Polymer-based composite slurry with periodic layered structure as well as preparation method and application of polymer-based composite slurry

Abstract

The invention belongs to an electrolyte slurry, and provides a polymer-based composite slurry with a periodic layered structure, a preparation method and an application in order to solve the technical problems that a current method for regulating and controlling a microstructure of the electrolyte slurry is difficult to apply on a large scale and is insufficient in multi-component synergistic ordered regulation and control capability. Wherein the polymer with the specific structure comprises a rigid structural unit, a flexible structural unit, a hydrophilic structural unit and a hydrophobic structural unit, and can be self-assembled to form an ordered structure under the induction of a solvent and a polar additive, so that the periodic layered nano self-assembled structure is obtained. In practical application, accurate control of structural parameters of the polymer-based composite slurry with the periodic layered structure can be realized by further optimizing the solvent and the polar additive and regulating and controlling the proportion of the solvent, the polar additive and the polymer with the specific structure, and the polymer-based composite slurry can be widely popularized and applied to various polymer structures and has wide application prospects. And large-scale popularization and use are facilitated, and precise regulation and control are achieved.

Description

Technical Field

[0001] This application pertains to an electrolyte slurry, specifically a periodic layered polymer-based composite slurry, its preparation method, and its application. Background Technology

[0002] Electrolyte slurries are key materials for fabricating electrochemical devices such as chemical power sources, capacitors, and sensors. Their performance directly determines the ion transport efficiency, interfacial stability, and overall electrochemical performance of these devices. Traditional electrolyte slurries typically consist of a polymer matrix, ion-conducting salts, solvents, and possible additives, prepared through mechanical mixing or stirring. During this process, the components often exhibit a random and disordered distribution, leading to problems such as tortuous ion transport paths, increased interfacial impedance, and uneven mechanical strength within the cured electrolyte membrane. This structural disorder has become one of the bottlenecks restricting the development of high-performance electrochemical devices, especially in advanced devices requiring high ion conductivity, rapid interfacial dynamics, or anisotropic functions.

[0003] In recent years, some studies have begun to attempt to regulate the microstructure of electrolyte slurries through external field induction (such as electric fields, magnetic fields, and shear fields) or template methods. For example, strong magnetic fields are used to orient fillers with magnetic anisotropy, or shear forces in casting are used to induce ordered orientation of polymer chains. Although these methods can improve ion transport pathways to some extent, they still have significant limitations: on the one hand, external field induction usually requires specific equipment and consumes a lot of energy, making it difficult to apply on a large scale; on the other hand, existing methods mostly focus on the orientation of single components (such as fillers or polymers), and lack the ability to regulate the synergistic ordering of multiple components, especially lacking the integrated design of the spatial arrangement of multifunctional units such as ion transport channels, interfacial stabilizing phases, and mechanically reinforcing phases. Summary of the Invention

[0004] This application addresses the technical problems of current methods for controlling the microstructure of electrolyte slurries, which are difficult to apply on a large scale and lack the ability to control the synergistic and orderly structure of multiple components. It provides a periodic layered polymer-based composite slurry, its preparation method, and its application.

[0005] To achieve the above objectives, this application adopts the following technical solution: In a first aspect, this application proposes a method for preparing a periodically layered polymer-based composite slurry, comprising: A slurry is obtained by dissolving a polymer with a specific structure in a solvent; the polymer with the specific structure simultaneously possesses rigid structural units, flexible structural units, hydrophilic structural units, and hydrophobic structural units. The slurry is left to stand and age to obtain a polymer-based composite slurry with a periodic layered structure.

[0006] Furthermore, before allowing the slurry to stand and age, the process also includes dissolving a polar additive into the slurry.

[0007] Furthermore, the mass ratio of the specific structure polymer, the solvent, and the polar additive is 1:(0.001~10):(0~10).

[0008] Further, the mass ratio of the specific structured polymer, the solvent, and the polar additive is 1:(0.1~0.7):(0.1~1).

