Wide-temperature-range polymer solid-state zinc secondary battery as well as preparation method and application thereof

Abstract

The invention discloses a wide-temperature-range polymer solid-state zinc secondary battery and a preparation method and application thereof. The wide-temperature-range polymer solid-state zinc secondary battery is composed of a polyaniline positive electrode, a zinc negative electrode and a polymer solid-state electrolyte. The polymer solid electrolyte is a multi-element cross-linked network formed by free radical polymerization cross-linking of rotaxane supramolecules, polyacrylamide, zinc salt, water and other components, and is rich in polar hydrogen bond functional groups and ion transmission channels. And the wide-temperature adaptability, the positive and negative electrode interface compatibility and the zinc ion rapid transmission capability of the polymer solid electrolyte can be enhanced. The polymer solid electrolyte and the wide-temperature-range polymer solid zinc secondary battery are simple in preparation process, high in designability, excellent in electrochemical performance and wide-temperature adaptability and wide in application prospect in wide-temperature-range water-based zinc ion batteries.

Description

Technical Field

[0001] The present invention relates to the technical field of rechargeable aqueous zinc ion batteries, and particularly to a wide-temperature polymer solid-state zinc secondary battery and a preparation method and application thereof. Background Art

[0002] Aqueous zinc ion batteries have the advantages of high safety, rich resources, and low cost, and are a new type of large-scale energy storage system with great development prospects. With the intensification of the global extreme temperature environment and the continuous increase of new special application scenarios such as deep-sea operations, polar expeditions, space exploration, and national defense technology, the demand for large-scale stable energy storage of aqueous zinc ion batteries in a relatively wide working temperature range (wide temperature range) is becoming more and more urgent. Therefore, broadening the working temperature range of rechargeable aqueous zinc batteries is of great significance for promoting the development of high-performance electrochemical energy storage devices and meeting the application requirements in different fields.

[0003] Polyaniline has the advantages of high conductivity, excellent redox reversibility, environmental friendliness, low cost, etc. Therefore, polyaniline-zinc secondary batteries have received wide attention. At present, most of the electrolytes of polyaniline-zinc batteries are based on aqueous electrolytes, and they face more severe problems such as zinc dendrite growth and water-induced parasitic reactions under wide-temperature conditions. The polymer solid electrolyte composed of organic polymers, water, salts and other components can inherit the dual advantages of liquid electrolytes and solid electrolytes, such as relatively high ionic conductivity, close contact with electrode materials, effective inhibition of water molecule leakage, and excellent cold and heat resistance, providing an effective way to solve the problems faced by the electrolyte of wide-temperature polyaniline-zinc secondary batteries. However, the polymer solid electrolyte has poor high and low temperature resistance, and there are still problems of slow kinetics and poor zinc negative electrode / electrolyte interface stability. Therefore, it is imperative to develop a regulation strategy to enhance the wide-temperature adaptability of polymer solid electrolytes.

[0004] In recent years, domestic and foreign researchers have adopted a variety of methods to improve the wide temperature performance of polymer solid-state electrolysis in aqueous zinc-ion batteries, mainly including the introduction of inorganic salts, polyionic liquids and organic solvents, and polymer network modification. Among them, the polymer network modification strategy allows the material to accommodate more components at the same time. This feature gives the polymer solid-state electrolysis a diversity of microstructures and interface properties, and achieves a synergistic enhancement effect between multiple materials. The Chinese patent (CN119340517A) previously applied by the inventor discloses a metal zinc negative electrode modified with a hydride boryne / polyrotaxane composite interface film, a preparation method and an application. An organic-inorganic hybrid artificial interface film is introduced on the surface of the zinc negative electrode to inhibit dendrite growth during the cycle process, improve the cycle life and cycle stability of the zinc battery, and mainly focuses on the modification and protection of the zinc negative electrode surface, which is applied to liquid aqueous zinc battery systems. The present invention mainly focuses on the design of a wide temperature range polymer solid-state secondary battery electrolyte and applies it to solid-state secondary batteries. The present invention introduces rotaxane supramolecules rich in hydroxyl structures into a polyacrylamide hydrogel matrix to form a multi-level cross-linked network structure containing a rotaxane dynamic pulley structure, which is conducive to breaking hydrogen bonds between water molecules and stabilizing free water molecules, thereby effectively inhibiting the low-temperature coagulation and high-temperature water loss problems of polymer solid-state electrolysis, and is conducive to enhancing the wide temperature performance of polyaniline-zinc secondary batteries. At the same time, the dynamic pulley structure of the rotaxane supramolecule can promote the rapid transmission of zinc ions, thereby accelerating the zinc deposition reaction kinetics, which can fundamentally solve the problems of slow low-temperature kinetics and uncontrollable growth of dendrites in aqueous zinc ion batteries, and is conducive to the wide application of wide temperature range polyaniline-zinc secondary batteries. Summary of the invention

