is an integer greater than or equal to 0, for example, it can be 0, 1, 2, 3, 4, 5, 6, 7, etc.; n5 is an integer greater than or equal to 1, for example, it can be 1, 2, 3, 4, 5, 6, 7, etc. For connecting points.

[0016] In this application, the star-shaped polymer possesses high branching degree and excellent solution / melt rheological properties. After the star-shaped polymer is film-formed, the physical entanglement between its star-shaped arms and the subsequent chemical cross-linking work synergistically to form a denser and more stable mechanical network, thereby improving its structural strength. It also possesses efficient lithium-ion transport channels and ultra-high interfacial adhesion. R1 is the core of the star-shaped polymer, serving as its star-shaped network framework, laying the foundation for high strength and the formation of efficient ion transport, ultra-high interfacial adhesion, and intelligent dynamic response functions. The rigid fluorocarbon segment (R2) is a random copolymer of symmetrical fluorinated olefin (A) and amorphous fluorinated olefin (B), possessing good strength and flexibility. It can serve as the mechanical framework and electrochemical stabilizing layer of the star-shaped polymer, providing the polymer with basic mechanical strength, electrochemical redox stability, and certain hydrophobicity and basic adhesion to the current collector. The ion-conducting segment (R3) includes polyol ether ester groups (R7) and a large-volume rigid segment. The ester group (R9) of the functional groups (cycloalkyl, phenyl, and tert-butyl) has good flexibility and low glass transition temperature, which can serve as the basic framework of lithium-ion transport channels. The polyol ether ester group (R7) has the ability to solubilize lithium ions and move the chain segments. The ester group (R9) with large volume rigid groups can inhibit the crystallization of polyol ether ester groups, thereby widening the working temperature range of star polymers. -SO3Li can provide lithium source, thus forming a highly efficient lithium-ion transport channel. The catechol group of the interfacial bonding / crosslinking segment (R4) can form strong coordination bonds with the electrode surface, thereby adhering to the electrode surface. The epoxy group can be used for subsequent crosslinking reaction to form a dynamic covalent network. Constructing the rigid fluorocarbon segment (R2), ion conduction segment (R3), and interfacial bonding / crosslinking segment (R4) from the core (R1) outward can achieve physical separation of structures with different functions, reduce mutual interference between functions, and at the same time follow the functional space partitioning principle to achieve optimal positioning and synergistic effect of each function at the molecular scale.

[0017] Understandably, the rigid fluorocarbon segment (R2), adjacent to the core (R1), serves as the mechanical foundation of the star polymer, providing a stable mechanical framework and electrochemical stability for the entire molecule. The ion-conducting segment (R3), located in the middle, acts as a transport bridge for the star polymer, constructing a continuous ion channel from the bulk phase to the interface, thus optimizing the ion transport path. The interfacial bonding / crosslinking segment (R4), located on the outermost edge, acts as an interfacial pioneer, preferentially contacting and strongly anchoring the electrode surface through its terminal-enriched catechol groups, while its inner epoxy groups can serve as crosslinking points to construct a dynamic network. This sequence design, characterized by inner rigidity and outer flexibility, inner support and outer anchoring, and bulk transport interface enrichment, achieves physical separation and spatial synergy of the three major functions of mechanical support, ion conduction, and interfacial bonding at the molecular chain level. It improves upon the drawbacks of mutual interference of functional groups in traditional random structures, overcoming the trade-off between strength and conductivity and achieving a synergistic improvement in overall performance.

[0018] Understandably, according to the IUPAC's 2020 guidelines on the nomenclature of structural groups for irregular linear, star, comb, and brush polymers, star polymers are characterized by a multiradical center (or junction unit) and three or more polymer arms extending radially from that center. Symmetrical fluorinated olefins have symmetrical side groups, regular molecular structure, and readily crystallize. Polymers formed from these monomers (such as PVDF) have highly regular molecular chain segments that can be tightly packed into crystals, exhibiting excellent crystallinity. Amorphous fluorinated olefins, on the other hand, have bulky or asymmetrical side groups (such as -CF3, -Cl, or ether bonds), which disrupt the regularity of the molecular chain, making it difficult for the polymer to form crystals, resulting in amorphous or low-crystallinity polymers.

[0019] In some embodiments of this application, R1 is an alkyl group with 3 to 6 carbon atoms or an ether group with 6 to 15 carbon atoms. For example, it can be an alkyl group with 3, 4, 5, or 6 carbon atoms, or an ether group with 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 carbon atoms.

[0020] In some embodiments of this application, R1 is , , , , , or .

[0021] In some embodiments of this application, the number-average molecular weight of R2 is 7 kDa to 14 kDa, for example, 7 kDa, 8 kDa, 9 kDa, 10 kDa, 11 kDa, 12 kDa, 13 kDa, or 14 kDa. This allows the star polymer to possess sufficient strength while also ensuring sufficient reactivity of its chain segments. If the number-average molecular weight of R2 is too low, the star polymer will lack sufficient strength, the chain segments will be too short, and the physical entanglement effect will be poor; if the number-average molecular weight of R2 is too high, the chain segments will be too long, the crystallinity will be too high, and the chain segment reactivity of the star polymer will be low.

[0022] In some embodiments of this application, A is -CH2-CF2-, -CF2-CHF-, or -CF2-CF2-.

[0023] In some embodiments of this application, the structural formula of B is -CF2-CFR 16 or -CF2-CR 17 R 16 , where R 16 For -Cl, -CF3, or -O-CF3, R 17 It can be -F, -Cl, -CF3, -O-CF3, or -H.

[0024] In some embodiments of this application, the ratio of m1 to m2 is (90~97):(3~10), for example, it can be 90:10, 91:9, 92:8, 93:7, 94:6, 95:5, 96:4, 97:3, etc., preferably 95:5. Thus, the side groups (such as CF3) of the amorphous monomer (B) disrupt the regularity of the symmetrical fluorinated olefin (A), reducing its crystallinity from 50~70% of the homopolymer to 30~40%, thereby increasing the mobility of the rigid fluorocarbon segment and providing a flexible basis for subsequent ion transport. If the content of the amorphous fluorinated olefin is too low (<3%), the crystallization inhibition effect is insufficient, and the chain segment mobility is insufficient; if the content of the amorphous fluorinated olefin is too high (>8%), the mechanical strength of the product decreases excessively, and the cost increases. A content of 5% for the amorphous fluorinated olefin represents the optimal balance between strength and flexibility.

[0025] In some embodiments of this application, the ratio of n1 to n2 is (85~95):(5~15), for example, it can be 85:15, 86:14, 88:12, 90:10, 91:9, 93:7, 94:6, 95:5, etc., preferably 91:9. This allows the ion-conducting segment (R3) to have good lithium-ion solvation and chain segment mobility capabilities, while also giving the star polymer a wider operating temperature range. Too few R9s with large-volume rigid groups result in insufficient crystallization inhibition, leading to a decrease in the polymer's low-temperature conductivity; too many R9s with large-volume rigid groups will excessively dilute the polyol ether segments, affecting lithium-ion transport.

[0026] In some embodiments of this application, the ratio of n3 to n1 is (0.8~1.0):1, for example, it can be 0.8:1, 0.85:1, 0.9:1, 0.95:1, 1.0:1, etc., preferably 0.9:1. This provides a sufficient lithium source, thereby forming an efficient lithium-ion transport channel. If the proportion of n3 is too small, the molar proportion of -SO3Li is too low, resulting in insufficient lithium source; if the proportion of n3 is too large, the molar proportion of -SO3Li is too high, which may form ion clusters that hinder ion transport.

[0027] In some embodiments of this application, the structural formula of R3 is as follows: The side of R3 closest to R7 is connected to R2.

[0028] It is understandable that the segments inside R3, including polyol ether ester R7 and ester R9 with large volume rigid groups, can serve as transport channels with low lithium salt concentrations. The segments have high degrees of freedom of movement, providing a fast migration channel for lithium ions, but they do not provide a large number of lithium ions themselves. The lithium sulfonate ion groups enriched on the outside of R3 can serve as ion sources with high lithium salt concentrations, providing lithium ions to participate in the interfacial reaction. This constructs a separation model of "bulk transport region (channel) - interfacial enrichment region (source)," achieving an efficient transport model of "source-channel separation."

[0029] In some embodiments of this application, the number-average molecular weight of R3 is 10 kDa to 17 kDa, for example, 10 kDa, 11 kDa, 12 kDa, 13 kDa, 14 kDa, 15 kDa, 16 kDa, 17 kDa, etc. This allows for the formation of a continuous lithium-ion transport channel while ensuring sufficient mobility of the ion-conducting segments, thereby improving lithium-ion transport efficiency. If the number-average molecular weight of R3 is too low, the ion channel will be discontinuous; if the number-average molecular weight of R3 is too high, the movement of the R3 chain segments will be hindered.

[0030] In some embodiments of this application, The number-average molecular weight is 6kDa~10kDa, for example, it can be 6kDa, 7kDa, 8kDa, 9kDa, 10kDa, etc. In this way, the lithium-ion fast migration channel formed by the ion conduction section (R3) can have sufficient continuity and mobility. The number-average molecular weight is too low, resulting in insufficient continuity of the rapid lithium-ion migration channels. The number-average molecular weight is too high, the chain segments are prone to crystallization, and the mobility is poor.

[0031] In some embodiments of this application, in In the middle, on the side closer to R1 The mole fraction is lower on the side furthest from R1. The mole fraction. In this way, the concentration of lithium sulfonate ion groups at the end of R3 can be greater than the concentration of lithium sulfonate ion groups on the side closer to R1, which can enhance ion exchange activity at the electrode / electrolyte interface.

[0032] Understandable, It is formed by copolymerization of three monomers. The mole fraction refers to the percentage of its mole fraction relative to the total moles of the three monomers. The concentration of lithium sulfonate ion groups at the end of R3 is greater than that on the side closer to R1, thus forming a directional migration channel driven by the concentration gradient. In the gradient structure, the lithium salt concentration increases from the inside to the outside, forming a chemical potential gradient. Driven by the concentration gradient, lithium ions tend to migrate directionally from the low concentration region (bulk phase) to the high concentration region (interface). This built-in driving force can reduce the activation energy of ion migration, making ion transport more efficient and directional. At the same time, the gradient structure can promote the formation of a continuous and continuous spatial distribution of lithium ion carriers (sulfonate groups) from the inside to the outside, rather than randomly distributed isolated points, so that lithium ions can jump along the shortest path between adjacent sulfonate groups, reducing the tortuosity of the lithium ion transport path.

[0033] In some embodiments of this application, in In the middle, from the side closer to R1 to the side farther away from R1, it successively includes a lithium sulfonate transition section and a lithium sulfonate enrichment section. The lithium sulfonate transition section on the side closer to R1... The mole fraction is lower on the side furthest from R1. The mole fraction of lithium sulfonate ion enrichment segment The mole fraction is greater than that of the lithium sulfonate transition zone. The mole fraction. Thus, a gradient ion concentration field can be constructed, creating a gradient structure where the concentration of lithium sulfonate ion groups gradually increases from the inside out, with high concentration enrichment at the very end. This simulates an efficient ion conduction model of "bulk transport-interface source," where the gradient change optimizes the ion migration path, and the terminal enrichment layer can greatly enhance the ion exchange kinetics at the electrode / electrolyte interface.

[0034] Understandably, in the high-concentration lithium sulfonate ion enrichment layer at the R3 end, the local concentration of lithium sulfonate groups is much higher than that in the bulk phase. During film formation, this segment spontaneously accumulates at the electrode interface, effectively constructing a nanoscale lithium-rich buffer layer on the electrode surface. When lithium ions need to migrate from the bulk phase to the electrode surface to participate in the reaction, the diffusion distance of the final path (from the bulk end to the electrode surface) is significantly shortened. According to Fick's diffusion law, diffusion flux is inversely proportional to diffusion distance; therefore, the lithium-rich buffer layer can reduce interfacial concentration polarization and improve the availability of lithium ions at the interface. According to the Butler-Volmer equation, the exchange current density (i0) of the electrode reaction is positively correlated with the concentration of reactants (lithium ions) at the interface. The lithium-rich buffer layer at the end of the gradient structure provides a locally high-concentration lithium-ion environment for the interfacial reaction, significantly increasing the exchange current density. The concentration gradient region in the gradient structure acts as a buffer and connector, allowing lithium ions transported from the bulk phase to smoothly enter the lithium-rich buffer layer, mitigating the potential increase in impedance caused by sudden concentration changes. This seamless connection ensures high-speed lithium-ion transport from the bulk phase to the interface. Simultaneously, the end-enrichment layer, in synergy with the catechol anchoring groups, achieves an ideal interface state with strong adhesion and a sufficient lithium source.

[0035] In some embodiments of this application, the lithium sulfonate ion transition section is from the side closer to R1 to the side farther away from R1. The mole fraction increases sequentially.

[0036] In some embodiments of this application, the lithium sulfonate ion transition section is from the side closer to R1 to the side farther away from R1. The mole fraction increases from 0% to 30%~60%.

[0037] In some embodiments of this application, the lithium sulfonate ion enrichment segment The mole fraction is greater than or equal to 80%.

[0038] In some embodiments of this application, the number-average molecular weight of the lithium sulfonate enrichment segment is 1 kDa to 4 kDa, for example, 1 kDa, 2 kDa, 3 kDa, 4 kDa, etc. This allows for the formation of a high lithium salt concentration layer. If the number-average molecular weight of the lithium sulfonate enrichment segment is too low, there will be insufficient lithium source at the end; if the number-average molecular weight of the lithium sulfonate enrichment segment is too high, it will result in material waste.

[0039] In some embodiments of this application, R7 is ; Among them, R 16 Each occurrence is independently selected from -H and -CH3, where m3 is an integer between 1 and 3, for example, 1, 2, 3, and m4 is an integer between 2 and 7, for example, 2, 3, 4, 5, 6, 7.

[0040] In some embodiments of this application, R7 is , or .

[0041] In some embodiments of this application, R9 is -COO-R 18 , where R 18 It is an alkyl group containing cycloalkyl, phenyl, or tert-butyl groups.

[0042] In some embodiments of this application, R9 is , , , or .

[0043] In some embodiments of this application, R 11 For -COO-R 20 -, where R 20 It is an alkyl group having 2 to 6 carbon atoms, for example, it can be an alkyl group having 2, 3, 4, 5, or 6 carbon atoms.