[0009] Furthermore, the specific structural polymer includes at least one of polyarylene ethers, polyarylene ether ketones, polyimides, polyarylene ether sulfones, polyurethanes, sulfonated polybenzimidazoles, sulfonated polystyrene, and sulfonated polyaryleneoxyphosphazenes; Alternatively, at least one of the following: sulfonated and aminated structures of polyarylene ethers, polyarylene ether ketones, polyimides, polyarylene ether sulfones, polyurethanes, sulfonated polybenzimidazoles, sulfonated polystyrene, and sulfonated polyaryleneoxyphosphazenes.

[0010] Furthermore, the rigid structural unit is a unit comprising a benzene ring structure or a benzene ring derivative.

[0011] Furthermore, the flexible structural unit is a unit including a saturated single bond structure.

[0012] Furthermore, the solvent includes at least one of water, alcohol solvents, ketone solvents, alkane solvents, ether solvents, aldehyde solvents, amide solvents, sulfoxide solvents, nitrile solvents, and ammonia solvents.

[0013] Furthermore, the polar additive includes at least one of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, tetrafluoroboric acid, hexafluorophosphate, photoinitiator, crosslinking agent, titanium dioxide, graphene, graphene oxide, boron nitride, molybdenum disulfide, MXene, sodium hydroxide, potassium hydroxide, organic amine, sulfonic acid, and sulfonate.

[0014] Secondly, this application proposes a periodic layered polymer-based composite slurry, which is obtained by the above-mentioned method for preparing periodic layered polymer-based composite slurry.

[0015] Thirdly, this application proposes the application of the above-mentioned periodic layered polymer-based composite slurry in ion transport, optical devices, information storage, and biosensing.

[0016] Compared with the prior art, this application has the following beneficial effects: This application proposes a method for preparing a periodically layered polymer-based composite slurry. The specific structural polymer in this slurry comprises rigid, flexible, hydrophilic, and hydrophobic structural units, which can self-assemble into an ordered structure under the induction of solvents and polar additives, resulting in a periodically layered nano-self-assembled structure. In practical applications, further optimization of the solvent and polar additives, combined with adjusting the ratio of the solvent, polar additives, and the specific structural polymer, allows for precise control of the structural parameters of the polymer-based composite slurry with a periodically layered structure. This method can be widely applied to various polymer structures, facilitating large-scale application and precise control.

[0017] This application also proposes a periodic layered polymer-based composite slurry and its application, which possesses all the advantages of the above-mentioned preparation method of the periodic layered polymer-based composite slurry. Attached Figure Description

[0018] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0019] Figure 1 This is a schematic flowchart of a method for preparing a periodically layered polymer-based composite slurry according to this application. Figure 2 This is a polarized image of the periodically layered polymer-based composite slurry of Sample 1 (sulfonated polyether ether ketone / sulfuric acid system) in the embodiments of this application. Figure 3 This is a polarized image of the periodic layered polymer-based composite slurry of Sample 2 (sulfonated fluorinated polyarylene ether / triethylamine system) in the embodiments of this application. Figure 4 This is a polarized image of the periodic layered polymer-based composite slurry of sample 3 (sulfonated polyethersulfone system) in the embodiments of this application; Figure 5 The above are electrochemical impedance spectroscopy diagrams of samples 1 to 3 in the embodiments of this application. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. The components of the embodiments of this application described and shown in the accompanying drawings can generally be arranged and designed in various different configurations.

[0021] Therefore, the following detailed description of the embodiments of this application provided in the accompanying drawings is not intended to limit the scope of the claimed application, but merely to illustrate selected embodiments of the application. All other embodiments obtained by those skilled in the art based on the embodiments of this application without inventive effort are within the scope of protection of this application.

[0022] It should be noted that similar labels and letters in the following figures indicate similar items. Therefore, once an item is defined in one figure, it does not need to be further defined and explained in subsequent figures.

