Preparation method of conductive polymer composite aluminum foil for solid-state battery and solid-state capacitor

Abstract

The application discloses a preparation method of a conductive polymer composite aluminum foil for solid-state batteries and solid-state capacitors, and relates to the technical field of conductive composite aluminum foils. The process takes conductive polymers as the main body, introduces specific doped acids to realize stable carrier doping, and is compounded with conductive fillers of a micron and / or submicron aluminum powder mixture, while adding tackifiers, silane coupling agents, dispersants and other additives. After preparing uniform conductive slurry, the conductive slurry is coated on the surface of the aluminum foil and dried and solidified to form a conductive layer. The obtained composite aluminum foil has a continuous conductive network and firm interface bonding, has relatively low resistance and good adhesion, and has relatively small resistance change under high-temperature aging conditions, so that the conductive stability and reliability of the current collector of the solid-state device can be effectively improved.

Description

Technical Field

[0001] This invention relates to the field of conductive composite aluminum foil technology, specifically to a method for preparing conductive polymer composite aluminum foil for solid-state batteries and solid-state capacitors. Background Technology

[0002] Solid-state batteries and capacitors, with their higher energy density, superior safety performance, and longer cycle life, have become the core development direction for next-generation energy storage and electronic devices. Their performance improvement is closely related to the innovation of key materials. Conductive composite aluminum foil, as the core current collector in these devices, not only needs to possess good conductivity and mechanical stability, but also needs to form a stable interface with the solid electrolyte and electrode materials to ensure the long-term reliability of the device. Among these, the conductivity of the conductive polymer coating is crucial to the overall performance of the composite aluminum foil, and the doping process, as the core means to improve the conductivity of the conductive polymer, directly affects the product application effect due to its technical rationality.

[0003] Conductive polymers inherently suffer from low charge carrier mobility, necessitating the introduction of charge carriers through doping to activate conductivity. Doping acids, as commonly used p-type dopants, play an irreplaceable role in conductive polymer composite systems. However, existing doping acids have several drawbacks: traditional inorganic doping acids (such as hydrochloric acid and sulfuric acid), while possessing high doping efficiency, are highly corrosive and readily react with aluminum foil substrates, compromising the integrity of the current collector structure. Furthermore, they are prone to dedoping during high-temperature curing or long-term use, leading to performance degradation of the conductive layer. Conventional organic acids (such as formic acid and acetic acid) suffer from insufficient doping depth and poor compatibility with conductive polymers, making it difficult to form stable charge transfer complexes. Consequently, the conductivity of the composite coating is insufficient to meet the high-power requirements of solid-state devices.

[0004] Furthermore, the synergistic effect between existing doped acids and conductive fillers is insufficient, failing to effectively reduce the contact resistance of the composite system. Some doped acids are also prone to volatilization or decomposition, resulting in loss during processes such as gradient drying, further affecting the uniformity and stability of the conductive coating. Simultaneously, traditional doped acids exhibit poor compatibility with tackifiers and functional additives, easily leading to insufficient adhesion between the coating and the aluminum foil substrate, resulting in peeling and detachment. This severely restricts the large-scale application of conductive composite aluminum foil in solid-state batteries and solid-state capacitors.

[0005] Therefore, developing a doped acid system with strong compatibility, high doping efficiency, excellent stability, and no corrosion to the substrate, and optimizing its dispersion and effect in conductive composite pastes, has become a key technological bottleneck for improving the performance of conductive polymer composite aluminum foil and promoting the industrialization of solid-state energy storage devices. Summary of the Invention

[0006] The purpose of this invention is to address the problems in existing technologies, such as the strong corrosiveness of doped acids, easy dedoping, insufficient conductivity of conductive coatings, poor adhesion to aluminum foil, and poor stability. This invention provides a method for preparing conductive polymer composite aluminum foil for solid-state batteries and solid-state capacitors, which uses a specific doped acid to construct a conductive system, achieving high conductivity, strong substrate adhesion, and long-term service stability, while also being a process that is controllable and suitable for large-scale production.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0008] A method for preparing conductive polymer composite aluminum foil for solid-state batteries and solid-state capacitors includes the following steps:

[0009] S1. Pretreatment of aluminum foil substrate: Industrial grade aluminum foil is selected as the current collector substrate. Its surface is cleaned and surface activated to remove surface grease and oxide layer, and increase surface roughness to obtain pretreated aluminum foil.