[0044] In some embodiments of this application, R 11 is -COO-CH2-CH2-CH2-, -COO-CH2-CH2-, -COO-CH2-CH2-CH2-, -COO-CH2-CH2-CH2-CH2-CH2- or -COO-CH2-(CH2)4-CH2-.

[0045] In some embodiments of this application, the number-average molecular weight of R4 is 4.3kDa to 10kDa, for example, it can be 4.3kDa, 5kDa, 6kDa, 7kDa, 8kDa, 9kDa, 10kDa, etc.

[0046] In some embodiments of this application, the structural formula of R4 is as follows: And close to R 13 One end is connected to R3. Thus, the epoxy groups in the inner polymerization segment of the interfacial bonding / crosslinking segment (R4) can provide crosslinking reaction sites for subsequent crosslinking reactions, forming a dynamic covalent network; the middle polymerization segment has both epoxy groups and catechol groups, which can simultaneously provide crosslinking sites and binding groups, achieving a balance between crosslinking ability and binding ability; the terminal polymerization segment has a high density of catechol groups, and based on the thermodynamic driving principle of interfacial migration, these catechol groups will spontaneously and preferentially enrich and anchor on the surface of the electrode active material, thereby improving the interfacial bonding strength.

[0047] In some embodiments of this application, The number-average molecular weight (Mn) is 0.8 kDa to 1.5 kDa, for example, it can be 0.8 kDa, 0.9 kDa, 1.0 kDa, 1.1 kDa, 1.2 kDa, 1.3 kDa, 1.4 kDa, 1.5 kDa, etc. In this way, sufficient epoxy crosslinking sites can be provided for subsequent reactions.

[0048] In some embodiments of this application, The number-average molecular weight (Mn) is 0.8 kDa to 1.0 kDa, for example, it can be 0.8 kDa, 0.9 kDa, 1.0 kDa, etc. This makes it suitable for applications where the flexibility of star-shaped polymers is required.

[0049] In some embodiments of this application, The number-average molecular weight (Mn) is 1.0 kDa to 1.2 kDa, for example, it can be 1.0 kDa, 1.1 kDa, 1.2 kDa, etc. In this way, sufficient epoxy crosslinking sites can be provided for subsequent reactions, and it has better connectivity with the ion-conducting segment.

[0050] In some embodiments of this application, The number-average molecular weight (Mn) is 1.2kDa to 1.5kDa, for example, it can be 1.2kDa, 1.3kDa, 1.4kDa, 1.5kDa, etc. In this way, more epoxy crosslinking sites can be provided, which is suitable for scenarios requiring high degree of crosslinking, while the rigidity and strength of the chain segments are increased.

[0051] In some embodiments of this application, The number-average molecular weight (Mn) is 2kDa~5kDa, for example, it can be 2kDa, 2.5kDa, 3kDa, 3.5kDa, 4kDa, 4.5kDa, 5kDa, etc. In this way, a smooth transition between crosslinking sites and adhesive properties can be achieved.

[0052] In some embodiments of this application, The number-average molecular weight (Mn) is 2kDa~3kDa, for example, it can be 2kDa, 2.2kDa, 2.4kDa, 2.6kDa, 2.8kDa, 3kDa, etc. In this way, the crosslinking and bonding equilibrium section is relatively short, which can achieve a smooth transition between crosslinking and bonding properties, making it suitable for scenarios requiring high flexibility.

[0053] In some embodiments of this application, The number-average molecular weight (Mn) is 3kDa~4kDa, for example, it can be 3kDa, 3.2kDa, 3.4kDa, 3.6kDa, 3.8kDa, 4kDa, etc. In this way, the star polymer can have good crosslinking ability and adhesion.

[0054] In some embodiments of this application, The number-average molecular weight (Mn) is 4kDa~5kDa, for example, it can be 4kDa, 4.2kDa, 4.4kDa, 4.6kDa, 4.8kDa, 5kDa, etc. In this way, the star polymer can have more functional groups, which is suitable for applications requiring higher functional density, while increasing the rigidity of the chain segments.

[0055] In some embodiments of this application, The number-average molecular weight (Mn) is 1.5 kDa to 3.5 kDa, for example, it can be 1.5 kDa, 1.7 kDa, 2.0 kDa, 2.5 kDa, 3.0 kDa, 3.2 kDa, 3.5 kDa, etc. This ensures that each arm of the star polymer is capped with a high density of catechol groups, providing sufficient molecular anchors for interfacial anchoring.

[0056] In some embodiments of this application, The number-average molecular weight (Mn) is 1.5 kDa to 2.0 kDa, for example, it can be 1.5 kDa, 1.6 kDa, 1.7 kDa, 1.8 kDa, 1.9 kDa, 2.0 kDa, etc. This can reduce production costs.

[0057] In some embodiments of this application, The number-average molecular weight (Mn) is 2.0 kDa to 2.5 kDa, for example, it can be 2.0 kDa, 2.1 kDa, 2.2 kDa, 2.3 kDa, 2.4 kDa, 2.5 kDa, etc. In this way, the interfacial anchoring effect and production cost can be balanced.

[0058] In some embodiments of this application, The number-average molecular weight (Mn) is 2.5 kDa to 3.5 kDa, for example, it can be 2.5 kDa, 2.7 kDa, 3.0 kDa, 3.2 kDa, 3.5 kDa, etc. In this way, the star polymer can have a better bonding effect, which is suitable for applications requiring high bonding strength, while the mobility of the chain segments is reduced.

[0059] In some embodiments of this application, R 13 It is an ester or ether group with 2 to 8 carbon atoms, for example, it can be an ester or ether group with 2, 3, 4, 5, 6, 7, or 8 carbon atoms.

[0060] In some embodiments of this application, R 13 It can be -COO-CH2-, -CH2-O-CH2-, or -C6H4-COO-CH2-.

[0061] In some embodiments of this application, R15 for , where R 19 Each occurrence is independently selected from -H and -CH3, R 20 Each occurrence is independently selected from -H and -OH or -COOH, and m5 is 1 or 2.

[0062] In some embodiments of this application, R 15 It can be -CO-NH-CH2-CH2-, -CO-NH-CH(COOH)-CH2-, -CO-NH-CH2-CH(OH)- or -CO-N(CH3)-CH2-CH2-.

[0063] This application also provides a method for preparing a star-shaped polymer, comprising: S1. A polyol and an α-haloacylating agent are mixed in a first solvent to carry out a first acylation reaction, thereby obtaining an initiator; S2. The initiator and the symmetrical fluorinated olefin and the amorphous fluorinated olefin are mixed in the second solvent to carry out an atom transfer radical addition reaction (ATRA) to obtain a reaction solution containing the first intermediate (M1). S3. Hydroxysulfonic acid and acylacrylic acid derivative are mixed in a third solvent to carry out a second acylation reaction to obtain acryloyloxysulfonate; Acryloyloxysulfonate was mixed with an alkaline lithium source in a fourth solvent and neutralized to obtain the first active monomer (denoted as SLiMA). S4. The reaction solution containing the first intermediate (M1) is mixed with polyol ether acrylate, an acrylate monomer containing at least one of cycloalkyl, phenyl and tert-butyl groups, and the first active monomer, and an atom transfer radical polymerization (ATRP) reaction is carried out to obtain a reaction solution containing the second intermediate (M2). S5. The catecholamine compound and the acylacrylic acid derivative are mixed in the fifth solvent and subjected to an amidation reaction to obtain the second active monomer (denoted as: DOPMA). S6. The reaction solution containing the second intermediate and the second active monomer are mixed in the sixth solvent to carry out the third atom transfer radical polymerization reaction to obtain a star polymer. Among them, polyols contain at least 3 alcohol hydroxyl groups.

[0064] In this application, a high-functionality (e.g., hexafunctionality) star structure derived from a polyol (such as sorbitol) is used as the core of the star polymer. By acylating the polyol and then adding symmetrical fluorinated olefins and amorphous fluorinated olefins, random copolymerization can be achieved. During the atom transfer radical addition reaction, both can randomly insert into the polymer chain, obtaining a first intermediate (M1) with a random copolymer of symmetrical fluorinated olefins and amorphous fluorinated olefins as the first block (rigid fluorocarbon segment). This first intermediate possesses good strength and good flexibility. M1 is a star-shaped macromolecular initiator, with each arm ending in a halogen atom (such as Br). It can polymerize with the second block monomer (polyol ether acrylate and acrylate monomers with large-volume rigid side groups (cycloalkyl, phenyl and tert-butyl)) and the first active monomer to form the second block (ion-conducting segment). The second intermediate M2 is a multi-armed star polymer, with each arm ending in a halogen atom (such as M2-Br). It can undergo a reversible activation-polymerization process with the third block monomer (the second active monomer) to form the third block (interfacial bonding segment).

[0065] Understandably, α-haloacylating agents are a class of highly reactive organic chemical reagents characterized by the attachment of a halogen atom (such as Cl, Br, I) at the α-position adjacent to the carbonyl group (on the other side of the carbonyl carbon). The polyol ether segment (-CH2CH2O-) of polyol ether acrylates... n It can form lithium-ion transport channels, and its ether oxygen atoms (-O-) can react with Li. + Coordination enables the solvation and transport of lithium ions, with acrylate groups participating in free radical polymerization. Acrylate monomers with large, rigid side groups act as crystallization inhibitors, their large, rigid side groups inserting between polyol ether segments, disrupting the regular arrangement of the polyol ether segments, inhibiting crystallization, and ensuring the mobility of the segments across the entire temperature range. The first active monomer contains -SO3Li, which can provide a lithium source, thus forming a highly efficient lithium ion transport channel. Hydroxysulfonic acid refers to compounds containing both hydroxyl and sulfonic acid groups. Its hydroxyl group (-OH) is used for acylation reactions with acylacrylic acid derivatives, and the sulfonic acid group (-SO3H) is used in subsequent neutralization reactions to form lithium sulfonate salts, providing a lithium ion source. Acylacrylic acid derivatives refer to organic chemical reagents with both double bond polymerization and acylation activity. They can polymerize double bonds (CH2=C(CH3)-) for subsequent free radical copolymerization; leaving groups (-Cl, -Br, -OH activated) are used for acylation reactions with hydroxyl groups. Alkaline lithium sources can provide Li... +Ions neutralize the sulfonic acid groups in acryloyloxysulfonate to form lithium sulfonate salts. Catecholamine compounds refer to compounds whose molecular structure contains a catechol group (i.e., two adjacent hydroxyl groups on a benzene ring) and a primary amine group (-NH2) (or its derivatives). The catechol group provides adhesion by forming strong coordination bonds with the electrode surface, while the primary amine (-NH2) is used for amidation reactions with acylacrylic acid derivatives. Acylacrylic acid derivatives refer to organic chemical reagents whose molecular structure simultaneously contains double bond polymerization and acylation activity. The polymerizable double bond (CH2=C(CH3)-) is used for subsequent free radical copolymerization; the leaving group (-Cl, -Br, -OH activated) is used for amidation reactions with the primary amine.

[0066] In step S1: As an example, the first solvent is dichloromethane.

[0067] In some embodiments of this application, the polyol includes one or more of sorbitol (6-hydroxy), pentaerythritol (4-hydroxy), glycerol (3-hydroxy), diglycerol (4-hydroxy), erythritol (4-hydroxy), dipentaerythritol (6-hydroxy), and tripentaerythritol (8-hydroxy).

[0068] In some embodiments of this application, the α-haloacylated agent includes one or more of α-haloacyl halides, α-halocarboxylic acids, and α-haloanhydrides.

[0069] In some embodiments of this application, the α-haloacyl halide includes one or more of 2-bromoisobutyryl bromide, 2-bromoisobutyryl chloride, and 2-chloroisobutyryl bromide, preferably 2-bromoisobutyryl bromide. Thus, 2-bromoisobutyryl bromide offers a better balance in terms of reaction efficiency, initiation activity, and synthetic controllability, allowing for better acylation of all hydroxyl groups in polyols.

[0070] In some embodiments of this application, the molar ratio of the hydroxyl group of the polyol to the acyl group of the α-haloacylating agent is 1:(1.3~2.5), for example, it can be 1:1.3, 1:1.4, 1:1.6, 1:1.8, 1:2.0, 1:2.2, 1:2.5, etc., preferably 1:(1.6~2).

[0071] It is understandable that the theoretical stoichiometric ratio of the hydroxyl group of the polyol to the acyl group of the α-haloacylated agent is 1:1. However, since the α-haloacylated agent is extremely sensitive to moisture, trace amounts of water in the reaction system can lead to hydrolysis and consumption of the α-haloacylated agent. Simultaneously, the hydroxyl group of the polyol may experience increased steric hindrance (e.g., the last two hydroxyl groups of sorbitol), resulting in a decreased reaction rate. According to Le Chatelier's principle, increasing the concentration of the α-haloacylated agent can shift the equilibrium towards the product, promoting complete substitution. Furthermore, minor losses during operation must be considered. Therefore, while a molar ratio below 1:1.3 is less expensive, it carries the risk of incomplete acylation, potentially leading to inaccurate numbers of star polymer arms in the subsequent reaction. A molar ratio within the preferred range of 1:(1.6~2) allows for complete acylation of the hydroxyl groups, exhibiting good reaction kinetics and high yield, representing the optimal balance between reaction efficiency and cost. While a molar ratio above 1:2.5 can ensure complete reaction, especially for industrial scale-up, post-treatment requires more thorough washing to remove excess acyl bromide, resulting in higher costs. Experimental data show that when the molar ratio is 1:1 (the theoretical amount), the actual yield is less than 30% and NMR shows obvious hydroxyl residue.

[0072] In some embodiments of this application, the temperature at which the polyol and the α-haloacylating agent are mixed is below 5°C. This effectively suppresses side reactions, controls the reaction rate, and improves reaction selectivity.

[0073] Understandably, α-haloacylating agents are prone to hydrolysis and self-polymerization side reactions at higher temperatures. Low-temperature conditions can selectively promote the main reaction (acylation) and suppress side reactions. The acylation reaction between α-haloacylating agents and alcohols is a strongly exothermic reaction. Slow dropwise addition at low temperatures can control the reaction rate and avoid local overheating. Low-temperature conditions are favorable for the selective acylation of primary hydroxyl groups, ensuring that all hydroxyl groups are completely acylated.