[0023] In the description of the embodiments of this application, it should be noted that if terms such as "upper," "lower," "horizontal," or "inner" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship commonly used when the product of the invention is in use, they are only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation on this application. In addition, terms such as "first" and "second" are only used to distinguish descriptions and should not be construed as indicating or implying relative importance.

[0024] Furthermore, the use of the term "horizontal" does not imply that the component must be absolutely horizontal, but rather that it can be slightly tilted. For example, "horizontal" simply means that its direction is more horizontal than "vertical," and does not mean that the structure must be completely horizontal, but can be slightly tilted.

[0025] In the description of the embodiments of this application, it should also be noted that, unless otherwise explicitly specified and limited, the terms "set," "install," "connect," and "link" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this application according to the specific circumstances.

[0026] Electrolyte slurry is a key functional material for core electrochemical devices such as chemical power sources, electrochemical capacitors, and electrochemical sensors. Its microstructure and performance directly determine the ion transport efficiency, electrode-electrolyte interface stability, and overall electrochemical performance of the device, and are one of the core factors affecting the energy density, power density, and cycle life of the device.

[0027] Traditional electrolyte slurry preparation typically uses a polymer matrix as the basic framework, compounded with ionicly conductive salts (such as lithium salts and sodium salts), solvents, and functional additives (such as plasticizers and stabilizers), and is prepared through physical mixing methods such as mechanical stirring and high-speed dispersion. During this process, the polymer chains, ionicly conductive salts, additives, and other components often exhibit a random and disordered distribution. This structural characteristic leads to three core problems in the cured electrolyte membrane: First, the ion transport path is tortuous and discontinuous, requiring ions to overcome more obstacles during transport, directly reducing the ionic conductivity of the electrolyte; second, poor interfacial compatibility between components easily leads to numerous interfacial defects, resulting in a significant increase in interfacial impedance and affecting the charge transfer efficiency between the electrode and the electrolyte; third, the disordered stacking of the polymer matrix causes uneven distribution of the electrolyte membrane's mechanical strength, making it prone to cracking and peeling under dynamic conditions such as charge-discharge cycles, shortening the device's lifespan.

[0028] The aforementioned structural disorder has become a key bottleneck restricting the development of high-performance electrochemical devices, especially in advanced applications with stringent performance requirements. However, existing modulation methods still have insurmountable limitations, failing to meet the demands for large-scale and high-performance advanced electrochemical devices, specifically in the following ways: (1) Preparation cost and scale bottleneck: The external field induction method requires special high-power equipment, which has a large investment and high energy consumption. The operation process is complicated and it is difficult to adapt to industrial continuous production. Although the template method does not require a complex external field, the preparation, filling and removal of the template are complicated, which can easily introduce impurities. Moreover, the template cost is high, making it difficult to achieve large-area, low-cost preparation.

[0029] (2) Insufficient multi-component synergistic and ordered regulation: Existing methods mostly focus on the structural regulation of single components, while electrolyte slurries, as multi-component composite systems, depend on the synergistic effect of multiple components such as polymer matrix, ion-conducting salt, and functional additives. The lack of integrated design of the spatial arrangement of multifunctional units such as "ion transport channels-interfacial stabilizing phase-mechanically reinforcing phase" makes it impossible to form a multi-component synergistic and ordered microstructure, resulting in the electrolyte membrane having difficulty simultaneously possessing high ionic conductivity, low interfacial impedance, and excellent mechanical properties.

[0030] (3) Poor structural controllability and universality: The orientation effect induced by the external field is easily affected by factors such as slurry concentration and component compatibility, making it difficult to accurately control the period, size and distribution of the ordered structure; the template method is limited by the pore size and morphology of the template itself, and cannot flexibly adjust the microstructure of the electrolyte membrane according to the needs of different devices, resulting in poor universality.