[0010] S2. Preparation of conductive composite slurry: Weigh the following raw materials by mass: 40-85 parts of conductive polymer dispersion, 0.8-3.5 parts of conductive filler, 0.5-5 parts of thickener, 0.1-3 parts of functional additive, and 10-50 parts of solvent; mix and disperse the above raw materials evenly to obtain conductive composite slurry;

[0011] S3. Coating and film formation: The conductive composite paste described in step S2 is uniformly coated onto one or both sides of the pretreated aluminum foil described in step S1 using a coating process.

[0012] S4. Curing and post-treatment: The coated aluminum foil is subjected to gradient drying at 60-300℃ to form a conductive polymer composite coating with a thickness of 80-120μm on the surface of the aluminum foil, thus obtaining the conductive polymer composite aluminum foil.

[0013] The conductive polymer dispersion is obtained by mixing a conductive polymer dispersion with a doped acid, wherein the mass ratio of the conductive polymer dispersion to the doped acid is 1:0.001-0.08, preferably 1:0.01-0.03;

[0014] The doped acid is: .

[0015] Furthermore, the name of the doped acid is: 4-((3-phosphonopropyl)amino)-3-(trifluoromethyl)benzenesulfonic acid.

[0016] Furthermore, the mass ratio of the conductive polymer dispersion to the conductive filler is 1:0.01-0.04.

[0017] Furthermore, the surface activation treatment described in S1 involves alkaline washing and degreasing with sodium hydroxide solution, followed by etching with hydrochloric acid solution.

[0018] Furthermore, the concentration of the sodium hydroxide solution is 1-10 wt%, and the treatment time is 10-120 s.

[0019] Furthermore, the concentration of the hydrochloric acid solution is 1-10 wt%, and the treatment time is 10-60 s.

[0020] Furthermore, the conductive polymer dispersion is selected from one or more of polyaniline, polypyrrole, polythiophene in water or in organic solvent.

[0021] Furthermore, the concentration of the conductive polymer dispersion is 0.5-8 wt%.

[0022] Furthermore, the organic solvent is one or more of dimethyl sulfoxide, N-methylpyrrolidone, and dimethylformamide.

[0023] Furthermore, the conductive filler is selected from a mixture of micron-sized and / or submicron-sized aluminum powders, with a mass ratio of 1-20:1-20.

[0024] Furthermore, the tackifier is selected from waterborne polyurethane or acrylic emulsion.

[0025] Furthermore, the functional additive is a mixture of polyvinylpyrrolidone K30, γ-aminopropyltriethoxysilane and polyether-modified polydimethylsiloxane, with a mass ratio of 4-8:1-3:1-3.

[0026] Furthermore, the solvent is dimethyl sulfoxide.

[0027] Further, the mixing and dispersion process in step S2 is specifically as follows: first, the conductive polymer dispersion is mixed with the solvent and pre-stirred for 5-20 minutes; then, the thickener and functional additives are added sequentially, and stirring is continued for 10-30 minutes; then, the conductive filler is added in batches, and high-speed shear dispersion is performed at 1000-3000 rpm for 10-40 minutes; then, sand milling or ultrasonic dispersion is performed for 20-120 minutes to further refine the agglomerates; finally, the mixture is filtered through a 100-300 mesh filter and vacuum degassed for 5-30 minutes to obtain the conductive composite slurry.

[0028] Furthermore, the coating process in step S3 controls the wet film thickness so that the surface density of the dried conductive layer is controlled at 80-250 g / m². 2 Within the range.