[0005] The present invention aims to provide a wide temperature range polymer solid-state zinc secondary battery to overcome the problems of slow ion transfer kinetics, poor environmental adaptability and interface compatibility of polyaniline-zinc batteries in the prior art.

[0006] In order to solve the above technical problems, the technical solution adopted by the present invention is: A wide temperature range polymer solid-state zinc secondary battery, the secondary battery consists of a polyaniline positive electrode, a zinc negative electrode and a polymer solid-state electrolyte, wherein the positive electrode active material is a polyaniline organic material, the negative electrode active material is mainly a zinc element material, and the polymer solid-state electrolyte is formed by cross-linking components such as rotaxane supramolecules, polyacrylamide, zinc salt and water through free radical polymerization.

[0007] The method for preparing the wide temperature range polymer solid-state zinc secondary battery of the present invention comprises the following steps: 1) Preparation of polymer solid electrolyte: The rotaxane supramolecular solution A and the polyacrylamide precursor solution B are fully mixed to obtain solution C, which is evenly dripped onto the mold surface and polymerized to obtain a polymer solid electrolyte.

[0008] 2) Preparation of polyaniline positive electrode and zinc negative electrode; 3) Preparation of polymer solid secondary battery: Assemble the above-mentioned polyaniline positive electrode, zinc negative electrode and polymer solid electrolyte into a polymer solid zinc secondary battery by a conventional method.

[0009] Furthermore, the preparation method of the rotaxane supramolecular solution A in step (1) is as follows: At room temperature (25 °C), dissolve cyclodextrin (CD) and polyethylene glycol (PEG) in deionized water, and mix and stir at 45 °C for 30 - 60 minutes, and self-assemble by host-guest interaction to obtain the rotaxane supramolecular solution A.

[0010] Furthermore, the cyclodextrin is α-CD, β-CD or γ-CD, and the cyclodextrin concentration is 10 - 800 g / L; the molecular weight of the polyethylene glycol is 500 - 50000, and the polyethylene glycol concentration is 2 - 50 g / L.

[0011] Furthermore, the preparation method of the polyacrylamide precursor solution B in step (1) is as follows: Add monomer acrylamide, initiator potassium persulfate and crosslinking agent N,N'-methylenebisacrylamide to an aqueous solution containing zinc salt, and fully mix at 4 °C for 30 minutes to obtain the polyacrylamide precursor solution B.

[0012] Furthermore, in the polyacrylamide precursor solution B, the acrylamide concentration is 50 - 200 g / L, the potassium persulfate concentration is 0.1 - 2 g / L, and the N,N'-methylenebisacrylamide is 0.1 - 5 g / L; the zinc salt concentration is 1 - 3 mol / L, and the zinc salt is one or more of zinc sulfate, zinc chloride, zinc acetate, zinc nitrate, zinc fluoride, zinc trifluoromethanesulfonate, zinc bis(trifluoromethylsulfonyl)imide.

[0013] Furthermore, the volume ratio of the rotaxane supramolecular solution A and the polyacrylamide precursor solution B in step (1) is (0.1 - 10):1, the polymerization temperature is 25 °C, and the polymerization time is 60 - 90 minutes.