[0074] In some embodiments of this application, the first acylation reaction is carried out at room temperature, and the time of the first acylation reaction is 12h to 36h, for example, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h, 36h, etc., preferably 18h to 24h.

[0075] In some embodiments of this application, the first acylation reaction is carried out in the presence of a first catalyst. As an example, the first catalyst is 4-dimethylaminopyridine (DMAP).

[0076] In some embodiments of this application, it also includes: The reaction solution after the first acylation reaction was washed, dried, rotary evaporated, and concentrated to obtain the crude product; The crude product is purified and recrystallized.

[0077] As an example, the washing process involves sequentially washing the reaction solution with 5% dilute hydrochloric acid, saturated NaHCO3 solution, and brine. The 5% dilute hydrochloric acid removes alkaline impurities, such as alkaline catalysts, which can react with hydrochloric acid to form water-soluble ammonium salts, transferring them from the organic phase to the aqueous phase. The saturated NaHCO3 solution removes acidic impurities, such as HBr generated in the reaction, 2-bromoisobutyric acid produced by the hydrolysis of unreacted α-haloacylating agents, and residual hydrochloric acid after the first washing step. Simultaneously, NaHCO3 reacts with acids to generate CO2 gas and water-soluble salts, which can neutralize acidic substances in the organic phase. The brine solution utilizes the salting-out effect to reduce the water solubility of the organic phase, decreasing the solubility of organic solvents in the aqueous phase, removing water-soluble impurities, including residual water, water-soluble salts, and polar byproducts, and drying the organic phase.

[0078] As an example, anhydrous MgSO4 was used as the drying reagent. Purification was performed by silica gel column chromatography, with the mobile phase consisting of petroleum ether and ethyl acetate in a volume ratio of 10:1, gradually increasing the proportion of ethyl acetate to 4:1. Recrystallization was performed in n-hexane at -20°C.

[0079] In step S2: As an example, the second solvent is anhydrous N,N-dimethylformamide (DMF).

[0080] In some embodiments of this application, the symmetrical fluorinated olefins include one or more of vinylidene fluoride (VDF), trifluoroethylene (TrFE), and tetrafluoroethylene (TFE).

[0081] In some embodiments of this application, the amorphous fluorinated olefins include at least one of hexafluoropropylene (HFP), trifluorochloroethylene (CTFE), and perfluoromethyl vinyl ether (PMVE).

[0082] In some embodiments of this application, the molar ratio of symmetrical fluorinated olefins to amorphous fluorinated olefins is (90~97):(3~10), for example, 90:10, 91:9, 92:8, 93:7, 94:6, 95:5, 96:4, 97:3, etc., preferably 95:5. In this way, the side groups of the amorphous monomers (such as CF3) disrupt the regularity of the molecular chains formed by the symmetrical fluorinated olefins, reducing the crystallinity from 50-70% of the homopolymer to 30-40%, thereby reducing the crystallinity of the first intermediate (M1) and increasing the mobility of the rigid fluorocarbon segment it incorporates, providing a flexible basis for subsequent ion transport. If the content of amorphous fluorinated olefins is too low (<3%), the crystallization inhibition effect is insufficient; if the content of amorphous fluorinated olefins is too high (>8%), the mechanical strength of the product decreases excessively, and the cost increases. A content of 5% for amorphous fluorinated olefins represents the optimal balance between strength and flexibility.

[0083] In some embodiments of this application, the molar ratio of the halogen atom at the end of the initiator to the symmetrical fluorinated olefin and the amorphous fluorinated olefin is 1:(25~50):(0.8~3.0), for example, 1:25:0.8, 1:30:1.0, 1:35:1.5, 1:40:2.0, 1:45:2.5, 1:50:3.0, etc., preferably 1:35.2:1.67. This balances the molecular weight and crystallinity of the first block, resulting in a star polymer with sufficient strength and segmental mobility.

[0084] Understandably, the amount of symmetrical fluorinated olefin determines the number-average molecular weight (Mn) of the first block. Too low a amount results in insufficient strength of the rigid framework formed by the first block, while too high a amount reduces its mobility. Similarly, too low a amount of amorphous fluorinated olefin leads to poor inhibition of crystallization of the first intermediate (M1), while too high a amount results in excessive loss of mechanical strength in the first block. A molar ratio of 1:35.2:1.67 represents the optimal balance between strength and flexibility, allowing the first block to provide a stable mechanical framework while maintaining appropriate segmental mobility, thus laying the structural foundation for the subsequent construction of gradient ion channels and the realization of interfacial anchoring functions.

[0085] In some embodiments of this application, the atom transfer radical addition reaction is carried out under the catalysis of transition metal halides. As examples, transition metal halides include CuBr, CuCl, CuI, and FeBr2.

[0086] In some embodiments of this application, the atom transfer radical addition reaction is carried out in the presence of a nitrogen-containing polydentate ligand. As examples, nitrogen-containing polydentate ligands include pentamethyldiethyltriamine (PMDETA), tris[2-(dimethylamino)ethyl]amine (Me6TREN), and tris(2-pyridylmethyl)amine (TPMA).

[0087] In some embodiments of this application, the first catalyst comprises copper bromide and the ligand comprises pentamethyldiethyltriamine.

[0088] In some embodiments of this application, the molar ratio of the acyl group of the initiator, the catalyst, and the ligand is (1.5~2.5):1:1, for example, 1.5:1:1, 1.7:1:1, 1.9:1:1, 2.0:1:1, 2.2:1:1, 2.5:1:1, etc., preferably 2:1:1. In this way, the catalyst and ligand can form an active complex (such as [CuBr / PMDETA]) in a 1:1 ratio. The molar ratio of this complex to the acyl group of the initiator determines the position of the activation-deactivation equilibrium. If the ratio is too low (<1.5:1:1), there is insufficient activator, the polymerization rate is too slow, and chain termination may occur due to incomplete deactivation; if the ratio is too high (>2.5:1:1), excess catalyst may trigger side reactions and increase the difficulty of post-processing. The 2:1:1 ratio ensures a sufficient activator concentration to achieve rapid initiation and a moderate polymerization rate, while maintaining a good activation-deactivation balance, keeping the molecular weight distribution controlled at PDI < 1.3, which provides a guarantee for the subsequent accurate construction of multi-block structures.

[0089] In some embodiments of this application, the temperature of the atom transfer radical addition reaction is 70°C to 110°C, for example, 70°C, 80°C, 90°C, 100°C, 110°C, etc., preferably 80°C to 100°C, and the time of the atom transfer radical addition reaction is 4h to 10h, for example, 4h, 5h, 6h, 7h, 8h, 9h, 10h, etc., preferably 5h to 8h.

[0090] In step S3: As an example, the third solvent is anhydrous tetrahydrofuran (THF).

[0091] In some embodiments of this application, the hydroxysulfonic acid includes one or more of 3-hydroxypropanesulfonic acid, 2-hydroxyethanesulfonic acid, 4-hydroxybutyric acid, 5-hydroxypentanesulfonic acid, and 6-hydroxyhexanesulfonic acid, with 3-hydroxypropanesulfonic acid being preferred. Thus, the 3-hydroxypropanesulfonic acid (C3 chain) has a moderate carbon chain length, ensuring reactivity while maintaining an appropriate distance between the final lithium sulfonate group and the polymer backbone, reducing the impact of steric hindrance on ion conduction. Simultaneously, the synthesis cost of the C3 chain is relatively low.

[0092] In some embodiments of this application, the acylacrylic acid derivative includes one or more of methacryloyl chloride, acryloyl chloride, and methacrylic anhydride, preferably methacryloyl chloride. Thus, methacryloyl chloride exhibits high reactivity, reacting rapidly with hydroxyl groups under mild conditions, and the α-methyl group of the methacryloyl group contributes to the formation of stable polymer segments.

[0093] In some embodiments of this application, the alkaline lithium source includes one or more of lithium hydroxide (LiOH), lithium carbonate (Li2CO3), lithium acetate (CH3COOLi), and lithium methoxide (CH3OLi).

[0094] In some embodiments of this application, the molar ratio of the hydroxyl group of the hydroxysulfonic acid to the acyl group of the acylacrylic acid derivative is 1:(1.2~1.8), for example, it can be 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, etc., preferably 1:1.5.

[0095] Understandably, acylacrylic acid derivatives are extremely sensitive to water. Trace amounts of moisture in the reaction system can consume some acyl groups, causing hydrolysis and the formation of acrylic acid and HCl. Furthermore, acylacrylic acid derivatives may undergo slight degradation during storage and transfer. Therefore, an excess of acylacrylic acid derivative is necessary to ensure complete hydroxyl conversion. If the ratio is too low (<1:1.2), insufficient acylacrylic acid derivative results in incomplete acylation of hydroxyl groups, and unreacted hydroxyl groups will trigger side reactions in subsequent polymerization or lead to a decrease in monomer purity. If the ratio is too high (>1:1.8), the excess acylacrylic acid derivative will hydrolyze during post-processing, generating excessive acrylic acid, increasing the difficulty of washing and purification, and causing raw material waste. A ratio of 1:1.5 achieves the optimal balance between ensuring complete hydroxyl conversion and avoiding excessive waste, yielding a high-purity (>95%) acylated intermediate, laying the foundation for subsequent neutralization reactions and the optimal performance of the polymer.

[0096] In some embodiments of this application, the second acylation reaction is carried out in the presence of a second catalyst. As an example, the second catalyst comprises 4-dimethylaminopyridine (DMAP).

[0097] In some embodiments of this application, the temperature during mixing of hydroxysulfonic acid and acylacrylic acid derivatives is below 5°C. This effectively suppresses side reactions, controls the reaction rate, and improves reaction selectivity.

[0098] It is understandable that acylinters are prone to hydrolysis and self-polymerization side reactions at higher temperatures, while low-temperature conditions can selectively promote the main reaction (acylation) and inhibit side reactions. The acylation reaction between acylinters and alcohols is a strongly exothermic reaction; slow dropwise addition at low temperatures can control the reaction rate and avoid localized overheating.

[0099] In some embodiments of this application, the second acylation reaction is carried out at room temperature, and the time of the second acylation reaction is 8h to 24h, for example, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, etc., preferably 10h to 16h.

[0100] In some embodiments of this application, the reaction mixture after the second acylation reaction is further filtered and concentrated.

[0101] As an example, filtration can be performed using a Buchner funnel to obtain a clear filtrate. Concentration can be achieved by rotary evaporation at 50°C under reduced pressure to remove hydrochloric acid, residual acylacrylic acid derivatives, and anhydrous THF from the reaction mixture.

[0102] As an example, the fourth solvent is deionized water.

[0103] In some embodiments of this application, the molar ratio of the sulfonic acid group of the acryloyl oxysulfonate to the lithium ion of the alkaline lithium source is 1:(0.95~1.05), for example, it can be 1:0.95, 1:0.98, 1:1, 1:1.02, 1:1.05, etc., preferably 1:(0.98~1.02), and most preferably 1:1.

[0104] Understandably, a sulfonic acid group (-SO3H) theoretically requires an equivalent of lithium ions for complete neutralization to generate lithium sulfonate (-SO3Li) and water. This reaction is a typical acid-base neutralization reaction, rapid and complete, without kinetic obstacles or competing side reactions. Therefore, theoretically, it should be strictly quantified at a 1:1 ratio. If the ratio is too low (<1:0.95), the sulfonic acid group will not be completely neutralized, and the residual acidic group may affect the catalyst activity in subsequent polymerization or cause side reactions with electrode materials in battery applications. If the ratio is too high (>1:1.05), excessive alkaline lithium source will remain in the product, introducing alkaline impurities that may affect the catalytic balance of the atom transfer radical polymerization (ATRP) reaction or react with the electrolyte in the battery system to generate undesirable byproducts. A 1:1 ratio is the optimal choice to ensure complete conversion of the sulfonic acid group to lithium sulfonate without introducing excess impurities, resulting in high-purity active monomer SLiMA, providing high-quality lithium source units for the subsequent precise construction of gradient ion conduction sections.

[0105] In step S4: In some embodiments of this application, a reaction solution containing a first intermediate is mixed with polyol ether acrylate, an acrylate monomer containing at least one of cycloalkyl, phenyl, and tert-butyl groups, and a first active monomer to carry out an atom transfer radical polymerization reaction, including: The reaction solution containing the first intermediate (M1) is mixed with polyol ether acrylate and an acrylate monomer containing at least one of cycloalkyl, phenyl and tert-butyl groups to carry out the first atom transfer radical polymerization (ATRP) reaction. After the reaction is completed, the first active monomer is added to carry out the second atom transfer radical polymerization reaction.

[0106] Understandably, the first intermediate (M1) is a star-shaped macromolecular initiator, with each arm terminally ending in a halogen atom (such as Br). It can undergo a reversible activation-polymerization process with the second block monomer (polyol ether acrylate and acrylate monomers with large-volume rigid side groups (cycloalkyl, phenyl, and tert-butyl)) to obtain an active polymer with halogen atoms still at the ends (such as M1-[PGMEM-co-IBOMA]-Br). The polyol ether acrylate contains a polyol ether segment (-CH2CH2O-). n It can form lithium-ion transport channels, and its ether oxygen atoms (-O-) can react with Li. + Coordination enables the solvation and transport of lithium ions; acrylate groups participate in free radical polymerization; acrylate monomers with large-volume rigid side groups act as crystallization inhibitors, their large-volume rigid side groups can insert between polyol ether segments, disrupting the regular arrangement of polyol ether segments, inhibiting crystallization, and ensuring the mobility of segments across the entire temperature range. After the polymerization of the first intermediate (M1) and the second block monomer is completed, the system yields an active polymer with halogen atoms at the ends (such as M1-[PGMEM-co-IBOMA]-Br). At this point, SLiMA is injected at a uniform rate through an injection pump, which can cause further chain extension reactions, ensuring the formation of flexible channel segments of pure polyol ether acrylate and acrylate monomers with large-volume rigid side groups.

[0107] In some embodiments of this application, the polyol ether acrylate includes one or more of polyethylene glycol monomethyl ether methacrylate (PGMEM), polyethylene glycol methyl ether acrylate (PEGA), methoxy polyethylene glycol methacrylate (mPEG-MA), and polypropylene glycol monomethyl ether methacrylate.