[0029] Furthermore, the specific process of gradient drying in step S4 is as follows:

[0030] First stage: Bake at 50-90℃ for 10-30 minutes;

[0031] Second stage: Heat to 90-140℃ and dry for 5-15 minutes;

[0032] The third stage: high-temperature heat treatment at 140-200℃ for 5-20 minutes.

[0033] Furthermore, step S2 is performed under a nitrogen atmosphere.

[0034] A solid-state battery includes a composite aluminum foil prepared by the above-described method for preparing a conductive polymer composite aluminum foil for a solid-state battery and a solid-state capacitor.

[0035] This invention uses a conductive polymer dispersion as the main component, specifying that it is composed of a conductive polymer dispersion and a specific doping acid in a mass ratio of 1:0.01-0.03. This allows the dopant to effectively introduce charge carriers into the system, enhancing the intrinsic conductivity of the conductive polymer. Furthermore, the doping system, with its "stronger compatibility and gentler effect on the substrate," reduces corrosion of the aluminum foil and the risk of dedoping under high temperatures / long-term use, thus improving conductivity retention and service stability from the source. Secondly, conductive fillers are introduced to build continuous conductive pathways outside the conductive polymer phase, compensating for the doped polymer and reducing the contact resistance of the composite system, improving in-plane / out-of-plane conduction efficiency, thereby directly addressing the problems of insufficient conductivity in conductive coatings and poor filler synergy. Thirdly, a thickener and... The functional additives work together: the tackifier provides film toughness and an interfacial bonding framework; silane coupling promotes a more stable interfacial bond between the coating and the aluminum foil surface (after cleaning and activation, the roughness and active sites are improved); PVP helps with dispersion stability and inhibits agglomeration; and modified siloxanes improve wetting leveling and defect control, thereby significantly reducing the risk of peeling / detachment and improving coating uniformity and long-term stability. Finally, the solvent and the prescribed mixing and dispersion process together ensure the uniform distribution of doped acid, conductive filler, and binder system in the slurry. Combined with subsequent gradient drying and curing, a dense, continuous, low-defect ultrathin conductive layer is achieved while avoiding component migration and volatilization loss. Ultimately, a balance is achieved between conductivity, adhesion, and durability, thus achieving the technical objectives described in this invention.

[0036] Compared with the prior art, the beneficial effects of the present invention are:

[0037] 1. By constructing a more continuous conductive network through a specific doping system and in conjunction with conductive fillers, the surface resistance and volume resistivity of the composite aluminum foil show an overall decreasing trend and better consistency.

[0038] 2. The improved process system enhances the bonding between the coating and the aluminum foil interface, resulting in a better overall adhesion level. Compared to traditional systems that are prone to interface damage, the coating is less likely to peel off.

[0039] 3. The overall resistance change rate is smaller under high temperature aging conditions, indicating that the doping and interface structure are less prone to instability, and the performance degradation trend is slower during long-term service. Attached Figure Description

[0040] Figure 1 The NMR spectrum of 4-((3-phosphonopropyl)amino)-3-(trifluoromethyl)benzenesulfonic acid. Detailed Implementation

[0041] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are merely some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0042] Preparation Example 1

[0043] Preparation of doped acid: 4-((3-phosphonopropyl)amino)-3-(trifluoromethyl)benzenesulfonic acid:

[0044] ;