[0014] Furthermore, the preparation method of the polyaniline positive electrode in step (2) is as follows: Mix PANI active material, conductive carbon (Ketjen black), and binder (10 wt% PTFE aqueous solution) in a mass ratio of 8:1:1, and uniformly mix with absolute ethanol as a solvent for 60 - 120 minutes. Use a glass rod to roll the slurry into a film with a uniform thickness, then cut it into a disc with a diameter of 10 mm, and press it onto the surface of a titanium mesh with a diameter of (control the active material loading to be 1 - 3 mg / cm 2 ) and vacuum dry at 50 - 80 °C for 24 - 48 hours to obtain the polyaniline positive electrode.

[0015] Further, the preparation method of the zinc metal anode in step (2) is as follows: clean the surface of the zinc foil with deionized water and absolute ethanol, dry it at room temperature (25 °C), and then press it into a circular electrode sheet as the anode.

[0016] Advantages and beneficial effects of the present invention: 1. The wide-temperature-range polymer solid-state zinc secondary battery described in the present invention is composed of a polyaniline cathode, a zinc anode, and a polymer solid electrolyte. The polymer solid electrolyte is formed by free radical polymerization crosslinking of components such as rotaxane supramolecule, polyacrylamide, zinc salt, and water, and has high interfacial compatibility with the polyaniline cathode and the zinc anode.

[0017] 2. The present invention introduces a rotaxane supramolecule rich in hydroxyl groups into the polyacrylamide hydrogel matrix to form a dynamic multi-level cross-linked network structure, which is beneficial to enhancing the wide-temperature performance of the gel electrolyte. At the same time, the dynamic pulley structure of the rotaxane supramolecule can promote the rapid transport of zinc ions, thereby accelerating the zinc deposition reaction kinetics, and can fundamentally solve the problems of slow low-temperature kinetics and uncontrollable dendrite growth in polyaniline-zinc secondary batteries.

[0018] 3. The components of the wide-temperature-range polymer solid-state zinc secondary battery described in the present invention are all fully solid-state and free of free water solvents. Its preparation process is simple, highly designable, has excellent electrochemical performance and wide-temperature adaptability, and has broad application prospects in wide-temperature-range aqueous zinc-ion batteries. Description of the drawings

[0019] Figure 1 a~c are cyclic voltammograms of the polymer solid electrolytes prepared in Comparative Examples 1~4 and Examples 3~5, 8, 9; Figure 2 is a statistical chart of the zinc ion transference numbers of the polymer solid electrolytes prepared in Comparative Examples 2~4 and Example 4; Figure 3 is a SEM image of the zinc deposition morphology of the polymer solid electrolytes prepared in Comparative Examples 2~4 and Example 4; Figure 4 is the room temperature Coulombic efficiency of the polymer solid electrolytes prepared in Comparative Example 2 and Example 4; Figure 5 is the wide-temperature performance of the polymer solid electrolytes prepared in Comparative Example 2 and Example 4; Figure 6 is the wide-temperature performance of the polymer solid-state zinc secondary battery assembled using the electrolytes prepared in Comparative Example 2 and Example 4. Specific embodiments

[0020] Next, in combination with the embodiments of the present invention, the technical solutions of the present invention will be clearly and completely described, but the implementation manners of the present invention are not limited thereto. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0021] Example 1 The preparation process of the polyaniline positive electrode is as follows: First, the polyaniline (PANI) positive electrode was prepared by the coating-rolling method: The PANI active material, conductive carbon (Ketjen black), and binder (10 wt% PTFE aqueous solution) were mixed evenly in a 2 mL small beaker with a stainless steel spatula for 1 h at a mass ratio of 8:1:1, using absolute ethanol as the solvent. The slurry was rolled into a thin film with a uniform thickness using a glass rod, and then cut into circular pieces with a diameter of 10 mm, and pressed onto the surface of a Ti mesh with a diameter of 16 mm (controlling the active material loading to be 1 - 3 mg / cm 2 ) The electrode sheet was placed in a vacuum oven and dried at 50 °C for 24 h.