[0108] In some embodiments of this application, the acrylate monomers include one or more of isobornyl methacrylate (IBOMA), cyclohexyl methacrylate (CHMA), tert-butyl methacrylate (tBMA), adamantane methacrylate (AdMA), and benzyl methacrylate (BzMA).

[0109] In some embodiments of this application, the molar ratio of polyol ether acrylate to acrylate monomer is (85~95):(5~15), for example, it can be 85:15, 86:14, 88:12, 90:10, 91:9, 93:7, 94:6, 95:5, etc., preferably 91:9.

[0110] Understandably, if the molar percentage of acrylate monomers with large-volume rigid side groups is too low, the crystallization inhibition effect will be insufficient, leading to a decrease in the low-temperature conductivity of the polymer. If the molar percentage is too high, the polyol ether segments will be over-diluted, affecting ion transport.

[0111] In some embodiments of this application, the molar ratio of the first active monomer to polyol ether acrylate is (0.8~1.0):1, for example, it can be 0.8:1, 0.85:1, 0.9:1, 0.95:1, 1.0:1, etc., preferably 0.9:1.

[0112] Understandably, if the molar percentage of the first active monomer in both is too low, there will be insufficient lithium source; if it is too high, it may form ion clusters that hinder ion transport.

[0113] In some embodiments of this application, the molar ratio of the halogen atom at the end of the first intermediate (M1), the polyol ether acrylate, the acrylate monomer, and the first active monomer is 1:(120~200):(10~30):(100~180), for example, 1:120:10:100, 1:140:15:120, 1:160:20:140, 1:180:25:160, 1:200:30:180, etc., preferably 1:158:18.8:143.

[0114] Understandably, the amount of polyol ether acrylate monomers used determines the main body length of the ion transport segment. Too low a amount results in discontinuous ion channels, while too high a amount hinders chain segment movement. Insufficient use of acrylate monomers with large-volume rigid side groups leads to insufficient crystallization inhibition of the polyol ether segments, resulting in decreased low-temperature conductivity of the star polymer; excessive use over-dilutes the polyol ether segments, affecting ion transport. The amount of the primary active monomer determines the total lithium supply; too low a amount results in insufficient lithium supply, while excessive use may form ion clusters that impede ion transport. Using a ratio of 1:158:18.8:143 achieves the optimal balance between flexible channel length, crystallization inhibition effect, and lithium supply, enabling the ion transport segment to construct a continuous ion transport channel while simultaneously optimizing bulk transport and interfacial enrichment through gradient distribution.

[0115] In some embodiments of this application, the temperature of the first atom transfer radical polymerization reaction is 60°C to 80°C, for example, 60°C, 65°C, 70°C, 75°C, 80°C, etc., preferably 65°C to 75°C, and most preferably 70°C. The time of the first atom transfer radical polymerization reaction is 3h to 6h, for example, 3h, 4h, 5h, 6h, etc., preferably 3.5h to 5h. This ensures that the copolymer segment of polyol ether acrylate and acrylate monomers with large-volume rigid side groups reaches the target molecular weight and has a sufficiently high conversion rate. At this point, SLiMA injection can begin, allowing for further chain extension based on the flexible channel segment formed by the polyol ether acrylate and acrylate monomers with large-volume rigid side groups, thus forming a gradient structure.

[0116] In some embodiments of this application, the temperature of the second atom transfer radical polymerization reaction is 60℃-80℃, for example, 60℃, 65℃, 70℃, 75℃, 80℃, etc., preferably 65℃-75℃, most preferably 70℃, and the time of the first atom transfer radical polymerization reaction is 2h-5h, for example, 2h, 3h, 4h, 5h, etc., preferably 2h-4h, most preferably 3h.

[0117] Understandably, atom transfer radical polymerization (ATRP) reactions typically occur in the range of 60℃-80℃, with the polymerization rate increasing approximately 2 to 3 times for every 10℃ increase in temperature. 70℃ is the optimal temperature for the ATRP polymerization of PGMEM, IBOMA, and SLiMA methacrylate monomers, ensuring both a reasonable polymerization rate and a good activation-deactivation balance.

[0118] In some embodiments of this application, a first active monomer (denoted as SLiMA) is added to carry out a second atom transfer radical polymerization reaction, including: A first active monomer of a first mass is added at a first speed and at a constant rate to carry out a first stage of second atom transfer radical polymerization reaction. Then, a second mass of the first active monomer is added at once to carry out a second stage of second atom transfer radical polymerization reaction.

[0119] Understandably, after the first atom transfer radical polymerization reaction, the first active monomer is continuously and uniformly injected to carry out the first stage of the second atom transfer radical polymerization reaction. By controlling the injection rate and time, the instantaneous concentration of the first active monomer in the reaction system gradually increases from 0% during the injection process, thus creating a continuous and gently increasing gradient distribution of the content of the first active monomer from near the core (content ≈0%) to far from the core. After the first stage of the second atom transfer radical polymerization reaction, the first active monomer is injected again in a single, rapid motion to carry out the second stage of the second atom transfer radical polymerization reaction, forming short chain segments with a high content of the first active monomer, thereby constructing a locally highly concentrated "enriched layer" at the end of the ion-conducting segment.

[0120] In some embodiments of this application, the first injection rate is 1 g / h to 4 g / h, preferably 1.5 to 2.5 g / h. This allows for the formation of a continuous, gently increasing lithium-ion concentration gradient. If the injection rate is too low, the resulting lithium-ion concentration gradient is too gentle, and the end-capacity enrichment effect is not significant; if the injection rate is too high, the resulting lithium-ion concentration gradient is too steep, which may cause abrupt changes in concentration and affect ion transport.

[0121] In some embodiments of this application, the mass ratio of the first active monomer in the first mass to the first active monomer in the second mass is (3~6):1, for example, it can be 3:1, 4:1, 5:1, 6:1, etc., preferably (4~5):1.

[0122] In some embodiments of this application, the time for the first stage of the second atom transfer radical polymerization reaction is 1.5 h to 3 h, for example, 1.5 h, 2 h, 2.5 h, 3 h, etc., preferably 1.5 h to 2.5 h, and most preferably 2 h. This ensures that the uniformly injected SLiMA fully polymerizes and forms a gradient distribution with gradually increasing lithium salt concentration from the inside out. Too short a time may lead to incomplete SLiMA conversion and an incomplete gradient structure; too long a time will reduce efficiency.

[0123] In some embodiments of this application, the time for the second-stage second atom transfer radical polymerization reaction is 0.5 h to 2 h, for example, 0.5 h, 1 h, 1.5 h, 2 h, etc., preferably 0.5 h to 1.5 h, and most preferably 1 h. This ensures that the high-concentration SLiMA injected in a single, rapid reaction is fully polymerized, forming a high-lithium salt concentration enriched layer at the very end of the second block. Too short a time may result in incomplete polymerization of the enriched layer; too long a time may lead to chain termination or chain transfer side reactions due to monomer depletion.

[0124] In step S5: As an example, the fifth solvent is anhydrous tetrahydrofuran (THF).

[0125] In some embodiments of this application, the catecholamine compounds include one or more of dopamine, L-DOPA, norepinephrine, methyldopamine, and 3,4-dihydroxyphenylethylamine derivatives, preferably dopamine. Thus, the carbon chain length (C2) of dopamine (free base) is moderate, and the distance between the catechol and amino groups is appropriate, ensuring both reactivity and a suitable distance between the final catechol groups and the polymer backbone, thereby reducing the impact of steric hindrance on the adhesion function.

[0126] In some embodiments of this application, the acylacrylic acid derivative includes one or more of methacryloyl chloride, acryloyl chloride, and methacrylic anhydride, preferably methacryloyl chloride. Thus, methacryloyl chloride exhibits high reactivity, reacting rapidly with hydroxyl groups under mild conditions, and the α-methyl group of the methacryloyl group contributes to the formation of stable polymer segments.

[0127] In some embodiments of this application, the amidation reaction is carried out in the presence of an acid-binding agent and a catalyst. As an example, the acid-binding agent and catalyst are triethylamine.

[0128] In some embodiments of this application, the molar ratio of the amino group of the catecholamine compound to the acyl group of the acylacrylic acid derivative is 1:(1.2~1.8), for example, it can be 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, etc., preferably 1:(1.4~1.6), and most preferably 1:1.5.

[0129] Understandably, acylacrylic acid derivatives are extremely sensitive to water. Trace amounts of water in the reaction system can consume some acyl groups, causing hydrolysis side reactions. Simultaneously, the catechol groups in catecholamine compounds may oxidize under alkaline conditions, requiring protection through rapid amidation. Excess acyl groups can accelerate the main reaction. If the ratio is too low (<1:1.2), insufficient acyl groups result in incomplete amino acylation, and unreacted catecholamine compounds may trigger side reactions in subsequent polymerization or lead to a decrease in monomer purity. If the ratio is too high (>1:1.8), excess acyl groups will hydrolyze to generate more acrylic acid during post-processing, increasing the difficulty of washing and purification. Furthermore, the amount of acid-binding agent and triethylamine catalyst needs to be increased accordingly, leading to increased triethylamine hydrochloride byproducts and raw material waste. A ratio of 1:1.5 achieves the optimal balance between complete amino acylation and avoiding excessive waste, yielding high-purity (>95%) DOPMA monomers, laying the foundation for the high-density anchoring function of the catechol groups in the subsequent third block.

[0130] In some embodiments of this application, the amidation reaction is carried out in an ice bath for a time of 8h to 24h, such as 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, etc., preferably 10h to 16h.

[0131] In some embodiments of this application, the reaction mixture after the amidation reaction is further filtered and concentrated.

[0132] As an example, filtration can be performed using a Buchner funnel to remove the byproduct triethylamine hydrochloride, yielding a clear filtrate. Concentration can be achieved by rotary evaporation at 50°C under reduced pressure to remove residual acylacrylic acid derivatives and anhydrous THF from the reaction mixture.

[0133] In step S6: The reaction solution containing the second intermediate and the second active monomer are mixed in a sixth solvent to carry out a third atom transfer radical polymerization reaction, including: The reaction solution containing the second intermediate (M2), the epoxy vinyl monomer, and the second active monomer are mixed in the sixth solvent to carry out the third atom transfer radical polymerization (ATRP) reaction.

[0134] Understandably, the second intermediate M2 is a multi-armed star polymer, with each arm ending in a halogen atom (such as M2-Br). It can undergo a reversible activation-polymerization process with the third block monomer (epoxy vinyl monomer and the second active monomer) to form (interfacial bonding / crosslinking segments). Epoxy vinyl monomers refer to monomers containing vinyl double bonds (C=C) and epoxy groups, which can participate in free radical polymerization reactions and undergo epoxy ring-opening reactions during curing.

[0135] As an example, the sixth solvent is anhydrous N,N-dimethylformamide (DMF).

[0136] In some embodiments of this application, the third atom transfer radical polymerization reaction is carried out under the catalysis of transition metal halides. As examples, transition metal halides include CuBr, CuCl, CuI, and FeBr2.

[0137] In some embodiments of this application, the third atom transfer radical polymerization reaction is carried out in the presence of nitrogen-containing polydentate ligands. As examples, nitrogen-containing polydentate ligands include pentamethyldiethyltriamine (PMDETA), tris[2-(dimethylamino)ethyl]amine (Me6TREN), and tris(2-pyridylmethyl)amine (TPMA).

[0138] In some embodiments of this application, the first catalyst comprises copper bromide and the ligand comprises pentamethyldiethyltriamine.

[0139] In some embodiments of this application, the epoxy vinyl monomer includes one or more of glycidyl methacrylate (GMA), glycidyl acrylate, allyl glycidyl ether, glycidyl 4-vinylbenzoate, and glycidyl methacrylate (EPMA), with glycidyl methacrylate (GMA) being preferred. Thus, GMA has moderate ATRP polymerization activity of the methacrylate double bond and high epoxy group reactivity, making it a preferred monomer for introducing epoxy crosslinking sites.

[0140] In some embodiments of this application, the molar ratio of the halogen atom at the end of the second intermediate (M2), the epoxy vinyl monomer, and the second active monomer is 1:(350~550):(200~350), preferably 1:442:266. This allows the third block to have good crosslinking density and anchoring density.

[0141] Understandably, the amount of epoxy vinyl monomer determines the number of epoxy crosslinking sites. If the amount is too low, the crosslinking will be insufficient, and the strength of the crosslinking network will be insufficient. If the amount is too high, the crosslinking network will be too rigid and may interfere with the interfacial enrichment of the terminal second active monomer. The amount of the second active monomer determines the density of catechol anchoring groups. If the amount is too low, the interfacial bonding strength will be insufficient. If the amount is too high, intramolecular oxidative coupling may occur, reducing the effective anchoring density.

[0142] In some embodiments of this application, the molar ratio of the epoxy vinyl monomer and the second active monomer is (1.2~2.0):1. This balances the crosslinking and anchoring functions of the third block.

[0143] In some embodiments of this application, the temperature of the third atom transfer radical polymerization (ATRP) reaction is 60°C to 80°C, for example, 60°C, 65°C, 70°C, 75°C, 80°C, etc., preferably 65°C to 75°C, most preferably 70°C, and the reaction time is 3.5h to 10h, preferably 4.5h to 8h, for example, 4.5h, 5h, 6h, 7h, 8h, etc., most preferably 6h.

[0144] In some embodiments of this application, a reaction solution containing a second intermediate (M2), an epoxy vinyl monomer, and a second active monomer are mixed in a sixth solvent to carry out a third atom transfer radical polymerization (ATRP) reaction, including: The reaction solution containing the second intermediate (M2) and the first mass of epoxy vinyl monomer are mixed in the sixth solvent to carry out the first stage of third atom transfer radical polymerization. Then, the second mass of epoxy vinyl monomer and the first mass of the second active monomer are added to carry out the second stage of third atom transfer radical polymerization. Then, the second mass of the second active monomer is added to carry out the third stage of third atom transfer radical polymerization.