[0045] In a dry round-bottom flask, 5 g of sodium 4-fluoro-3-(trifluoromethyl)benzenesulfonate and 3.14 g of (3-aminopropyl)phosphonic acid were added, along with 50 mL of a mixed solvent DMSO / H2O (50 mL, volume ratio 3:1). The mixture was stirred until homogeneous, and then 6.49 g of anhydrous potassium carbonate was added. The mixture was heated to 95 °C under a continuous nitrogen flow and reacted for 16 h. After the reaction was complete, 50 mL of pure water was added to dilute the reaction mixture. The aqueous phase was washed three times with 30 mL of ethyl acetate. The aqueous phase was retained and its pH was adjusted to 2-3 with 1 M hydrochloric acid. The mixture was filtered, and the filter cake was washed with a small amount of cold water and dried under vacuum to obtain the crude product. The crude product was purified by preparative HPLC (C18 reversed-phase column, mobile phase: acetonitrile / water + 0.1% formic acid). The fraction containing the target product was collected, freeze-dried, and 4.94 g of 4-((3-phosphonopropyl)amino)-3-(trifluoromethyl)benzenesulfonate was obtained.

[0046] Mass spectrometry (MS+H) of 4-((3-phosphonopropyl)amino)-3-(trifluoromethyl)benzenesulfonic acid + 364;

[0047] 4-((3-phosphonopropyl)amino)-3-(trifluoromethyl)benzenesulfonic acid 1HNMR-CDCl3: δ 9.14 (s, 2H), 9.04 (s, 1H), 7.20 (s, 1H), 7.11 (m, 1H), 6.97 (dd, 1H), 3.26 (t, 1H), 3.05 (m, 2H), 2.08-1.91 (m, 2H), 1.91-1.75 (m, 2H).

[0048] Example 1

[0049] A method for preparing conductive polymer composite aluminum foil for solid-state batteries and solid-state capacitors:

[0050] 1. Raw material composition by weight:

[0051] A conductive polymer dispersion, wherein the conductive polymer dispersion is a 3wt% aqueous solution of polyaniline, and the doped acid is 4-((3-phosphonopropyl)amino)-3-(trifluoromethyl)benzenesulfonic acid, with a mass ratio of 1:0.02, totaling 60 parts;

[0052] The conductive filler is a mixture of micron-sized aluminum powder (D50 of 5-10μm) and submicron-sized aluminum powder (D50 of 0.2-0.5μm) in a mass ratio of 2:1, totaling 1.8 parts.

[0053] The tackifier is a water-based polyurethane emulsion (30wt% solids content), 2 parts;

[0054] The functional additives are polyvinylpyrrolidone K30, γ-aminopropyltriethoxysilane, and polyether-modified polydimethylsiloxane, in a mass ratio of 6:2:2, totaling 1 part;

[0055] The solvent is dimethyl sulfoxide, 30 parts.

[0056] 2. Preparation method:

[0057] S1. Pretreatment of aluminum foil substrate: Industrial-grade aluminum foil with a thickness of 12μm was selected as the current collector substrate. First, the surface dust was rinsed off with deionized water, followed by surface activation treatment: First, the aluminum foil was immersed in a 5wt% sodium hydroxide solution for alkaline washing and degreasing for 60s to remove surface grease and part of the oxide layer; then, the aluminum foil was quickly transferred to a 3wt% hydrochloric acid solution for etching treatment for 30s to further remove the residual oxide layer and increase the surface roughness; finally, it was repeatedly rinsed with deionized water until neutral, and dried with hot air at 60℃ to obtain the pretreated aluminum foil;

[0058] S2. Preparation of conductive composite slurry (under nitrogen atmosphere): Weigh each raw material according to the above-mentioned mass proportions. The specific mixing and dispersion process is as follows: First, add the conductive polymer dispersion and dimethyl sulfoxide solvent to a high-speed dispersion vessel, turn on the stirrer and pre-stir for 10 minutes at a speed of 500 rpm to ensure that the two are initially mixed evenly; add the thickener (waterborne polyurethane emulsion) and functional additives to the system in sequence, adjust the speed to 800 rpm, and continue stirring for 20 minutes to fully disperse the additives and make them compatible with the base material; add the conductive filler to the mixture in 3 batches, each batch After adding materials at 5-minute intervals, increase the rotation speed to 2000 rpm and perform high-speed shear dispersion for 25 minutes to initially break up the filler agglomerates. Transfer the above materials to an ultrasonic dispersion device and ultrasonically disperse for 60 minutes at a power of 300W to further refine the agglomerates and improve the uniformity of the slurry. After ultrasonication, filter the slurry through a 200-mesh filter cloth to remove large particulate impurities. Then, place the filtered slurry in a degassing tank with a vacuum degree of -0.09MPa and degas for 15 minutes to remove air bubbles from the system, resulting in a uniform and stable conductive composite slurry.