[0022] Example 2 The preparation process of the zinc negative electrode is as follows: The surface of the zinc negative electrode (with a thickness of 0.05 mm) was washed and dried multiple times with deionized water and absolute ethanol, and then pressed into a circular electrode sheet (with a diameter of 12 mm) for use as the zinc negative electrode.

[0023] Example 3 The preparation process of the polymer solid electrolyte specifically includes the following steps: (1) At room temperature (25 °C), 0.4 g of α-cyclodextrin (α-CD) and 0.04 g of polyethylene glycol (PEG2000, molecular weight M w is 2000) were dissolved in 3 mL of deionized water and stirred at 45 °C for 0.5 h to obtain the rotaxane supramolecular solution A, where the concentration of α-CD is 133 g / L and the concentration of PEG2000 is 13.3 g / L; (2) An 8 mL aqueous ZnSO4 solution was prepared at a concentration of 2 mol / L, and then 0.8 g of monomer acrylamide (AM) powder, 0.0064 g of initiator potassium persulfate, and 0.008 g of crosslinking agent N,N'-methylenebisacrylamide were added, and stirred at 4 °C for 0.5 h to disperse evenly to obtain the polyacrylamide precursor solution B; The concentration of acrylamide in the polyacrylamide precursor solution B is 100 g / L, the concentration of potassium persulfate is 0.8 g / L, and the concentration of N'N-methylenebisacrylamide is 1 g / L; (3) The rotaxane supramolecular solution A and the polyacrylamide precursor solution B were fully mixed at a volume ratio of 0.375:1 to obtain solution C. Then, 0.1 mL of solution C was evenly drop-coated on the surface of the metal zinc negative electrode sheet and polymerized at 25°C for 1 h. The polymerization of acrylamide monomer was initiated by the strong reducing property of the initiator and metal zinc, and a wide-temperature gel polymer solid electrolyte was obtained by polymerization in a mold.

[0024] Example 4 The preparation process of the polymer solid electrolyte in this embodiment is different from that in Embodiment 3 only in that the concentration of α-CD in step (1) is 200 g / L.

[0025] Example 5 The preparation process of the polymer solid electrolyte in this embodiment differs from that in Embodiment 3 only in that the concentration of α-CD in step (1) is 267 g / L.

[0026] Example 6 The preparation process of the polymer solid electrolyte in this embodiment differs from that in Embodiment 3 only in that the concentration of α-CD in step (1) is 333 g / L.

[0027] Example 7 The preparation process of the polymer solid electrolyte in this embodiment is different from that in Embodiment 3 only in that the concentration of α-CD in step (1) is 400 g / L.

[0028] Example 8 The preparation process of the polymer solid electrolyte in this embodiment is different from that in Embodiment 3 only in that the concentration of α-CD in step (1) is 200 g / L and the polyethylene glycol used is PEG1000.

[0029] Example 9 The only difference between the preparation process of the polymer solid electrolyte in this embodiment and that in embodiment 3 is that the concentration of α-CD in step (1) is 200 g / L and the polyethylene glycol used is PEG3500.

[0030] Comparative Examples 1-4 In Comparative Examples 1-4, except that the components of the electrolyte precursor solution are prepared as shown in Table 1, the rest of the experimental process is the same as that of Example 3.

[0031] Table 1 Components of the electrolyte precursor solutions prepared in Comparative Examples 1 to 4 Example type α-CD concentration Polyethylene glycol 40 g / L AM monomer concentration Zinc salt concentration and type Comparative example 1 − − − <![CDATA[2mol / L ZnSO4]]> Comparative example 2 − − 100 g / L <![CDATA[2mol / L ZnSO4]]> Comparative example 3 − PEG2000 100 g / L <![CDATA[2mol / L ZnSO4]]> Comparative example 4 200 g / L − 100 g / L <![CDATA[2mol / L ZnSO4]]> Test Example 1 Cyclic voltammetry tests of the polymer solid electrolytes prepared in Comparative Examples 1-4 and Examples 3-5, 8 and 9.