[0145] Understandably, the first stage of the third atom transfer radical polymerization reaction is an atom transfer radical polymerization of the epoxy vinyl monomer, which participates in ATRP copolymerization through its methacrylate double bond to form a pure GMA segment, adjacent to the second block, providing epoxy groups as reaction sites for subsequent crosslinking with cystamine. The second stage of the third atom transfer radical polymerization reaction is a copolymerization reaction of the epoxy vinyl monomer and the second active monomer, forming a GMA / DOPMA copolymer segment, which can simultaneously provide epoxy crosslinking sites and catechol adhesion groups, achieving a balance between crosslinking and adhesion. The third stage of the third atom transfer radical polymerization reaction is an atom transfer radical polymerization reaction of the second active monomer, forming a pure DOPMA end-capped segment, used to provide a high density of catechol groups to achieve strong anchoring with the electrode surface. Thus, the third block comprises a pure GMA segment, a GMA / DOPMA copolymer segment, and a pure DOPMA end-capping segment connected in sequence, which can realize the sequential construction and functional space partitioning of the third block. The pure GMA segment adjacent to the second block is used to provide dense epoxy crosslinking sites, the GMA / DOPMA copolymer segment provides both epoxy crosslinking sites and catechol groups, and the terminal pure DOPMA segment is used to provide high-density catechol groups.

[0146] In some embodiments of this application, the mass ratio of the first mass of epoxy vinyl monomer to the second mass of epoxy vinyl monomer is (50~80):(20~50), for example, it can be 50:50, 60:40, 70:30, 80:20, etc.

[0147] In some embodiments of this application, the mass ratio of the first mass of the second active monomer to the second mass of the second active monomer is (20~50):(50~80), for example, it can be 20:80, 30:70, 40:60, 50:50, etc.

[0148] Understandably, by adding components in stages to achieve spatial partitioning, the inner pure epoxy vinyl monomer segment provides the crosslinking core, the middle pure epoxy vinyl monomer and second active monomer copolymer segment achieves functional transition, and the terminal pure second active monomer segment ensures that high-density catechol is located at the very end of the molecular chain, facilitating interface enrichment. This allows the third block to provide sufficient epoxy crosslinking sites to build a stable network, while also achieving strong anchoring to the electrode surface through the terminal high-density catechol. At the same time, spatial partitioning avoids functional interference, laying the structural foundation for the synergistic achievement of ultra-high bonding strength and excellent cycle stability.

[0149] In some embodiments of this application, the time for the first stage of the third atom transfer radical polymerization reaction is 0.5 h to 2 h, for example, 0.5 h, 1 h, 1.5 h, 2 h, etc., preferably 0.5 h to 1.5 h. In this way, the GMA monomer conversion rate can be guaranteed to be about 90%, and the number average molecular weight (Mn) of the pure GMA segment can be controlled, providing sufficient epoxy crosslinking sites for subsequent reactions.

[0150] In some embodiments of this application, the time for the second-stage third atom transfer radical polymerization reaction is 2h to 5h, for example, 2h, 3h, 4h, 5h, etc., preferably 2.5h to 4h. In this way, the copolymerization conversion rate of GMA and DOPMA can be guaranteed to be about 90%, and the number-average molecular weight (Mn) of the copolymerization segment can be controlled to achieve an appropriate balance between crosslinking sites and binding groups.

[0151] In some embodiments of this application, the time for the third-stage atom transfer radical polymerization reaction is 1 to 3 hours, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, etc., preferably 1.5 hours to 2.5 hours. This ensures a DOPMA monomer conversion rate of approximately 90% and allows control over the number-average molecular weight (Mn) of the pure DOPMA end-capping segments, ensuring that each arm is end-capped with a high density of catechol groups, providing sufficient molecular anchors for interfacial anchoring.

[0152] In some embodiments of this application, the reaction solution after the third atom transfer radical polymerization (ATRP) reaction is added to a seventh solvent to precipitate the star polymer, followed by drying.

[0153] As an example, the seventh solvent includes ethyl acetate, which allows the star polymer to precipitate and removes catalyst residue. Drying can be performed under vacuum at 40°C for 48 hours.

[0154] This application also provides an adhesive comprising the star-shaped polymer described above.

[0155] In some embodiments of this application, the adhesive further includes a crosslinking agent, which is a polyamine compound comprising dynamic covalent bonds.

[0156] Understandably, the epoxy groups in star polymers can undergo ring-opening addition reactions with the amino groups in polyamine compounds to form hydroxyamine structures, thereby introducing dynamic covalent bonds from the polyamine compounds into the star polymer network. Ring-opening addition reactions can occur between multiple star arms of the star polymer, forming a three-dimensional dynamic covalent network. Each crosslinking point in the network contains reversible dynamic covalent bonds. When the temperature rises to the exchange temperature of the dynamic covalent bonds (e.g., disulfide bonds are typically >60~80°C), the dynamic covalent bonds can undergo reversible breakage and rearrangement, allowing the dynamic covalent network to rearrange the topology of the star polymer without reducing the crosslinking density, thus achieving stress relaxation and shape memory functions.

[0157] It is understood that polyamines refer to compounds containing at least two amino groups. As examples, polyamines that include dynamic covalent bonds include cystamine, dithioethylenediamine, bis(3-fluoro-4-aminophenyl)disulfide, diamines containing diselenyl bonds, diamines containing diene synthesis bonds (Diels-Alder bonds), and diamines containing borate ester bonds.

[0158] In some embodiments of this application, the dynamic covalent bond includes at least one of disulfide bond, diselenide bond, dielene synthesis bond (Diels-Alder bond), and borate ester bond.

[0159] Understandably, in a reducing environment (such as the local reducing atmosphere that may be generated at the negative electrode of a battery), disulfide bonds and diselenide bonds can be reduced to two thiol groups and two selenool groups, respectively, thereby temporarily reducing the crosslinking density of the dynamic covalent network and making the network deformable or degraded; when the reducing conditions disappear, the thiol groups and selenool groups can be oxidized to reform disulfide bonds and diselenide bonds, respectively, thus achieving network reconstruction.

[0160] In some embodiments of this application, the polyamine compound includes at least one of cystamine, dithioethylenediamine, bis(3-fluoro-4-aminophenyl)disulfide, 1,3,4-selenodiazole-2-amine, and diethanolamine borate.

[0161] In some embodiments of this application, the binder also includes polyvalent metal ions.

[0162] Understandably, polyvalent metal ions can undergo ion exchange reactions with the lithium sulfonate ion groups of star polymers, forming ion bridges centered on the polyvalent metal ions. These bridges then connect the sulfonate ion groups on the two star arms of the star polymer, forming a three-dimensional ion-crosslinked network. These ion bonds can reversibly break under stress to dissipate energy and reform after stress removal, significantly improving the toughness and fatigue resistance of the adhesive, with far less hindrance to ion transport than covalent crosslinking. Simultaneously, the ion exchange reaction provides immediate pre-bonding at room temperature, ensuring close contact between crack surfaces; the dynamic covalent network formed by the ring-opening addition reaction completes permanent repair upon heating. The synergistic effect of both reactions creates a fast-slow combined healing mechanism, thereby enhancing the self-healing ability of the adhesive. The ion exchange reaction and the ring-opening addition reaction can proceed independently without interference, jointly forming a dual dynamic crosslinked network.

[0163] In some embodiments of this application, the multivalent metal ions include Zn. 2+ Ca 2+ Cu 2+ Al 3+ Mg 2+ and Sr 2+ At least one of them.

[0164] As an example, the polyvalent metal ions originate from Zn(TFSI)2, Zn(CF3SO3)2, Zn(BF4)2, Zn(Ac)2, Ca(TFSI)2, Ca(CF3SO3)2, Cu(TFSI)2, Cu(CF3SO3)2, Al(TFSI)3, Mg(TFSI)2, Mg(CF3SO3)2, and Sr(TFSI)2.

[0165] In some embodiments of this application, the binder further includes zinc bis(trifluoromethanesulfonyl)imide (Zn(TFSI)2). Thus, Zn 2+ The coordination bond strength with sulfonate ions is moderate, allowing for energy dissipation during fracture under stress and recombination after stress removal, achieving an optimal balance between toughness and strength. Zn(TFSI)2 exhibits good stability in battery systems, reducing harmful side reactions and demonstrating excellent electrochemical compatibility. Zn(TFSI)2 maintains a good balance between free radical cation generation and ion mobility, resulting in high efficiency and stability in ion exchange reactions. Furthermore, Zn(TFSI)2 shows good compatibility with star polymer matrices, enabling uniform blending and facilitating processing.

[0166] In some embodiments of this application, the molar ratio of the epoxy group of the star polymer to the amino group of the polyamine compound is 1:(1.4~2.0). This allows the resulting covalently cross-linked network to have moderate strength. If the amount of polyamine compound is too low, insufficient covalent cross-linking results in an inadequate network strength; if the amount of polyamine compound is too high, excessive cross-linking leads to excessive network rigidity and may consume the active groups at the ends of the star polymer.

[0167] In some embodiments of this application, the molar ratio of lithium sulfonate ion groups to polyvalent metal ions in the star polymer is 1:(0.1~0.3), for example, 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, etc. This allows the formed ionic crosslinking network to have good stress dissipation effects while ensuring effective lithium ion transport. If the amount of polyvalent metal ions is too low, the ionic crosslinking is insufficient, resulting in poor stress dissipation; if the amount of polyvalent metal ions is too high, excessive ion clusters may form, hindering ion transport and reducing free lithium. + concentration.

[0168] This application also provides an electrode material, including a positive active material and the binder described above, or a negative active material and the binder described above.

[0169] It is understandable that electrode materials may also include conductive agents and solvents.

[0170] In some embodiments of this application, the electrode material includes a positive electrode active material, and the ratio of m1 to m2 is (90~95):(5~10), for example, it can be 90:10, 91:9, 93:7, 94:6, 95:5, etc. In this way, the oxidation resistance of the electrode material can be enhanced.

[0171] In some embodiments of this application, the electrode material includes a negative electrode active material, and the ratio of m1 to m2 is (92~97):(3~8), for example, it can be 92:8, 93:7, 94:6, 95:5, 96:4, 97:3, etc., preferably 95:5.

[0172] This application also provides an electrode sheet, including an active layer formed by curing the above-mentioned electrode material.

[0173] It is understood that the binder of this application can be used in both positive and negative electrode sheets. As an example, the positive electrode sheet can be a high-nickel positive electrode (NCM811, etc.), where the catechol in the star-shaped polymer has a strong coordination ability with transition metal oxides, which can improve the binding effect of the binder; the positive electrode sheet can be a lithium iron phosphate positive electrode, which can provide sufficient bonding strength; the positive electrode active material can be a lithium cobalt oxide positive electrode. The negative electrode sheet can be a silicon-carbon negative electrode, which can improve its toughness and resistance to volume expansion.

[0174] This application also provides a method for preparing an electrode sheet, comprising: The above electrode material is placed on the surface of the current collector and cured to form an active layer, thus obtaining an electrode sheet.

[0175] In some embodiments of this application, the curing temperature is 70℃~100℃, for example, 70℃, 75℃, 80℃, 85℃, 90℃, 100℃, etc., preferably 75℃~85℃, and the curing time is 8h~24h, for example, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, etc., preferably 10h-16h. This allows the star-shaped polymer, crosslinking agent, and Zn(TFSI)2 to undergo a crosslinking reaction, while simultaneously removing the solvent from the electrode material. If the temperature is too low, the crosslinking reaction is incomplete, and solvent residue is easily left, which may affect battery performance; if the temperature is too high, it may cause oxidation of catechol groups or thermal degradation of the polymer. If the time is too short, the crosslinking reaction is incomplete, and solvent residue is easily left; if the time is too long, efficiency decreases, and there is no additional benefit.

[0176] This application also provides a battery comprising the aforementioned electrode.

[0177] The present invention will now be described in conjunction with preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the appended claims summarize the scope of the present invention. Under the guidance of the inventive concept, those skilled in the art should realize that any changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention.

[0178] The organic reagents used in the embodiments and comparative examples of this application and their chemical structures are shown below: Sorbitol: Molecular weight = 182.17; 2-Bromoisobutyryl bromide: Molecular weight = 229.91; 4-Dimethylaminopyridine (DMAP): Molecular weight = 122.17; Vinylidene fluoride (VDF): Molecular weight = 64.03; Hexafluoropropylene (HFP): Molecular weight = 150.02; Polyethylene glycol monomethyl ether methacrylate (PGMEM): n represents the degree of polymerization, which is an integer from 2 to 7, and the number average molecular weight is 300. Isobornyl methacrylate (IBOMA): Molecular weight = 222.32; Methacryl chloride: Molecular weight = 104.53; 3-Hydroxypropanesulfonic acid: Molecular weight = 140.16; Triethylamine: Molecular weight = 101.19; Glycidyl methacrylate (GMA): Molecular weight = 142.15; Dopamine: Molecular weight = 153.18.

[0179] Example 1 A star-shaped polymer and its preparation method, comprising: (1) In a dry 500 mL three-necked flask, add anhydrous sorbitol (3.64 g, 20.0 mmol), 4-dimethylaminopyridine (DMAP, 0.24 g, 2.0 mmol), and 150 mL of anhydrous dichloromethane. Stir until the reactants are completely dissolved. Place the system in an ice bath and, under nitrogen protection, add a mixture of 2-bromoisobutyryl bromide (29.5 mL, 240 mmol) and anhydrous dichloromethane (30 mL) dropwise using a constant pressure dropping funnel, keeping the internal temperature below 5 °C. After the addition is complete, remove the ice bath and allow the mixture to react at room temperature for 24 h. The reaction solution was washed successively with 5% dilute hydrochloric acid, saturated NaHCO3 solution, and brine. The organic phase was dried over anhydrous MgSO4, then rotary evaporated and concentrated to obtain a crude product. The crude product was then purified by silica gel column chromatography (the mobile phase consisted of petroleum ether and ethyl acetate in a volume ratio of 10:1, with the ethyl acetate ratio gradually increased to 4:1) to obtain a colorless viscous liquid. The colorless viscous liquid was recrystallized in n-hexane at -20℃ to obtain the initiator (white crystals with 6 active sites and a molecular weight of 1076.17; its specific structural formula and the reaction equation of step 1 are shown below).