[0059] S3. Coating and Film Formation: Using a micro-gravure coating process, the conductive composite paste prepared in step S2 is uniformly coated onto both sides of the pretreated aluminum foil obtained in step S1. During the coating process, the wet film thickness is controlled by adjusting the coating roller speed and pressure to ensure that the single-sided surface density of the conductive layer is 120 g / m² after drying. 2 ;

[0060] S4. Curing and Post-treatment: The coated aluminum foil is then fed into a continuous gradient drying oven for curing. The specific gradient drying process is as follows:

[0061] First stage: Low-temperature drying, temperature 70℃, processing time 15 minutes, to remove most of the free solvent in the slurry;

[0062] Second stage: medium-temperature drying, temperature 120℃, treatment time 10 minutes, to further remove residual solvent and promote uniform film formation of coating.

[0063] The third stage: high-temperature heat treatment at 160℃ for 10 minutes to enhance the charge transfer between the conductive polymer and the doped acid, improve the adhesion between the coating and the aluminum foil substrate and the density of the coating; after drying and curing, a conductive polymer composite coating with a thickness of 100μm is formed on the surface of the aluminum foil, thus obtaining the conductive polymer composite aluminum foil.

[0064] Example 2

[0065] A method for preparing conductive polymer composite aluminum foil for solid-state batteries and solid-state capacitors:

[0066] 1. Raw material composition by weight:

[0067] Conductive polymer dispersion: The conductive polymer dispersion is a 5wt% polypyrrole N-methylpyrrolidone dispersion, and the doped acid is 4-((3-phosphonopropyl)amino)-3-(trifluoromethyl)benzenesulfonic acid, with a mass ratio of 1:0.015, totaling 75 parts;

[0068] Conductive filler: a mixture of micron-sized aluminum powder (D50 of 8-12μm) and submicron-sized aluminum powder (D50 of 0.3-0.8μm) in a mass ratio of 1:1, totaling 2.5 parts;

[0069] Tackifier: Acrylic emulsion (25wt% solids), 3 parts;

[0070] Functional additives: polyvinylpyrrolidone K30, γ-aminopropyltriethoxysilane, and polyether-modified polydimethylsiloxane, in a mass ratio of 4:3:3, totaling 1.5 parts;

[0071] Solvent: Dimethyl sulfoxide, 20 parts.

[0072] 2. The preparation method is the same as in Example 1.

[0073] Example 3

[0074] A method for preparing conductive polymer composite aluminum foil for solid-state batteries and solid-state capacitors:

[0075] 1. Raw material composition by weight:

[0076] Conductive polymer dispersion: The conductive polymer dispersion is a 2wt% polythiophene aqueous solution, and the doped acid is 4-((3-phosphonopropyl)amino)-3-(trifluoromethyl)benzenesulfonic acid, with a mass ratio of 1:0.03, totaling 50 parts;

[0077] Conductive filler: a mixture of micron-sized aluminum powder (D50 of 5-10μm) and submicron-sized aluminum powder (D50 of 0.2-0.5μm) in a mass ratio of 1:2, totaling 1.2 parts;

[0078] Tackifier: 1 part of waterborne polyurethane emulsion (35wt% solids content);

[0079] Functional additives: polyvinylpyrrolidone K30, γ-aminopropyltriethoxysilane, and polyether-modified polydimethylsiloxane, in a mass ratio of 8:1:1, totaling 0.8 parts;

[0080] Solvent: Dimethyl sulfoxide, 45 parts.

[0081] 2. The preparation method is the same as in Example 1.