[0031] Therefore, developing an electrolyte slurry that requires no complex external fields or templates, has a simple and controllable process, and enables the coordinated and orderly arrangement of multiple components with a designable microstructure is of paramount importance for overcoming the performance limitations of current high-performance electrochemical devices. Such an electrolyte slurry must meet three core requirements: first, it must form a continuous and orderly ion conduction network and a stable interface structure through a simple process, solving the problems of tortuous ion transport paths and high interface impedance; second, it must achieve a spatially ordered arrangement of multiple components, balancing ion transport efficiency, interface stability, and mechanical strength; and third, it must be feasible for industrial-scale preparation, balancing process simplification and cost-effectiveness to meet the application requirements of various advanced electrochemical devices such as lithium-ion batteries, flexible electrochemical sensors, and high-power capacitors.

[0032] Based on the above, this application proposes a periodic layered polymer-based composite slurry, its preparation method, and its application. The following detailed description of this application is provided in conjunction with embodiments and accompanying drawings.

[0033] like Figure 1 The diagram shown is a schematic representation of a method for preparing a periodically layered polymer-based composite slurry according to this application, which may include: S101, a slurry is obtained by dissolving a specific structured polymer in a solvent; the specific structured polymer simultaneously possesses rigid structural units, flexible structural units, hydrophilic structural units, and hydrophobic structural units.

[0034] In this application, the specific structured polymer possesses four structural units that can work synergistically during subsequent preparation. Among them, the rigid structural units ensure that the material has certain structural stability and mechanical properties, the flexible structural units increase the material's flexibility and processability, and the hydrophilic and hydrophobic structural units can form specific interfacial interactions in the solvent, promoting the formation of a layered structure.

[0035] As an example, when dissolving a polymer with a specific structure, one or a combination of mechanical stirring dissolution, heating dissolution, ultrasonic-assisted dissolution, high-pressure dissolution, microwave-assisted dissolution, co-solvent synergistic dissolution, vacuum degassing dissolution, and centrifugal degassing dissolution can be used.

[0036] S102, allow the slurry to stand and age to obtain a periodic layered polymer-based composite slurry.

[0037] During the static aging process, the molecules in the system can gradually self-assemble to form an ordered, periodic layered structure. In practical applications, by controlling the static aging time, temperature, and other conditions, parameters such as the period and thickness of the layered structure can be adjusted to obtain products with specific structures and properties.

[0038] In some embodiments of this application, polar additives may also be dissolved in the slurry. The addition of polar additives can further modulate the interfacial properties and interactions of the system, promoting the formation and stabilization of periodic layered structures. By selecting appropriate types and amounts of polar additives, the performance of the final product can be controlled to meet different application requirements. As examples, methods such as mechanical stirring, high-shear dispersion, ultrasonic dispersion, ball milling / sand milling, three-roll milling, static mixing, chemical dispersion, and temperature-controlled assisted dispersion can be used when dissolving polar additives.

[0039] As an example, aging can be achieved through physical aging, chemical aging, environmentally controlled aging, etc.

[0040] In some embodiments of this application, the mass ratio of the specific structural polymer, solvent, and polar additive is 1:(0.001~10):(0~10). During the slurry preparation process, the periodic structure exhibits a pattern of first appearing and then disappearing as the solvent content increases. Within the mass ratio range defined in this application, a moderate solvent content ensures good interaction between the components, allowing for the successful formation of a complete periodic layered structure. If the mass ratio of the solvent is too low, the specific structural polymer is difficult to dissolve fully, and the polymer lacks self-assembly capability, affecting the subsequent formation of the layered structure; if the mass ratio of the solvent is too high, the system concentration is too low, and the polymer exhibits excessive disorder in the solvent, making it difficult to assemble a periodic layered structure. Regarding the degree of order in the periodic layered structure, the degree of order decreases with increasing solvent content, eventually leading to complete disorder. Similarly, with increasing polar additive content, the periodic structure exhibits a pattern of first appearing and then disappearing. Within the proportion range defined in this application, a moderate polar additive content ensures good interaction between the components, allowing for the successful formation of a complete periodic layered structure. If the mass ratio of polar additives is too high, it may alter the interfacial properties of the system and disrupt the formation of the layered structure; if the mass ratio of polar additives is too low, their regulatory effect cannot be fully realized. Furthermore, in practical applications, when the mass ratio of a specific polymer structure, solvent, and polar additive is 1:(0.1~0.7):(0.1~1), the interactions between the components are more optimized, enabling the preparation of polymer-based composite slurries with more regular structures and superior performance in periodic layered structures.