[0032] The zinc deposition / stripping kinetic behaviors of the polymer solid electrolytes prepared in Comparative Examples 1-4 and Examples 3-5, 8, 9 were characterized by cyclic voltammetry tests using an electrochemical workstation at a scan rate of 1 mV / s. The results are as Figure 1 shown in Figs. Figure 1 a-c. It can be analyzed that the response currents of zinc deposition / precipitation both show a trend of first increasing and then decreasing with the increase of the α-CD concentration and the PEG molecular weight, and are significantly better than those of the comparative examples. The polymer solid electrolytes prepared in Examples 3-5, 8, 9 have good zinc deposition / precipitation kinetics. Among them, the polymer solid electrolyte prepared in Example 4 has the highest response current of zinc deposition / precipitation, indicating the fastest reaction kinetics.

[0033] Test Example 2 Zinc ion transference numbers of the polymer solid electrolytes prepared in Comparative Examples 2-4 and Example 4.

[0034] First, Zn / Zn symmetric cells were assembled using the polymer solid electrolytes prepared in Comparative Examples 2-4 and Example 4. Then, the symmetric cells were polarized at a voltage of 15 mV for 2 h to make the current reach a steady state, and the zinc ion transference numbers were measured by the steady-state current method. The results are as Figure 2 shown.

[0035] It can be Figure 2 analyzed that the zinc ion transference number of the polymer solid electrolyte provided in Example 4 of the present invention can reach 0.57, indicating good selectivity for zinc ion transport during the charge and discharge process.

[0036] Test Example 3 Observation of the surface zinc deposition morphology of constant current electrodeposition in the polymer solid electrolytes prepared in Comparative Examples 2-4 and Example 4.

[0037] First, Zn / Zn symmetric cells were assembled using the polymer solid electrolytes prepared in Comparative Examples 2-4 and Example 4, and were subjected to constant current deposition for 10 h at 25 °C using a battery tester, and the current density was set to 1 mA / cm 2 . Then, the zinc deposition morphology was observed and compared using a scanning electron microscope (SEM) at an accelerating voltage of 15 kV. The results are as Figure 3 shown.

[0038] It can be Figure 3 analyzed that obvious massive dendrites appeared on the surface of the zinc negative electrode during constant current electrodeposition in the electrolytes of Comparative Example 2 (PAM), Comparative Example 3 (PEG + PAM), and Comparative Example 4 (α-CD + PAM). Obviously, the surface of the zinc deposited in the electrolyte of Example 4 (α-CD@PEG + PAM) is flatter and denser.

[0039] Test Example 4 Coulombic efficiency test at room temperature of the polymer solid electrolytes prepared in Comparative Example 2 and Example 4.

[0040] First, Zn / Cu asymmetric cells were assembled using the polymer solid electrolytes prepared in Comparative Example 2 and Example 4. Then, a constant current charge-discharge cycle test was carried out using a battery tester at a constant temperature of 25 °C, with a current density of 1 mA / cm 2 , a deposition areal capacity of 1 mAh / cm 2 , and a stripping cut-off voltage of 0.5 V vs. Zn 2+ / Zn. The results are as Figure 4 shown.

[0041] It can be Figure 4 seen from the analysis that the Zn / Cu asymmetric cell assembled using the electrolyte of Comparative Example 2 (PAM) showed a significant fluctuation in Coulombic efficiency after 79 cycles under the test conditions of 1 mA / cm 2 , 1 mAh / cm 2 . However, in the case of using the electrolyte of Example 4 (α-CD@PEG+PAM), the Zn / Cu asymmetric cell could stably cycle 500 times, indicating a significant improvement in the reversibility of zinc deposition / stripping.

[0042] Test Example 5 Wide-temperature cycle stability test of the polymer solid electrolytes prepared in Comparative Example 2 and Example 4.