[0082] Comparative Example 1

[0083] A method for preparing conductive polymer composite aluminum foil for solid-state batteries and solid-state capacitors, referring to the preparation process of Example 1, but replacing the doping acid with... The rest remains the same as in Example 1.

[0084] Comparative Example 2

[0085] A method for preparing conductive polymer composite aluminum foil for solid-state batteries and solid-state capacitors is described, referring to the preparation process of Example 1, except that the doping acid is replaced with p-toluenesulfonic acid, and the rest remains the same as in Example 1.

[0086] Comparative Example 3

[0087] A method for preparing conductive polymer composite aluminum foil for solid-state batteries and solid-state capacitors is described, referring to the preparation process of Example 1, except that the doping acid is replaced with dodecylbenzenesulfonic acid, and the rest remains the same as in Example 1.

[0088] Comparative Example 4

[0089] A method for preparing conductive polymer composite aluminum foil for solid-state batteries and solid-state capacitors is the same as that in Example 1, except that no doping acid is added.

[0090] Performance testing:

[0091] 1. Conductivity Test: A four-probe method was used, with probes pressed vertically onto the sample coating surface (1 mm apart). Five different test points were selected for each sample (excluding the area within 10 mm of the edge), and the surface resistance at each point was recorded (unit: Ω / □). The volume resistivity was calculated using the formula: ρ v =R s ×d(ρ v Volume resistivity, unit: Ω·m; R s d represents surface resistance (Ω / □); d represents coating thickness (m). The data are shown in Table 1.

[0092] 2. Coating adhesion test: Refer to GB / T9286-1998 to test the coating adhesion level. The data are shown in Table 1.

[0093] 3. High-Temperature Stability Test: Place the test sample in a high-temperature aging chamber and record the initial surface resistance R0. Then, place the sample in the high-temperature aging chamber at 160℃ and maintain this temperature for 72 hours. During the aging process, avoid overlapping or contact between the samples and the chamber. After aging, remove the sample and allow it to stand in a standard environment (23℃, 50%RH) for 2 hours. Test the surface resistance R1 again. Calculate the resistance change rate: ΔR = |(R1-R0) / R0| × 100%. The data are shown in Table 1.

[0094] Table 1

[0095]

[0096] The example group showed lower overall volume resistivity with less fluctuation and better adhesion, as well as a smaller resistance change rate after high-temperature aging. This indicates that the synergistic effect of this specific doped acid with conductive fillers / tackifiers / additives can simultaneously ensure the continuity of the conductive network and the stability of the interfacial bonding. In the comparative examples, the inorganic strong acid system often showed good initial conductivity but poor adhesion and significant high-temperature decay, reflecting the instability caused by corrosion / dedoping. The conventional organic sulfonic acid system showed limited conductivity improvement and moderate aging decay. The sample without doped acid had the worst conductivity, weakest adhesion, and worst high-temperature stability, indicating that "doping" is key to conductivity activation and long-term maintenance.

[0097] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing conductive polymer composite aluminum foil for solid-state batteries and solid-state capacitors, characterized in that, Includes the following steps: S1. Pretreatment of aluminum foil substrate: Industrial grade aluminum foil is selected as the current collector substrate. Its surface is cleaned and surface activated to remove surface grease and oxide layer, and increase surface roughness to obtain pretreated aluminum foil. S2. Preparation of conductive composite slurry: Weigh the following raw materials by mass: 40-85 parts of conductive polymer dispersion, 0.8-3.5 parts of conductive filler, 0.5-5 parts of thickener, 0.1-3 parts of functional additive, and 10-50 parts of solvent; mix and disperse the above raw materials evenly to obtain conductive composite slurry; S3. Coating and film formation: The conductive composite paste described in step S2 is uniformly coated onto both sides of the pretreated aluminum foil described in step S1 using a coating process. S4. Curing and post-treatment: The coated aluminum foil is subjected to gradient drying at 60-300℃ to form a conductive polymer composite coating with a thickness of 80-120μm on the surface of the aluminum foil, thus obtaining the conductive polymer composite aluminum foil. The conductive polymer dispersion is obtained by mixing a conductive polymer dispersion with a doped acid, wherein the mass ratio of the conductive polymer dispersion to the doped acid is 1:0.001-0.08; The doped acid is: ; The mass ratio of the conductive polymer dispersion to the conductive filler is 1:0.01-0.04; The conductive filler is a mixture of micron-sized and submicron-sized aluminum powder.