[0041] It should be noted that as the solvent content increases, the periodic layered structure exhibits a pattern of first appearing and then disappearing. When the solvent content is extremely low or absent, the polymer with the specific structure lacks the ability to self-assemble. When the solvent content is moderate, the periodic layered structure appears and is complete. When the solvent content is too high, the polymer with the specific structure becomes too disordered in the solvent, making it difficult to assemble into a periodic layered structure.

[0042] Furthermore, the effect of polar additive content on periodic layered structures follows a similar trend to that of the solvent. Regarding the degree of order in the periodic layered structures, the degree of order decreases with increasing solvent content, eventually leading to complete disorder.

[0043] In some embodiments of this application, the specific structural polymer may include at least one of polyarylene ethers, polyarylene ether ketones, polyimides, polyarylene ether sulfones, polyurethanes, sulfonated polybenzimidazoles, sulfonated polystyrene, and sulfonated polyaryleneoxyphosphazenes; or at least one of the sulfonated and aminated structures of polyarylene ethers, polyarylene ether ketones, polyimides, polyarylene ether sulfones, polyurethanes, sulfonated polybenzimidazoles, sulfonated polystyrene, and sulfonated polyaryleneoxyphosphazenes. A common feature of these polymers is that their repeating units adopt an "ABC" structural pattern: where A is a strongly polar hydrophilic segment, C is a weakly polar hydrophobic segment, and B is a rotatable flexible connecting segment. Segments A and C drive the periodic separation of hydrophilic and hydrophobic phases in the polymer chain, while segment B, while connecting A and C, also allows them to rotate spatially around it to meet specific requirements for arrangement orientation and angle during self-assembly. These polymer materials possess excellent chemical stability, thermal stability, and mechanical properties. Furthermore, rigid structural units, flexible structural units, hydrophilic structural units, and hydrophobic structural units can be simultaneously introduced into the molecular structure, thereby effectively supporting the formation of periodic layered structures.

[0044] Table 1 below lists the specific structural formulas of the above examples of special-structure polymers: Table 1

[0045] In addition, rigid structural units can include units of benzene ring structures or benzene ring derivatives. Benzene ring structures or benzene ring derivatives have high rigidity, providing good structural stability and mechanical properties for polymer materials and facilitating the formation of regular layered structures. Specifically, examples include -Ar-O-, -Ar-C-, -Ar-Ar-, -Ar-N-, and -Ar-S-, where Ar represents a benzene ring structure or benzene ring derivative. Flexible structural units can include units including saturated single-bond structures. Saturated single-bond structures have good flexibility, increasing the flexibility and processability of polymer materials, and can also play a certain regulatory role in the formation of layered structures, making the layered structure more stable. Examples include -CC-, -CO-, -Si-O-, and -CC-. The hydrophilic structural unit may contain the following hydrophilic groups: hydroxyl (-OH), amide (-CONH2, -CONHR, -CONR2), carboxyl (-COOH), amino (-NH2, -NHR, -NR2), thiol (-SH), carboxyl (-COO⁻), sulfonic acid (-SO3⁻), phosphate (-PO4⁻). 2 Hydrophobic structural units can include alkyl chains, cycloalkanes / aromatics, siloxane chains, thioethers, haloalkanes, sterol skeletons, polycyclic aromatic hydrocarbons, etc.