[0180] (2) The initiator (2.15 g, 2.0 mmol, based on 6 initiation sites), the catalyst copper bromide (CuBr, 0.86 g, 6.0 mmol), the ligand pentamethyldiethyltriamine (PMDETA, 1.26 mL, 6.0 mmol), and anhydrous N,N-dimethylformamide (DMF, 50 mL) were added to a 200 mL high-pressure reactor. After three cycles of freezing, vacuuming, and nitrogen purging to remove oxygen, vinylidene fluoride (VDF, 27 g) and hexafluoropropylene (HFP, 3 g) were introduced into the reactor under liquid nitrogen cooling. g) (VDF and HFP molar ratio is 95:5), place the reactor in a 90℃ oil bath, mechanically stir the reaction, monitor the monomer consumption with a pressure gauge, and when the pressure drops to half of the initial value (6 hours), stop heating, quickly cool to room temperature, release the unreacted monomer, and obtain a reaction solution containing the first intermediate M1 (the first intermediate M1 is a star-shaped PVDF-co-HFP-Br macromolecular initiator containing a first block: a rigid fluorocarbon segment, with bromine atoms at the end of each arm, and its structural formula and the reaction equation of step 2 are shown below).

[0181] (3) Add 3-hydroxypropanesulfonic acid (14 g, 0.1 mol), catalyst 4-dimethylaminopyridine (DMAP, 1.2 g, 0.01 mol), and anhydrous tetrahydrofuran (THF, 100 mL) to a 250 mL three-necked flask. Stir until the reactants are completely dissolved. Then place the system in an ice bath under nitrogen protection and add a mixture of methacryloyl chloride (15.7 g, 0.15 mol) and anhydrous tetrahydrofuran (THF, 50 mL) dropwise using a constant pressure dropping funnel, keeping the internal temperature below 5 °C. After the addition is complete... Afterwards, the ice bath was removed, and the reaction was allowed to proceed at room temperature for 12 hours. After the reaction was completed, the reaction mixture was filtered through a Buchner funnel to obtain a clear filtrate. The clear filtrate was then concentrated by rotary evaporation under reduced pressure at 50°C to obtain a golden yellow viscous liquid. Deionized water (50 ml) and lithium hydroxide (2.4 g, 0.1 mol) were then added, and the mixture was stirred at room temperature for 20 min to carry out an acid-base neutralization reaction. The deionized water was then removed by rotary evaporation to obtain the first active monomer (denoted as SLiMA, whose structural formula and reaction process are shown below).

[0182] (4) Pour the reaction solution containing the first intermediate M1 obtained in step 2 into a 250ml dry three-necked flask, and add polyethylene glycol monomethyl ether methacrylate (PGMEM, 9.5g) and isobornyl methacrylate (IBOMA, 0.5g) in sequence (the molar ratio of PGMEM and IBOMA is 93:7). After three cycles of freezing-vacuuming-nitrogen purging, turn on magnetic stirring and react in an oil bath at 70℃ for 4 hours. Then, start injecting the DMF solution of the first active monomer (concentration of 2g / 10mL, a total of 4g of the first active monomer) at a uniform rate over 2 hours using a syringe pump. After the injection is completed, continue the reaction for 2 hours. Then, inject another DMF solution of the first active monomer (concentration of 2g / 10mL, a total of 1g of the first active monomer) at once. After reacting for 1 hour, cool and stop the reaction to obtain the reaction solution containing the second intermediate M2 (the second intermediate M2 contains a rigid fluorocarbon segment and an ion-conducting segment. The schematic diagram of the structure of intermediate M2 and the schematic diagram of the reaction equation in step 4 are shown below).

[0183] (5) Weigh dopamine (15.3 g, 0.1 mol), triethylamine (15.2 g, 0.15 mol) and anhydrous THF (100 mL) and add them to a 250 mL dry three-necked flask. Stir and stir until the reactants are completely dissolved. Then place the system in an ice bath and add a mixture of methacryloyl chloride (15.7 g, 0.15 mol) and anhydrous THF (50 mL) dropwise using a constant pressure dropping funnel under nitrogen protection. After the addition is complete, react in an ice bath for 12 h. After the reaction is complete, filter the reaction mixture through a Buchner funnel to obtain a clear filtrate. Then concentrate the clear filtrate by rotary evaporation under reduced pressure at 50 °C to obtain the second active monomer (denoted as DOPMA, whose structural formula and the reaction equation of step 5 are shown below).

[0184] (6) Under nitrogen protection, glycidyl methacrylate (GMA, 5g) and anhydrous DMF (20ml) were added to the reaction solution containing the second intermediate M2 obtained in step 4. The reaction was carried out at 70°C for 1h. Then, glycidyl methacrylate (GMA, 2.5g), the second active monomer (DOPMA, 2.5g) and anhydrous DMF (20ml) were added. The reaction was carried out at 70°C for 3h. Then, the second active monomer (DOPMA, 5g) and anhydrous DMF (20ml) were added. The reaction was carried out at 70°C for 2h. After the reaction was completed, the reaction solution was dropped into ethyl acetate for precipitation. The precipitate was collected, dissolved in THF, and then precipitated again in ethyl acetate. This process was repeated three times. The obtained product was vacuum dried at 40°C for 48 hours to obtain the star polymer (the structural schematic of the star gradient block polymer and the reaction equation of step 6 are shown below).

[0185]

[0186] An adhesive and its preparation method, comprising: Cystamine dihydrochloride (0.86 g, 3.8 mmol) was dissolved in a mixture of deionized water (10 mL) and methanol (10 mL), and triethylamine (2 mL) was added to release cystamine, thus obtaining a cystamine solution. Zn(TFSI)2 (1.1 g, 1.9 mmol) was dissolved in anhydrous N-methylpyrrolidone (NMP, 10 mL) to obtain a Zn(TFSI)2 solution; The star-shaped polymer (10g) was dissolved in anhydrous NMP (85g) and magnetically stirred until completely transparent. While stirring, cystamine solution and Zn(TFSI)2 solution were added in sequence, and stirring was continued for 2 hours to obtain the adhesive.

[0187] Example 2 This embodiment is basically the same as embodiment 1, except that in step 2 of the star polymer preparation process in this embodiment, the monomer consumption is monitored by a pressure gauge and heating is stopped when the pressure drops to half of the initial value (6 hours). Instead, the monomer consumption is monitored by a pressure gauge and heating is stopped when the pressure drops to 1 / 4 of the initial value (10 hours).

[0188] Example 3 This embodiment is basically the same as Embodiment 1, except that step 4 in the star polymer preparation process is changed to: The reaction solution containing the first intermediate M1 obtained in step 2 was poured into a 250 ml dry three-necked flask. Polyethylene glycol monomethyl ether methacrylate (PGMEM, 4.75 g) and isobornyl methacrylate (IBOMA, 0.25 g) were added sequentially (the molar ratio of PGMEM to IBOMA was 93:7). After three cycles of freezing-vacuuming-nitrogen purging, magnetic stirring was started, and the reaction was carried out in an oil bath at 70 °C for 2 hours. Then, the DMF solution of the first active monomer (concentration of 2 g / 10 mL, a total of 8 g of the first active monomer) was injected uniformly over 2 hours using a syringe pump. After the injection was completed, the reaction was continued for 4 hours. Then, another DMF solution of the first active monomer (concentration of 2 g / 10 mL, a total of 2 g of the first active monomer) was injected at once. After the reaction was completed for 2 hours, the mixture was cooled and the reaction was stopped to obtain the reaction solution containing the second intermediate M2.

[0189] Example 4 This embodiment is basically the same as Embodiment 1, except that step 6 in the star polymer preparation process is changed to: Under nitrogen protection, glycidyl methacrylate (GMA, 5g) and anhydrous DMF (20ml) were added to the reaction solution containing the second intermediate M2 obtained in step 4, and the reaction was carried out at 70°C for 1h. Then, glycidyl methacrylate (GMA, 1.7g), the second active monomer (DOPMA, 3.4g), and anhydrous DMF (20ml) were added, and the reaction was carried out at 70°C for 3h. Then, the second active monomer (DOPMA, 5g) and anhydrous DMF (20ml) were added, and the reaction was carried out at 70°C for 2h. After the reaction was completed, the reaction solution was dropped into ethyl acetate for precipitation. The precipitate was collected, dissolved in THF, and then precipitated again in ethyl acetate. This process was repeated three times. The obtained product was vacuum dried at 40°C for 48 hours to obtain the star polymer.

[0190] Example 5 This embodiment is basically the same as Embodiment 1, except that the amount of Zn(TFSI)2 in the adhesive in this embodiment is 2.2g (3.8mmol).

[0191] Example 6 This embodiment is basically the same as that of Embodiment 1, except that the anhydrous sorbitol (3.64g, 20.0mmol) in step 1 of the star polymer preparation process is replaced with anhydrous pentaerythritol (2.72g, 20.0mmol).

[0192] Example 7 This embodiment is basically the same as Embodiment 1, except that step 6 in the star polymer preparation process is changed to: Under nitrogen protection, glycidyl methacrylate (GMA, 7.5 g), the second active monomer (DOPMA, 7.5 g), and anhydrous DMF (60 ml) were added to the reaction solution containing the second intermediate M2 obtained in step 4 in one step. The reaction was carried out at 70 °C for 6 h. After the reaction was completed, the reaction solution was added dropwise to ethyl acetate for precipitation. The precipitate was collected, dissolved in THF, and then precipitated again in ethyl acetate. This process was repeated three times. The obtained product was dried under vacuum at 40 °C for 48 h to obtain the star polymer.

[0193] Example 8 This embodiment is basically the same as Embodiment 1, except that hexafluoropropylene (HFP) is replaced with trifluorochloroethylene (CTFE), and the molar ratio of VDF to CTFE is 95:5.

[0194] Example 9 This embodiment is basically the same as Example 1, except that polyethylene glycol monomethyl ether methacrylate (PGMEM) is replaced with polyethylene glycol methyl ether acrylate (PEGA, Mn is 500), isobornyl methacrylate (IBOMA) is replaced with cyclohexyl methacrylate (CHMA), and 3-hydroxypropanesulfonic acid is replaced with 2-hydroxyethanesulfonic acid. The molar amounts of each substance are the same as the original substances.

[0195] Example 10 This embodiment is basically the same as Example 1, except that glycidyl methacrylate (GMA) is replaced with allyl glycidyl ether (AGE) and dopamine is replaced with levodopa. The molar amounts of each substance are the same as the original substances.

[0196] Comparative Example 1 This comparative example is essentially the same as Example 1, except that the initiator obtained in step 1 of the star polymer preparation process is replaced with ethyl 2-bromoisobutyrate (12.0 mmol, linear initiator based on 1 initiation site), and steps 4 and 6 are replaced with the following processes: (4) Pour the reaction solution containing the first intermediate M1 obtained in step 2 into a 250ml dry three-necked flask, add polyethylene glycol monomethyl ether methacrylate (PGMEM, 9.5g), isobornyl methacrylate (IBOMA, 0.5g) and DMF solution of the first active monomer (concentration of 2g / 10mL, a total of 5g of the first active monomer is added), after three cycles of freezing-vacuuming-nitrogen purging, turn on magnetic stirring, react in an oil bath at 70℃ for 9h, cool and stop the reaction to obtain the reaction solution containing the second intermediate M2; (6) Under nitrogen protection, glycidyl methacrylate (GMA, 7.5 g), second active monomer (DOPMA, 7.5 g) and anhydrous DMF (60 ml) were added to the reaction solution containing the second intermediate M2 obtained in step 4. The reaction was carried out at 70 °C for 6 h. After the reaction was completed, the reaction solution was dropped into ethyl acetate for precipitation. The precipitate was collected, dissolved in THF, and then precipitated again in ethyl acetate. This process was repeated three times. The obtained product was dried under vacuum at 40 °C for 48 h to obtain a linear polymer.

[0197] Comparative Example 2 This comparative example is basically the same as Example 1, except that step 4 in the preparation process of the star polymer is changed to: The reaction solution containing the first intermediate M1 obtained in step 2 was poured into a 250ml dry three-necked flask, and polyethylene glycol monomethyl ether methacrylate (PGMEM, 10g) and a DMF solution of the first active monomer (concentration of 2g / 10mL, a total of 5g of the first active monomer) were added in sequence. After three cycles of freezing-vacuuming-nitrogen purging, magnetic stirring was turned on, and the reaction was carried out in an oil bath at 70℃ for 6h to obtain a reaction solution containing the second intermediate M2.

[0198] Comparative Example 3 This comparative example is essentially the same as Example 1, except that the initiator obtained in step 1 of the star polymer preparation process is replaced with ethyl 2-bromoisobutyrate (12.0 mmol), and steps 2, 4, and 6 are replaced with the following process, and step 7 is added: (2) Synthesis of random copolymer A: In a high-pressure reactor, ethyl 2-bromoisobutyrate (12.0 mmol) was used as the initiator, and copper bromide (CuBr, 0.86 g, 6.0 mmol), pentamethyldiethyltriamine (PMDETA, 1.26 mL, 6.0 mmol), and anhydrous N,N-dimethylformamide (DMF, 50 mL) were added as catalysts. After three cycles of freezing-vacuuming-nitrogen circulation to remove oxygen, vinylidene fluoride (VDF, 27 g) and hexafluoropropylene (HFP, 3 g) (VDF and HFP molar ratio of 95:5) were introduced into the reactor under liquid nitrogen cooling. The reactor was placed in a 90°C oil bath and mechanically stirred. The reaction was stopped after 6 hours, and then purified to obtain VDF-HFP random copolymer A. (4) Synthesis of random copolymer B: In a 250 mL three-necked flask, ethyl 2-bromoisobutyrate (12.0 mmol) was used as the initiator, and copper bromide (CuBr, 0.86 g, 6.0 mmol), pentamethyldiethyltriamine (PMDETA, 1.26 mL, 6.0 mmol), anhydrous N,N-dimethylformamide (DMF, 50 mL), polyethylene glycol monomethyl ether methacrylate (PGMEM, 9.5 g), isobornyl methacrylate (IBOMA, 0.5 g) and SLiMA (5 g) were added at once. The mixture was reacted at 70 °C for 7 hours and then purified to obtain PGMEM-IBOMA-SLiMA random copolymer B. (6) Synthesis of random copolymer C: In a 250 mL three-necked flask, ethyl 2-bromoisobutyrate (12.0 mmol) was used as the initiator, and copper bromide (CuBr, 0.86 g, 6.0 mmol), pentamethyldiethyltriamine (PMDETA, 1.26 mL, 6.0 mmol), anhydrous N,N-dimethylformamide (DMF, 50 mL) were added one at a time. Glycidyl methacrylate (GMA, 7.5 g) and the second active monomer (DOPMA, 7.5 g) were added in one go. The reaction was carried out at 70 °C for 6 hours, and then purified to obtain GMA-DOPMA random copolymer C. (7) Physical blending and crosslinking: Dissolve random copolymer A, random copolymer B and random copolymer C in THF, stir and mix evenly, and then remove THF by rotary evaporation.