2. The method for preparing a conductive polymer composite aluminum foil for solid-state batteries and solid-state capacitors according to claim 1, characterized in that, The surface activation treatment described in S1 involves alkaline washing and degreasing with sodium hydroxide solution, followed by etching with hydrochloric acid solution. The concentration of the sodium hydroxide solution is 1-10 wt%, and the treatment time is 10-120 s; The concentration of the hydrochloric acid solution is 1-10 wt%, and the treatment time is 10-60 s.

3. The method for preparing a conductive polymer composite aluminum foil for solid-state batteries and solid-state capacitors according to claim 1, characterized in that, The conductive polymer dispersion is selected from one or more of the following: aqueous dispersions or organic solvent dispersions of polyaniline, polypyrrole, and polythiophene. The concentration of the conductive polymer dispersion is 0.5-8 wt%; The organic solvent is one or more of dimethyl sulfoxide, N-methylpyrrolidone, and dimethylformamide.

4. The method for preparing a conductive polymer composite aluminum foil for solid-state batteries and solid-state capacitors according to claim 1, characterized in that, The mass ratio of the micron-sized and submicron-sized particles is 1-20:1-20.

5. The method for preparing a conductive polymer composite aluminum foil for solid-state batteries and solid-state capacitors according to claim 1, characterized in that, The tackifier is selected from waterborne polyurethane or acrylic emulsion; The functional additive is a mixture of polyvinylpyrrolidone K30, γ-aminopropyltriethoxysilane and polyether-modified polydimethylsiloxane, with a mass ratio of 4-8:1-3:1-3. The solvent is dimethyl sulfoxide.

6. The method for preparing a conductive polymer composite aluminum foil for solid-state batteries and solid-state capacitors according to claim 1, characterized in that, The mixing and dispersion process in step S2 is as follows: First, the conductive polymer dispersion is mixed with the solvent and pre-stirred for 5-20 minutes; then, the thickener and functional additives are added sequentially, and stirring is continued for 10-30 minutes; then, the conductive filler is added in batches, and high-speed shear dispersion is carried out at 1000-3000 rpm for 10-40 minutes; then, sand milling or ultrasonic dispersion is used for 20-120 minutes to further refine the agglomerates; finally, the mixture is filtered through a 100-300 mesh filter and vacuum degassed for 5-30 minutes to obtain the conductive composite slurry.

7. The method for preparing a conductive polymer composite aluminum foil for solid-state batteries and solid-state capacitors according to claim 1, characterized in that, The coating process described in step S3 controls the wet film thickness so that the surface density of the conductive layer after drying is controlled at 80-250 g / m². 2 Within the range.

8. The method for preparing a conductive polymer composite aluminum foil for solid-state batteries and solid-state capacitors according to claim 1, characterized in that, The specific process of gradient drying in step S4 is as follows: First stage: Bake at 50-90℃ for 10-30 minutes; Second stage: Heat to 90-140℃ and dry for 5-15 minutes; The third stage: high-temperature heat treatment at 140-200℃ for 5-20 minutes.

9. The method for preparing a conductive polymer composite aluminum foil for solid-state batteries and solid-state capacitors according to claim 1, characterized in that, Step S2 is performed under a nitrogen atmosphere.

10. A solid-state battery comprising the composite aluminum foil prepared by the method for preparing a conductive polymer composite aluminum foil for a solid-state battery and solid-state capacitor according to any one of claims 1-9.

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