[0046] The solvent can be at least one of water, alcohols, ketones, alkanes, ethers, aldehydes, amides, sulfoxides, nitriles, and ammonia. These solvents have different polarities and solubilizing properties. A suitable solvent or solvent mixture can be selected based on the properties of the specific polymer structure to ensure that the polymer dissolves completely and forms a homogeneous slurry. For example, for highly polar polymers, polar solvents such as water, alcohols, and amides can be selected; for less polar polymers, nonpolar or weakly polar solvents such as alkanes and ethers can be selected.

[0047] Table 2 below shows examples of specific structural polymers and specific solvent ratios in some embodiments of this application. The embodiments in Table 2 do not contain polar additives.

[0048] Table 2

[0049] In some embodiments of this application, alcohol solvents may be methanol, ethanol, isopropanol, n-propanol, butanol, ethylene glycol, or glycerol. Ketone solvents may be acetone, butanone, cyclohexanone, or 2-pentanone; alkane solvents may be dichloromethane, chloroform, or carbon tetrachloride. Ether solvents may be diethyl ether, tetrahydrofuran, 1,4-dioxane, or diethylene glycol dimethyl ether. Aldehyde solvents may be formaldehyde, acetaldehyde, or benzaldehyde. Ester solvents may be ethyl acetate, butyl acetate, butyl lactate, or dimethyl carbonate. Amide solvents may be N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoric triamine, formamide, N,N-diethylformamide, N-ethylpyrrolidone, N-cyclohexylpyrrolidone, or N-octylpyrrolidone. Sulfoxide solvents may be dimethyl sulfoxide, diethyl sulfoxide, diphenyl sulfoxide, sulfolane, methylphenyl sulfoxide, or tetramethyl sulfoxide. Nitrile solvents can be acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, adiponitrile, acrylonitrile, valerate, or 3-methoxypropionitrile. Ammonia solvents can be pyridine, ethylenediamine, triethylamine, or N-methylmorpholine. Polar additives can include at least one of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, tetrafluoroboric acid, hexafluorophosphate, photoinitiators, crosslinking agents, titanium dioxide, graphene, graphene oxide, boron nitride, molybdenum disulfide, MXene, sodium hydroxide, potassium hydroxide, organic amines, sulfonic acids, and sulfonates. Different types of polar additives have different functions. For example, inorganic acids such as sulfuric acid and hydrochloric acid can adjust the pH of the system, change the dissolution state and interfacial properties of polymers with specific structures; nanomaterials such as titanium dioxide and graphene can increase the specific surface area of ​​the material and improve its specific properties; photoinitiators and crosslinking agents can achieve crosslinking and curing of the material in subsequent processing, further improving the material's performance.

[0050] Table 3 shows examples of the proportions of different specific polymer structures, solvents, and polar additives.

[0051] Table 3

[0052] As can be seen from the examples in Tables 1 to 3 above, polymer-based composite slurries with periodic layered structures can be obtained.

[0053] Furthermore, this application will be further described in detail through several specific examples: Example 1: (Proportions of polyarylethers in Table 2 and proportions 2-8 in Table 3) A periodically layered polymer-based composite slurry with a sulfonated polyether ether ketone (SPEEK) / sulfuric acid system was prepared, denoted as Sample 1: a) Dissolution: Sulfonated polyether ether ketone with a sulfonation degree of 50% was added to the sample tube in a mass ratio of 66.67:23.33:10.0 and stirred at 50°C until completely dissolved. Then, a polar additive was added (specific structure polymer + solvent: polar additive = 99.0:1.0). Hexafluorophosphate, photoinitiator 184, crosslinking agent PEGDA (polyethylene glycol diacrylate), and 3M sulfuric acid were selected as polar additives in a mass ratio of 0.08:0.02:0.1:0.80.

[0054] b) Degassing: After adding sulfuric acid, centrifuge at 4000 rpm for 15 min, then sonicate at 40 kHz for 30 min to eliminate bubbles.