[0199] (2) Under liquid nitrogen cooling, vinylidene fluoride (VDF, 27g) and hexafluoropropylene (HFP, 3g) (VDF and HFP molar ratio of 95:5) were introduced into the high-pressure reactor. The reactor was placed in a 90°C oil bath and mechanically stirred. The monomer consumption was monitored by a pressure gauge. When the pressure dropped to half of the initial value (6 hours), heating was stopped and the reactor was rapidly cooled to room temperature to release the unreacted monomers and obtain a random copolymer A of VDF and HPF. (4) A DMF solution of polyethylene glycol monomethyl ether methacrylate (PGMEM, 9.5g), isobornyl methacrylate (IBOMA, 0.5g), and the first active monomer (SLiMA) (concentration of 2g / 10mL, with a total of 5g of the first active monomer added) was poured into a 250ml dry three-necked flask. After three cycles of freezing-vacuuming-nitrogen purging, magnetic stirring was turned on, and the reaction was carried out in an oil bath at 70℃ for 9h. After cooling, the reaction was stopped to obtain random copolymer B of PGMEM, IBOMA and SLiMA. (6) Under nitrogen protection, glycidyl methacrylate (GMA, 7.5g) and the second active monomer (DOPMA, 7.5g) were added to anhydrous DMF (60ml) and reacted at 70℃ for 6h. After the reaction was completed, the reaction solution was dropped into ethyl acetate for precipitation. The precipitate was collected, dissolved in THF and precipitated again in ethyl acetate. This process was repeated three times. The obtained product was vacuum dried at 40℃ for 48h to obtain random copolymer C of GMA and DOPMA. (7) Dissolve ethyl 2-bromoisobutyrate (12.0 mmol), random copolymer A, random copolymer B and random copolymer C in THF, stir and mix, and then concentrate by rotary evaporation to remove THF.

[0200] The binders obtained from the examples and comparative examples were applied to the negative electrode sheets of the batteries and their performance was tested. The test results are shown in Table 1.

[0201] Method for preparing negative electrode sheet: The binder obtained in the examples and comparative examples is mixed with silicon-carbon negative electrode material (Si / C) and conductive carbon black in a planetary mixer at a weight ratio of 10:85:5. The mixture is then coated onto copper foil and vacuum dried at 80°C for 12 hours to complete cross-linking and remove solvent. Finally, the mixture is rolled to obtain the negative electrode sheet for experimental use.

[0202] Ionic conductivity testing method: Performed according to standard IEC 62620:2014 (AC impedance method). Specifically, a uniform (200 μm) thin film of binder was prepared and sandwiched between stainless steel blocking electrodes to assemble a symmetrical cell. Electrochemical impedance spectroscopy (EIS) was performed using an electrochemical workstation (Solartron 1470E) at 25°C and 0°C, with a frequency range of 1 MHz to 0.1 Hz and an amplitude of 10 mV. The bulk resistance (R) was obtained from the high-frequency region and the real axis intercept of the EIS spectrum. The ionic conductivity (σ) was calculated using the formula σ = L / (R × A), where L is the film thickness and A is the electrode area.

[0203] Peel strength test method: The test was conducted according to standard GB / T 2792-2014, "Test Method for Peel Strength of Adhesives". Specifically, the prepared negative electrode sheet (containing adhesive) was cut into strips 25 mm wide. High-strength double-sided adhesive was used to attach the adhesive layer to a clean, rigid substrate (such as a stainless steel sheet). The sample was fixed on a universal testing machine (Instron 5967) and peeled at a constant speed of 300 mm / min at a 180° angle. The force curve during the peeling process was recorded. The peel strength was calculated by dividing the average force (in N) during the stable peeling phase by the sample width (m).

[0204] Tensile strength and elongation at break test methods: Perform the test according to standard ISO 37:2017 "Determination of tensile stress-strain properties of vulcanized or thermoplastic rubber". Specifically, cast the adhesive slurry into a film, dry it, and cut it into standard dumbbell-shaped specimens. Perform tensile testing on a universal testing machine at a constant tensile rate (e.g., 50 mm / min) until the specimen breaks. Record the maximum tensile force and the original cross-sectional area, and calculate the tensile strength. Measure the elongation between the marks at fracture and calculate the elongation at break.

[0205] Cycle stability testing method for assembled batteries: Referring to the industry-standard full-cell testing method, the specific operation is as follows: using a silicon-carbon negative electrode sheet prepared with the binder of the example / comparative example as the working electrode, a lithium metal sheet as the counter electrode / reference electrode, and 1M LiPF6 dissolved in ethylene carbonate (EC) / diethyl carbonate (DEC) (1:1 vol%) as the electrolyte, CR2032 coin cells are assembled. Charge-discharge cycle tests are performed at a constant current (0.5C rate) on the Blue Battery testing system (voltage window 0.01-1.5V). The discharge capacity of each cycle is recorded, and the capacity retention rate after 100 cycles is calculated.

[0206] Self-healing efficiency test method: Referring to the general evaluation method for the self-healing performance of polymer materials, the specific operation is as follows: Use a sharp blade to create a standard scratch (1 cm in length and 50% of the film thickness) on the dry adhesive film. Heat-treat the film at 80°C for 2 hours. Compare the tensile strength recovery rate of the same batch of film samples before and after healing.

[0207] Table 1

[0208] As can be seen from Table 1: Compared with Example 1, Example 2 has higher peel strength and tensile strength. This is because the rigid fluorocarbon segment in the star polymer of Example 2 is longer. It can be seen that the strength of the star polymer can be improved by increasing the length of the rigid fluorocarbon segment in the star polymer.

[0209] Compared with Example 1, Example 3 has a higher ionic conductivity. This is because the star polymer in Example 3 has a higher proportion and content of SLiMA in the ion-conducting segment, which improves its conductivity. However, its peel strength and cycle retention rate are slightly lower, possibly because the increased proportion of SLiMA leads to an increase in the polarity of the ion-conducting segment, which in turn affects the interfacial enrichment efficiency at the end of the third block.

[0210] Compared with Example 1, Example 4 has higher peel strength and tensile strength. This is because the star polymer in Example 4 has more catechol groups and fewer epoxy groups in the interfacial bonding / crosslinking segments. It can be seen that the adhesion ability of the star polymer can be adjusted by adjusting the ratio of crosslinking groups and adhesive groups in the interfacial bonding / crosslinking segments.

[0211] Compared to Example 1, Example 5 showed higher elongation at break (398%) and higher self-healing efficiency (95.1%), but lower tensile strength and peel strength. This is because the dynamic disulfide bonds provided by cystamine mainly contributed to the thermally triggered self-healing, while Zn... 2+ Ionic crosslinking, as a dynamic bond with moderate strength and high reversibility, preferentially breaks under external force to dissipate energy, thereby endowing the material with extremely high toughness (high elongation at break). It can be seen that by adjusting the ratio of the two crosslinking agents, the strength, toughness and self-healing properties of the material can be directionally controlled within a certain range to meet the needs of different application scenarios.

[0212] Compared with Example 6, Example 1 has higher ionic conductivity, peel strength, tensile strength, elongation at break, capacity retention after 100 turns, and self-healing efficiency. This is because the star polymer synthesized in Example 1 based on sorbitol has more star arms than the star polymer synthesized in Example 5 based on pentaerythritol. It can be seen that by increasing the number of star arms of the star polymer, the performance of the star polymer can be improved.

[0213] Compared to Example 7, Example 1 exhibits higher ionic conductivity, peel strength, tensile strength, elongation at break, capacity retention after 100 turns, and self-healing efficiency. This is because Example 7 involves the one-time addition of glycidyl methacrylate (GMA) and the second active monomer (DOPMA), resulting in an interfacial bonding / crosslinking segment that is a random copolymer of GMA and DOPMA. It is evident that Example 1, by adding GMA and DOPMA stepwise during the formation of the interfacial bonding / crosslinking segment, creates a sequenced structure, including pure GMA segments, GMA-DOPMA copolymer segments, and pure DOPMA segments, thus achieving functional partitioning and enhancing the performance of the star polymer.

[0214] Compared with Example 1, Example 9 has a higher ionic conductivity. This is because the chain segments of the ion-conducting segment formed in Example 9 are more flexible. It can be seen that the ionic conductivity of the star polymer can be controlled by controlling the flexibility of the ion-conducting segment.

[0215] Compared with Example 10, Example 10 has a higher peel strength. This is because the L-DOPA used in Example 10 has more carboxyl groups than the dopamine used in Example 1, thus introducing carboxyl groups into the star polymer. Carboxyl groups can form hydrogen bonds, thereby improving the peel strength of the electrode.

[0216] Compared to Comparative Example 1, Example 1 exhibits higher ionic conductivity, peel strength, tensile strength, elongation at break, capacity retention after 100 turns, and self-healing efficiency. This is because Comparative Example 1 uses ethyl 2-bromoisobutyrate as a linear initiator, resulting in a linear polymer structure. It is evident that the star-shaped structure is crucial for constructing a high-strength three-dimensional network framework, with a much higher physical entanglement density than the linear structure. Furthermore, the random copolymerization method used in Comparative Example 1 leads to a disordered distribution of functional groups, resulting in tortuous and discontinuous ion channels, and rigid segments also hindering ion transport. In contrast, this application, through gradient polymerization, forms a gradient sequence, enabling spatial continuity of the ion-conducting segments (PEGMA / IBOMA / SLiMA), particularly the high-lithium salt enrichment layer at the ends, which significantly reduces interfacial impedance. Therefore, this application, by organically combining the star-shaped topology with the gradient sequence, simultaneously and effectively satisfies the seemingly contradictory requirements of high strength and high conductivity, producing a synergistic effect greater than the sum of its parts.

[0217] Compared to Comparative Example 2, Example 1 exhibits higher ionic conductivity, peel strength, tensile strength, elongation at break, capacity retention after 100 turns, and self-healing efficiency. This is because the star polymer in Comparative Example 2 lacks segments formed by isobornyl methacrylate (IBOMA), which causes PEG segments to crystallize at low temperatures, leading to a deterioration in ionic conductivity. Furthermore, in Comparative Example 2, the copolymerization of polyethylene glycol monomethyl ether methacrylate (PGMEM) and SliMA forms ion-conducting segments, resulting in a lack of gradient distribution of lithium sulfonate ions, a more tortuous lithium-ion transport path, and a decrease in ionic conductivity. Therefore, this application, by introducing segments with rigid side groups into the star polymer, can disrupt the regular arrangement of PEG chains, inhibit crystallization, and thus maintain the mobility of chain segments and the unobstructed ion transport channels at low temperatures, thereby improving the performance of the star polymer.

[0218] Compared to Comparative Example 3, Example 1 exhibits higher ionic conductivity, peel strength, tensile strength, elongation at break, capacity retention after 100 turns, and self-healing efficiency. This is because Comparative Example 3 uses a physical blending method to mix the random copolymers formed by the monomers, without forming a star-shaped topology and gradient sequence through chemical bonds. Therefore, this application, by organically combining a star-shaped topology and a gradient sequence, can simultaneously and at a high level satisfy the originally contradictory requirements of high strength and high conductivity, producing a synergistic effect greater than the sum of its parts (1+1>2).

[0219] Compared with Comparative Examples 1 to 3, Examples 1 to 6 exhibit higher ionic conductivity, peel strength, tensile strength, elongation at break, capacity retention after 100 turns, and self-healing efficiency. Furthermore, the self-healing efficiency of Examples 1 to 6 (>90%) is significantly higher than that of the comparative examples (≤50%). This is because the star-shaped polymers in these examples possess dual, complementary, dynamically reversible chemical bonds. The star-shaped topology and crystallization inhibition ensure high segment mobility, high density, and matchable active end groups. The star-shaped network also plays a role in uniform stress transfer and limiting crack propagation.

[0220] In summary, the adhesive prepared in this application, with its star-shaped gradient structure and dual dynamic cross-linking network, overcomes the technical bottleneck of simultaneously achieving high bonding strength and high ionic conductivity. This material exhibits excellent interfacial bonding strength (peel strength > 200 N / m) and efficient ion transport capability (conductivity > 5 × 10⁻⁶). -4 With its excellent cycle stability and self-healing properties, it provides a core material solution for building next-generation high-energy-density, long-life solid-state and high-expansion electrode battery systems, and has great potential for industrial application.

[0221] The foregoing has provided a detailed description of a star-shaped polymer and its preparation method, binder, electrode material, electrode sheet, and battery provided in the embodiments of this application. Specific examples have been used to illustrate the principles and implementation methods of this application. The descriptions of the above embodiments are only for the purpose of helping to understand the methods and core ideas of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. A star-shaped polymer, characterized in that, It has the following structure: R1-(OCO-R2-R3-R4-R5) n ; Wherein, R1 is an alkyl or ether group; The structural formula of R2 is -A m1 -B m2 - where A is a fluoroethyl group containing at least one fluorine atom, B is a fluoroethyl group containing a substituent, the substituent being an alkyl group, a fluoroalkyl group, a chlorine atom, an alkoxy group, or a fluoroalkoxy group, m1 is an integer greater than or equal to 50, and m2 is an integer greater than or equal to 2. The structural formula of R3 is: Among them, R6, R8, R 10 Each occurrence is independently selected from -H and -CH3, R7 is a polyol ether ester group, R9 is an ester group containing at least one of cycloalkyl, phenyl, and tert-butyl groups, R 11 It is an ester group; R4 includes and , where R 12 R 14 Each occurrence is independently selected from -H and -CH3, R 13 It is an ester group or an ether group, R 15 It is an amide group or an amide group containing a substituent, wherein the substituent is at least one of a carboxyl group and a hydroxyl group; Each occurrence of R5 is independently selected from a halogen atom; n is an integer between 3 and 12, n1 is an integer greater than or equal to 1, n2 is an integer greater than or equal to 1, n3 is an integer greater than or equal to 1, n4 is an integer greater than or equal to 0, and n5 is an integer greater than or equal to 1. For connecting points.