[0043] First, Zn / Zn symmetric cells were assembled using the polymer solid electrolytes prepared in Comparative Example 2 and Example 4. Then, a constant current charge-discharge cycle test was carried out using a battery tester under the wide-temperature condition of -10 °C to 60 °C, with a current density of 1 mA / cm 2 , a deposition / stripping areal capacity of 1 mAh / cm 2 , and the wide-temperature cycle stability of the zinc anode is as Figure 5 shown.

[0044] It can be Figure 5 seen from the analysis that the polarization voltage of the Zn / Zn symmetric cell assembled using the electrolyte of Comparative Example 2 (PAM) increased significantly after 82 h of cycling under the wide-temperature condition of -10 °C to 60 °C, resulting in battery failure. However, the Zn / Zn symmetric cell assembled using the electrolyte of Example 4 (α-CD@PEG+PAM) could stably operate within the wide-temperature range, indicating that such electrolytes have excellent wide-temperature performance.

[0045] Application Example 1 The Zn / PANI solid-state secondary battery was assembled with the polyaniline positive electrode prepared in Example 1, the zinc negative electrode prepared in Example 2, and the polymer solid electrolytes prepared in Comparative Example 2 and Example 4, and a wide-temperature cycling stability test was carried out.

[0046] First, the polymer solid-state zinc secondary battery was assembled with the polymer solid electrolytes prepared in Comparative Example 2 and Example 4. Then, a constant current charge-discharge cycling test was carried out using a battery tester under the wide-temperature condition of −10 °C to 60 °C, and the current density was 1 Ag −1 , and the voltage range was 0.5~1.5 V vs. Zn 2+ / Zn, and the results are as Figure 6 shown.

[0047] It can be Figure 6 analyzed that under the 1 Ag −1 test conditions, the reversible specific capacity of the Zn / PANI battery assembled with the electrolyte of Example 4 (α-CD@PEG+PAM) was higher than that of the electrolyte of Comparative Example 2 (PAM) under the wide-temperature condition of −10 °C to 60 °C, indicating that such polymer solid-state zinc secondary batteries have high cycling stability and reversibility in a wide temperature range.

[0048] Conclusion: A wide-temperature polymer solid-state zinc secondary battery provided by the present invention is composed of a polyaniline positive electrode, a zinc negative electrode, and a gel electrolyte. The polymer solid electrolyte is formed by free radical or free radical polymerization crosslinking of components such as rotaxane supramolecule, polyacrylamide, zinc salt, and water. The rotaxane supramolecule rich in hydroxyl structure and the polyacrylamide hydrogel matrix can form a dynamic multi-level crosslinked network structure, which is beneficial to breaking the hydrogen bonds between water molecules and stabilizing free water molecules, thereby effectively inhibiting the low-temperature solidification and high-temperature water loss of the polymer solid electrolyte, and is beneficial to enhancing the wide-temperature performance of the polyaniline-zinc secondary battery. At the same time, the dynamic pulley structure of the rotaxane supramolecule can promote the rapid transmission of zinc ions, thereby accelerating the zinc deposition reaction kinetics, and can fundamentally solve the problems of slow low-temperature kinetics and uncontrollable dendrite growth of aqueous zinc ion batteries. The components of the wide-temperature polymer solid-state zinc secondary battery described in the present invention are all all-solid-state and free of free water solvents, and the preparation process is simple, highly designable, has excellent electrochemical performance and wide-temperature adaptability, and has broad application prospects in wide-temperature aqueous zinc ion batteries.

[0049] In summary, the above embodiments are only to illustrate the relevant principles and implementation methods, aiming to enable those familiar with this technology to understand the content of the present invention and implement it accordingly, and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made to the present invention without departing from the principles of the present invention shall be covered within the protection scope of the present invention.

Claims

1. A wide-temperature-range polymer solid-state zinc secondary battery, characterized in that The secondary battery is composed of a polyaniline positive electrode, a zinc negative electrode, and a polymer solid electrolyte, wherein the polymer solid electrolyte is formed by free radical polymerization crosslinking of a rotaxane supramolecule, polyacrylamide, a zinc salt, and water.