[0055] c) Aging: The slurry is kept at a constant temperature of 50°C for 36 hours to achieve full and uniform self-assembly of sulfonated polyether ether ketone under the induction of solvent and polar additives, while eliminating the residual stress between polymers generated during the stirring and mixing process, forming a uniform and ordered structural phase.

[0056] Example 2: (Proportions of polyarylethers in Table 2 and proportions 2-3 in Table 3) A periodically layered polymer-based composite slurry with a sulfonated fluorinated polyarylene ether (SFPAE) / triethylamine system was prepared, designated as Sample 2. a) Dissolution: Sulfonated fluorinated polyarylene ether with a sulfonation degree of 80% was added to the sample tube along with water, N,N-dimethylacetamide, and dimethyl sulfoxide in a mass ratio of 99.9:0.08:0.01:0.01. The mixture was stirred at 60°C (250 rpm) for 6 hours until completely dissolved, forming a homogeneous and transparent solution. Subsequently, a polar additive was added (specific structure polymer + solvent: polar additive = 90.0:10.0). Photoinitiator 2959, crosslinking agent PEGDA, and triethylamine were selected as additives in a mass ratio of 1.00:2.00:7.00.

[0057] b) Degassing: After adding triethylamine, centrifuge at 3500 rpm for 10 minutes, then sonicate (35 kHz, 25 minutes) to eliminate bubbles.

[0058] c) Aging: The slurry is kept at a constant temperature of 40°C for 48 hours to allow the sulfonated fluorinated polyarylene ether to fully self-assemble under the induction of solvent and polar additives, while eliminating the residual stress generated between polymers during stirring and mixing, and forming a uniform and ordered structural phase.

[0059] Example 3: (Proportion of polyarylether(ether) sulfones in Table 2) A polymer-based composite slurry with a periodic layered structure of sulfonated polyether sulfone (SPUSS) was prepared and designated as sample 3.

[0060] a) Dissolution: Add sulfonated polyethersulfone with a sulfonation degree of 70% to the sample tube along with water, ethanol, ethyl acetate, N,N-dimethylformamide and dimethyl sulfoxide in a mass ratio of 50:30:5:5:5:5. Stir at low speed (150 rpm) at 30°C for 8 hours until completely dissolved (avoid shearing damage to the structure).

[0061] b) Degassing: After dissolving the slurry, centrifuge at 3000 rpm for 5 minutes, then sonicate (28 kHz, 2 hours) to eliminate air bubbles.

[0062] c) Aging: The slurry is kept at a constant temperature of 30°C for 60 hours to achieve full self-assembly of sulfonated polyethersulfone under solvent induction, while eliminating the micro-stress generated during processing and forming a uniform and ordered structural phase.

[0063] Verify the technical effectiveness of samples 1 to 3: Samples 1 to 3 were placed on the stage of a polarizing microscope equipped with a precision-controlled heated stage (temperature control accuracy ±0.1 °C, temperature range: -20 °C to 120 °C). The microscope was adjusted to crossed polarization (P and A polarization directions perpendicular), and the characteristic morphology of the samples was observed and recorded. The results for samples 1 to 3 are as follows: Figures 2 to 4 As shown, the images are polarized light photographs of samples 1 to 3 under a polarizing microscope. Samples 1 to 3 were then characterized using small-angle X-ray scattering (SAXS), and the numerical distribution of the first-order scattering peaks of the periodic layered polymer-based composite slurry was obtained, as shown in Table 4. Figure 2 , Figure 3 , Figure 4 As shown, samples 1, 2, and 3 exhibit obvious birefringence under a polarizing microscope, proving the existence of a periodic structure in the samples; at the same time, combined with the SAXS results, it is confirmed that a periodic layered structure has been successfully assembled in the samples.