2. The star-shaped polymer according to claim 1, characterized in that, The number-average molecular weight of R2 is 7 kDa to 14 kDa; and / or The number-average molecular weight of R3 is 10 kDa to 17 kDa; and / or The number-average molecular weight of R4 is 4.3 kDa to 10 kDa; and / or The ratio of n1 to n2 is (85~95):(5~15); and / or The ratio of n3 to n1 is (0.8~1.0):1 The ratio of m1 to m2 is (90~97):(3~10).

3. The star-shaped polymer according to claim 1, characterized in that, R1 is an alkyl group having 3 to 6 carbon atoms or an ether group having 6 to 15 carbon atoms; and / or The R7 is , where R 16 Each occurrence is independently selected from -H and -CH3, where m3 is an integer between 1 and 3, and m4 is an integer between 2 and 7; and / or R9 is -COO-R 18 , where R 18 It is an alkyl group containing cycloalkyl, phenyl, or tert-butyl; and / or The R 11 For -COO-R 20 -, where R 20 It is an alkyl group having 2 to 6 carbon atoms; and / or The R 13 It is an ester or ether group with 2 to 8 carbon atoms; and / or The R 15 for , where R 19 Each occurrence is independently selected from -H and -CH3, R 20 Each occurrence is independently selected from -H and -OH or -COOH, and m5 is 1 or 2.

4. The star-shaped polymer according to claim 1, characterized in that, R1 is , , , , , or ; and / or The A is -CH2-CF2-, -CF2-CHF-, or -CF2-CF2-; and / or The structural formula of B is -CF2-CFR 16 or -CF2-CR 17 R 16 , where R 16 For -Cl, -CF3, or -O-CF3, R 17 -F, -Cl, -CF3, -O-CF3, or -H; and / or The R7 is , or ; and / or The R9 is , , , or ; and / or The R 11 -COO-CH2-CH2-CH2-, -COO-CH2-CH2-, -COO-CH2-CH2-CH2-, -COO-CH2-CH2-CH2-CH2- or -COO-CH2-(CH2)4-CH2-; and / or The R 13 -COO-CH2-, -CH2-O-CH2-, or -C6H4-COO-CH2-; and / or The R 15 It can be -CO-NH-CH2-CH2-, -CO-NH-CH(COOH)-CH2-, -CO-NH-CH2-CH(OH)- or -CO-N(CH3)-CH2-CH2-.

5. The star-shaped polymer according to claim 1, characterized in that, The structural formula of R3 is: The side of R3 closest to R7 is connected to R2.

6. The star-shaped polymer according to claim 5, characterized in that, In the In the process, from the side closer to R1 to the side farther away from R1, it sequentially includes a lithium sulfonate transition section and a lithium sulfonate enrichment section, wherein the lithium sulfonate transition section is closer to R1. The mole fraction is lower on the side furthest from R1. The mole fraction of the lithium sulfonate enrichment segment The mole fraction is greater than that of the lithium sulfonate transition section. The mole fraction.

7. The star-shaped polymer according to claim 6, characterized in that, The The number-average molecular weight is 6 kDa to 10 kDa; and / or From the side closer to R1 to the side farther away from R1, the lithium sulfonate transition section The mole fraction increased from 0% to 30%~60%; and / or The lithium sulfonate enrichment segment The mole fraction is greater than or equal to 80%; and / or The number-average molecular weight of the lithium sulfonate enrichment segment is 1 kDa to 4 kDa.

8. The star-shaped polymer according to claim 1, characterized in that, The structural formula of R4 is: And close to R 13 One end is connected to R3.

9. The star-shaped polymer according to claim 8, characterized in that, The The number-average molecular weight (Mn) is 0.8 kDa to 1.5 kDa; and / or The The number-average molecular weight (Mn) is 2 kDa to 5 kDa; and / or The The number-average molecular weight (Mn) is 1.5 kDa to 3.5 kDa.

10. A method for preparing a star-shaped polymer, characterized in that, include: A polyol and an α-haloacylating agent are mixed in a first solvent to carry out a first acylation reaction, yielding an initiator; The initiator and symmetrical fluorinated olefins and amorphous fluorinated olefins are mixed in a second solvent and subjected to an atom transfer radical addition reaction to obtain a reaction solution containing the first intermediate. Hydroxysulfonic acid and acylacrylic acid derivative are mixed in a third solvent to carry out a second acylation reaction to obtain acryloyloxysulfonate; The acryloyloxysulfonate was mixed with an alkaline lithium source in a fourth solvent and neutralized to obtain the first active monomer. The reaction solution containing the first intermediate is mixed with polyol ether acrylate, an acrylate monomer containing at least one of cycloalkyl, phenyl and tert-butyl groups, and the first active monomer, and subjected to an atom transfer radical polymerization reaction to obtain a reaction solution containing the second intermediate. A catecholamine compound and an acylacrylic acid derivative are mixed in a fifth solvent and subjected to an amidation reaction to obtain a second active monomer; The reaction solution containing the second intermediate and the second active monomer are mixed in a sixth solvent to carry out a third atom transfer radical polymerization reaction to obtain a star polymer. The polyol contains at least three hydroxyl groups.

11. The method for preparing the star-shaped polymer according to claim 10, characterized in that, The sixth solvent also includes epoxy vinyl monomers; and / or The step of mixing the reaction solution containing the first intermediate with polyol ether acrylate, an acrylate monomer containing at least one of cycloalkyl, phenyl, and tert-butyl groups, and the first active monomer to carry out an atom transfer radical polymerization reaction includes: The reaction solution containing the first intermediate is mixed with polyol ether acrylate and an acrylate monomer containing at least one of cycloalkyl, phenyl and tert-butyl groups to carry out a first atom transfer radical polymerization reaction. After the reaction is completed, the first active monomer is added to carry out a second atom transfer radical polymerization reaction.

12. The method for preparing the star-shaped polymer according to claim 11, characterized in that, The polyol includes one or more of sorbitol, pentaerythritol, glycerol, diglycerol, erythritol, dipentaerythritol, and tripentaerythritol; and / or The α-haloacylating agent includes one or more of α-haloacyl halides, α-halocarboxylic acids, and α-haloanhydrides; and / or The symmetrical fluorinated olefins include one or more of vinylidene fluoride, trifluoroethylene, and tetrafluoroethylene; and / or The amorphous fluorinated olefins include one or more of hexafluoropropylene, trifluorochloroethylene, and perfluoromethyl vinyl ether; and / or The hydroxysulfonic acid includes one or more of 3-hydroxypropanesulfonic acid, 2-hydroxyethanesulfonic acid, 4-hydroxybutyric acid, 5-hydroxypentanesulfonic acid, and 6-hydroxyhexanesulfonic acid; and / or The acylacrylic acid derivative includes one or more of methacryloyl chloride, acryloyl chloride, and methacrylic anhydride; and / or The alkaline lithium source includes one or more of lithium hydroxide, lithium carbonate, lithium acetate, and lithium methoxide; and / or The polyol ether acrylates include polyethylene glycol monomethyl ether methacrylate, polyethylene glycol methyl ether acrylate, methoxy polyethylene glycol methacrylate, and polypropylene glycol monomethyl ether methacrylate; and / or The acrylate monomers include one or more of isobornyl methacrylate, cyclohexyl methacrylate, tert-butyl methacrylate, adamantane methacrylate, and benzyl methacrylate; and / or The catecholamine compounds include one or more of dopamine, levodopa, norepinephrine, methyldopamine, and 3,4-dihydroxyphenylethylamine derivatives; and / or The acylacrylic acid derivative includes one or more of methacryloyl chloride, acryloyl chloride, and methacrylic anhydride; and / or The epoxy vinyl monomer includes one or more of glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, glycidyl 4-vinylbenzoate, and glycidyl methacrylate.

13. The method for preparing the star-shaped polymer according to claim 11, characterized in that, The molar ratio of the hydroxyl group of the polyol to the acyl group of the α-haloacylating agent is 1:(1.3~2.5); and / or The molar ratio of the symmetrical fluorinated olefin to the amorphous fluorinated olefin is (90~97):(3~10); and / or The molar ratio of the halogen atom at the end of the initiator to that of the symmetrical fluorinated olefin and the amorphous fluorinated olefin is 1:(25~50):(0.8~3.0); and / or The molar ratio of the hydroxyl group of the hydroxysulfonic acid to the acyl group of the acylacrylic acid derivative is 1:(1.2~1.8); and / or The molar ratio of the sulfonic acid group in the acryloyl oxysulfonate to the lithium ion in the alkaline lithium source is 1:(0.95~1.05); and / or The molar ratio of the polyol ether acrylate to the acrylate monomer is (85~95):(5~15); and / or The molar ratio of the first active monomer to the polyol ether acrylate is (0.8~1.0):1; and / or The molar ratio of the halogen atom at the end of the first intermediate, the polyol ether acrylate, the acrylate monomer, and the first active monomer is 1:(120~200):(10~30):(100~180); and / or The molar ratio of the amino group of the catecholamine compound to the acyl group of the acylacrylic acid derivative is 1:(1.2~1.8); and / or The molar ratio of the halogen atom at the end of the second intermediate, the epoxy vinyl monomer, and the second active monomer is 1:(350~550):(200~350); and / or The molar ratio of the epoxy vinyl monomer to the second active monomer is (1.2~2.0):

1.

14. The method for preparing the star-shaped polymer according to claim 11, characterized in that, The polyol and the α-haloacylating agent are mixed at a temperature below 5°C; and / or The first acylation reaction was carried out at room temperature for a duration of 12 h to 36 h; and / or The atom transfer radical addition reaction is carried out under transition metal halide catalysis; and / or The atom transfer radical addition reaction is carried out in the presence of nitrogen-containing polydentate ligands; and / or The temperature of the atom transfer radical addition reaction is 70℃~110℃, and the time of the atom transfer radical addition reaction is 4h~10h; and / or The temperature at which the hydroxysulfonic acid and the acylacrylic acid derivative are mixed is below 5°C; and / or The second acylation reaction is carried out at room temperature for a period of 8 h to 24 h; and / or The temperature of the first atom transfer radical polymerization reaction is 60℃~80℃, and the time of the first atom transfer radical polymerization reaction is 3h~6h; and / or The temperature of the second atom transfer radical polymerization reaction is 60℃~80℃, and the time of the first atom transfer radical polymerization reaction is 2h~5h; and / or The amidation reaction is carried out in an ice bath for 8 to 24 hours; and / or The third atom transfer radical polymerization reaction is carried out under transition metal halide catalysis; and / or The third atom transfer radical polymerization reaction is carried out under the action of nitrogen-containing polydentate ligands; and / or The temperature of the third atom transfer radical polymerization reaction is 60°C to 80°C, and the time of the third atom transfer radical polymerization reaction is 3.5h to 10h.

15. The method for preparing the star-shaped polymer according to claim 11, characterized in that, The addition of the first active monomer to carry out the second atom transfer radical polymerization reaction includes: The first active monomer is added at a first speed and at a constant rate, and a first mass of the first active monomer is added to carry out a first stage of second atom transfer radical polymerization reaction. Then, a second mass of the first active monomer is added at once to carry out a second stage of second atom transfer radical polymerization reaction. Wherein, the first speed is 1 g / h to 4 g / h; and / or The mass ratio of the first active monomer in the first mass to the first active monomer in the second mass is (3~6):1; and / or The time for the first stage of the second atom transfer radical polymerization reaction is 1.5 h to 3 h; and / or The second stage of the second atom transfer radical polymerization reaction takes 0.5 h to 2 h.

16. The method for preparing the star-shaped polymer according to claim 11, characterized in that, The step of mixing the reaction solution containing the second intermediate and the second active monomer in a sixth solvent to carry out a third atom transfer radical polymerization reaction includes: The reaction solution containing the second intermediate and the first mass of epoxy vinyl monomer are mixed in a sixth solvent to carry out a first-stage third atom transfer radical polymerization reaction. Then, the second mass of epoxy vinyl monomer and the first mass of the second active monomer are added to carry out a second-stage third atom transfer radical polymerization reaction. Then, the second mass of the second active monomer is added to carry out a third-stage third atom transfer radical polymerization reaction. Wherein, the mass ratio of the first mass of epoxy vinyl monomer to the second mass of epoxy vinyl monomer is (50~80):(20~50); and / or The mass ratio of the first mass of the second active monomer to the second mass of the second active monomer is (20~50):(50~80); and / or The time for the first stage of the third atom transfer radical polymerization reaction is 0.5 h to 2 h; and / or The second stage of the third atom transfer radical polymerization reaction takes 2 to 5 hours; and / or The time for the third-stage atom transfer radical polymerization reaction is 1h to 3h.

17. An adhesive, characterized in that, Includes the star polymer as described in any one of claims 1-9, or the star polymer prepared by the method described in any one of claims 10-16.

18. The adhesive according to claim 17, characterized in that, The adhesive further includes a crosslinking agent, said crosslinking agent being a polyamine compound comprising dynamic covalent bonds; and / or The binder also includes polyvalent metal ions.

19. The adhesive according to claim 18, characterized in that, The dynamic covalent bond includes at least one of disulfide bond, diselenide bond, diene synthesis bond, and borate ester bond; and / or The multivalent metal ions include Zn 2+ Ca 2+ Cu 2+ Al 3+ Mg 2+ and Sr 2+ At least one of them.

20. The adhesive according to claim 18, characterized in that, The polyamine compounds include at least one of cystamine, dithioethylenediamine, bis(3-fluoro-4-aminophenyl)disulfide, 1,3,4-selenodiazole-2-amine, and diethanolamine borate; and / or The binder also includes zinc bis(trifluoromethanesulfonyl)imide.

21. The adhesive according to claim 18, characterized in that, The molar ratio of the epoxy group of the star polymer to the amino group of the polyamine compound is 1:(1.4~2.0); and / or The molar ratio of the lithium sulfonate ion group and the polyvalent metal ion in the star polymer is (1:0.1~0.3).

22. An electrode material, characterized in that, It includes a positive electrode active material and a binder as described in any one of claims 17-21, or a negative electrode active material and a binder as described in any one of claims 17-21.

23. An electrode sheet, characterized in that, It includes an active layer formed by curing the electrode material of claim 22.

24. A battery, characterized in that, Including the electrode as described in claim 23.

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