2. The preparation method of the wide-temperature-range polymer solid-state zinc secondary battery according to claim 1, wherein It includes the following steps: 1) Preparation of the polymer solid electrolyte: The rotaxane supramolecule solution A and the polyacrylamide precursor solution B are fully mixed to obtain a solution C, which is uniformly drop-coated on the surface of a mold, and the polymer solid electrolyte is obtained after polymerization. 2) Preparation of the polyaniline positive electrode and the zinc negative electrode; 3) Preparation of the polymer solid secondary battery: The above-mentioned polyaniline positive electrode, zinc negative electrode, and polymer solid electrolyte are assembled into a polymer solid zinc secondary battery by a conventional method.

3. The preparation method of the wide-temperature-range polymer solid-state zinc secondary battery according to claim 1, characterized in that The preparation method of the rotaxane supramolecule solution A in step (1) is as follows: At room temperature (25 °C), cyclodextrin (CD) and polyethylene glycol (PEG) are dissolved in deionized water, mixed and stirred at 45 °C for 30 to 60 minutes, and a rotaxane supramolecule solution A is obtained by self-assembly using host-guest interaction.

4. The preparation method of the wide-temperature-range polymer solid-state zinc secondary battery according to claim 3, wherein, The cyclodextrin is α-CD, β-CD, or γ-CD, and the cyclodextrin concentration is 10 to 800 g / L; the molecular weight of the polyethylene glycol is 500 to 50000, and the polyethylene glycol concentration is 2 to 50 g / L.

5. The preparation method of the wide-temperature-range polymer solid-state zinc secondary battery according to claim 1, characterized in that, The preparation method of the polyacrylamide precursor solution B in step (1) is as follows: The monomer acrylamide, the initiator potassium persulfate, and the crosslinking agent N,N'-methylenebisacrylamide are added to an aqueous solution containing a zinc salt, and they are fully mixed at 4 °C for 30 minutes to obtain the polyacrylamide precursor solution B.

6. The preparation method of the wide-temperature-range polymer solid-state zinc secondary battery according to claim 5, characterized in that, In the polyacrylamide precursor solution B, the acrylamide concentration is 50 to 200 g / L, the potassium persulfate concentration is 0.1 to 2 g / L, and the N,N'-methylenebisacrylamide is 0.1 to 5 g / L; the zinc salt concentration is 1 to 3 mol / L, and the zinc salt is one or more of zinc sulfate, zinc chloride, zinc acetate, zinc nitrate, zinc fluoride, zinc trifluoromethanesulfonate, and zinc bis(trifluoromethylsulfonyl)imide.

7. The preparation method of the wide-temperature-range polymer solid-state zinc secondary battery according to claim 1, characterized in that, In step (1), the volume ratio of the rotaxane supramolecule solution A to the polyacrylamide precursor solution B is (0.1 to 10):1, the polymerization temperature is 25 °C, and the polymerization time is 60 to 90 minutes.

8. The preparation method of the wide-temperature-range polymer solid-state zinc secondary battery according to claim 1, wherein The preparation method of the polyaniline positive electrode in step (2) is as follows: The PANI active material, conductive carbon, and binder are uniformly mixed in a mass ratio of 8:1:1 with absolute ethanol as a solvent for 60 to 120 minutes. The slurry is rolled into a thin film with a uniform thickness using a glass rod, and then cut into circular pieces with a diameter of 10 mm, and pressed onto the surface of a titanium mesh with a diameter using a tablet press, and vacuum dried at 50 to 80 °C for 24 to 48 hours to obtain the polyaniline positive electrode.

9. The preparation method of the wide-temperature-range polymer solid-state zinc secondary battery according to claim 1, characterized in that, The preparation method of the metal zinc negative electrode in step (2) is as follows: The surface of the metal zinc foil is cleaned with deionized water and absolute ethanol, dried at room temperature, and then pounded into a circular electrode sheet as the negative electrode.

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