[0064] Table 4

[0065] In addition, samples 1 to 3 were placed between two electrodes, and the ion transport performance of the samples was tested using the sandwich method and electrochemical impedance spectroscopy. The electrochemical method selected was impedance spectroscopy. The calculation results are shown in Table 5, and the impedance diagrams are as follows. Figure 5 As shown.

[0066] Table 5

[0067] It should be noted that the sandwich method specifically involves placing the slurry between two electrodes, both of which are connected to wires.

[0068] This application enables the formulation of a periodically structured polymer slurry by optimizing the ratio of solvent and additives, thereby achieving precise control over ordered structural parameters. Specifically, this includes precise control over the interlayer spacing of the single-period layered structure, the thickness of the ordered layer, and the thickness of the solvation layer. Based on this, the periodically layered polymer-based composite slurry prepared in this application can be used in the field of electrochemistry as a high-conductivity quasi-solid-state electrolyte. It also possesses the characteristic tunable optical birefringence effect, showing potential application value in areas such as optical modulation.

[0069] The above are merely preferred embodiments of this application and are not intended to limit this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A method for preparing a periodically layered polymer-based composite slurry, characterized in that, include: A slurry is obtained by dissolving a polymer with a specific structure in a solvent; the polymer with the specific structure simultaneously possesses rigid structural units, flexible structural units, hydrophilic structural units, and hydrophobic structural units. The slurry is left to stand and age to obtain a polymer-based composite slurry with a periodic layered structure.

2. The method for preparing the periodically layered polymer-based composite slurry according to claim 1, characterized in that, Before allowing the slurry to stand and age, the process also includes dissolving polar additives into the slurry.

3. The method for preparing the periodically layered polymer-based composite slurry according to claim 2, characterized in that, The mass ratio of the specific structured polymer, the solvent, and the polar additive is 1:(0.001~10):(0~10).

4. The method for preparing the periodically layered polymer-based composite slurry according to claim 3, characterized in that, The mass ratio of the specific structured polymer, the solvent, and the polar additive is 1:(0.1~0.7):(0.1~1).

5. The method for preparing the periodically layered polymer-based composite slurry according to claim 4, characterized in that, The specific structural polymers include at least one of polyarylene ethers, polyarylene ether ketones, polyimides, polyarylene ether sulfones, polyurethanes, sulfonated polybenzimidazoles, sulfonated polystyrene, and sulfonated polyaryleneoxyphosphazenes. Alternatively, at least one of the following: sulfonated and aminated structures of polyarylene ethers, polyarylene ether ketones, polyimides, polyarylene ether sulfones, polyurethanes, sulfonated polybenzimidazoles, sulfonated polystyrene, and sulfonated polyaryleneoxyphosphazenes.

6. The method for preparing the periodically layered polymer-based composite slurry according to claim 5, characterized in that, The rigid structural unit is a unit that includes a benzene ring structure or a benzene ring derivative.

7. The method for preparing the periodically layered polymer-based composite slurry according to claim 6, characterized in that, The flexible structural unit is a unit that includes a saturated single bond structure.

8. The method for preparing the periodically layered polymer-based composite slurry according to claim 7, characterized in that, The solvent includes at least one of water, alcohol solvents, ketone solvents, alkane solvents, ether solvents, aldehyde solvents, amide solvents, sulfoxide solvents, nitrile solvents, and ammonia solvents.

9. The method for preparing the periodically layered polymer-based composite slurry according to claim 8, characterized in that, The polar additives include at least one of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, tetrafluoroboric acid, hexafluorophosphate, photoinitiator, crosslinking agent, titanium dioxide, graphene, graphene oxide, boron nitride, molybdenum disulfide, MXene, sodium hydroxide, potassium hydroxide, organic amine, sulfonic acid, and sulfonates.

10. A periodically layered polymer-based composite slurry, characterized in that, It is obtained by the preparation method of the periodic layered polymer-based composite slurry according to any one of claims 1 to 9.

11. The application of the periodic layered polymer-based composite slurry of claim 10 in ion transport, optical devices, information storage and biosensing.

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