Preparation method and application of hybrid perovskite composite solid electrolyte

Abstract

The application relates to a preparation method of a hybrid perovskite composite solid electrolyte, comprising the following steps: adding a hybrid perovskite material into a mixed solution of polyethylene oxide and a lithium salt, and drying to obtain the hybrid perovskite composite solid electrolyte. Compared with the prior art, the application provides a preparation method of a hybrid perovskite composite solid electrolyte and application thereof. Through specific preparation technology and introduction of a hybrid agent, the hybrid perovskite composite solid electrolyte with excellent ion transmission performance and interface stability can be prepared. The solid electrolyte is expected to be widely applied in energy storage devices such as solid-state batteries, improve battery performance and safety, and promote the development of energy storage technology.

Description

Technical Field

[0001] This invention relates to the field of electrochemical technology, and in particular to a method for preparing and applying a hybrid perovskite composite solid electrolyte. Background Technology

[0002] Solid-state electrolytes are key materials primarily used in solid-state batteries, exhibiting high ionic conductivity and thermal stability. Among various solid-state electrolytes, perovskite-type solid-state electrolytes are promising candidates for application in all-solid-state lithium batteries. However, traditional pure perovskite materials face challenges in practical applications, such as slow ion transport rates and interface problems, limiting their use in solid-state electrolytes. To address these issues, research has been conducted on hybrid perovskites. Hybrid perovskite materials, as a novel type of solid-state electrolyte, demonstrate excellent ionic conductivity and application potential. Hybrid perovskites are formed by inserting organic ions or molecules into the inorganic perovskite lattice. By introducing organic molecules or ions into the perovskite structure, a hybrid structure is formed, improving the material's ionic conductivity and interface stability. This material structure possesses unique ion transport channels, contributing to improved solid-state battery performance and providing new possibilities for the application of solid-state electrolytes.

[0003] Chinese patent application CN105895916A discloses a method for preparing organic-inorganic hybrid perovskite materials and their novel applications. This invention marks the first successful application of organic-inorganic hybrid perovskite materials in lithium-ion batteries, achieving charge-discharge functionality. When used as an electrode material in lithium-ion batteries, this material not only boasts high capacity and numerous cycle times but also enables rapid charge-discharge. However, this invention primarily focuses on using hybrid perovskite materials as an electrode material. This invention envisions applying hybrid perovskite to the solid-state electrolyte of lithium-ion batteries. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a highly crystalline hybrid perovskite composite solid electrolyte with excellent ion transport performance and stability, low cost, simple operation, and mild conditions.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] This invention provides a method for preparing a hybrid perovskite composite solid electrolyte, comprising the following steps:

[0007] (1) Preparation of hybrid perovskite material: Add hydrochloric acid to organic raw materials and react fully, then dry to obtain a white solid; dissolve inorganic raw materials in water and add a small amount of hydrochloric acid to dissolve fully to obtain a purple solution; add the white solid to the purple solution to dissolve fully, add hydrochloric acid to react fully, and finally dry to obtain hybrid perovskite material.

[0008] (2) Stir the polyethylene oxide (PEO) powder evenly in deionized water, then add lithium salt and stir magnetically to dissolve it completely to obtain a mixed solution;

[0009] (3) The obtained hybrid perovskite material was added to the mixed solution and stirred magnetically and sonicated;

[0010] (4) The PEO solution of the doped hybrid perovskite was dropped onto the mold and dried to obtain the hybrid perovskite composite solid electrolyte.

[0011] Further, in step (1), the organic raw material is preferably dodecylamine (C 12 H 25 The inorganic raw material is preferably CoCl2, and even more preferably CoCl2·4H2O.

[0012] Furthermore, in step (1), the final drying time is 12-15 hours and the temperature is 50-70℃.

[0013] Further, in step (1), the concentration of hydrochloric acid is 38%, and the amount of hydrochloric acid added is 200-300 ml, preferably 300 ml.

[0014] Furthermore, in step (2), the molecular weight of the PEO selected is 100,000 to 600,000, and the mass ratio of lithium salt to PEO is 1-1.5:10.

[0015] Further, in step (2), the lithium salt is preferably lithium bis(trifluoromethanesulfonyl)imide (LiTFSi).

[0016] Furthermore, in step (2), the magnetic stirring time is 12-24 hours, preferably 20 hours.

[0017] Furthermore, in step (3), the mass ratio of the hybrid perovskite material to the PEO powder is 1:5-30, preferably 1:6.

[0018] Furthermore, in step (3), the magnetic stirring time is 12-24 hours, preferably 20 hours.

[0019] Furthermore, in step (3), the frequency of the ultrasound is 200W and the duration is 10-15h, preferably 13h.

[0020] Furthermore, in step (4), the drying temperature is 40-50°C, preferably 45°C.

[0021] On the other hand, the present invention provides a hybrid perovskite composite solid electrolyte, which is prepared by the above method.

[0022] On the other hand, the present invention also provides an application of a hybrid perovskite composite solid electrolyte, which can be used in lithium-ion batteries, sodium-ion batteries, lead-acid batteries or supercapacitors.

[0023] This invention proposes a method for preparing a hybrid perovskite composite solid electrolyte and its application. Through specific preparation processes and the introduction of hybrid agents, a hybrid perovskite composite solid electrolyte with excellent ion transport performance and interfacial stability can be prepared. This solid electrolyte is expected to be widely used in energy storage devices such as solid-state batteries, improving battery performance and safety, and promoting the development of energy storage technology.

[0024] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0025] (1) Simple operation: The present invention mixes hybrid perovskite material and PEO and then dries it on a mold to finally obtain a uniformly dispersed hybrid perovskite filler PEO polymer solid electrolyte. The method is simple, the raw materials are designable, and the application is wide.

[0026] (2) High ion transport efficiency: The composite polymer solid electrolyte material prepared by the method of the present invention incorporates hybrid perovskite as a filler. Since hybrid perovskite has excellent ion transport performance, it can provide high ion conductivity of the electrolyte, which is beneficial to the rapid transport of ions in the battery, thereby improving the performance and efficiency of the battery. Attached Figure Description

[0027] Figure 1 The image shows the morphology of the hybrid perovskite composite solid electrolyte in Example 1.

[0028] Figure 2 This is a comparison chart of the crystallinity of the hybrid perovskite composite solid electrolyte material obtained in Example 1 and the pure PEO polymer solid electrolyte.

[0029] Figure 3 This is a comparison chart of the ionic conductivity of the hybrid perovskite composite solid electrolyte obtained in Example 1 under different feed masses of hybrid perovskite materials;

[0030] Figure 4 This is a graph showing the ionic conductivity of the pure PEO polymer solid electrolyte without the addition of hybrid perovskite in Example 3. Detailed Implementation

[0031] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. The following embodiments are implemented based on the technical solution of the present invention, providing detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0032] In the following embodiments, unless otherwise specified, the raw materials, reagents or processing techniques are all conventional commercial products or conventional processing techniques in the art.

[0033] Example 1

[0034] This embodiment provides a method for preparing a hybrid perovskite composite solid electrolyte, including the following steps:

[0035] (1) Preparation of hybrid perovskite materials: 3g C 12 H 25 NH2 was added to 300 ml of 38 wt% hydrochloric acid and stirred at room temperature for 1 h to react fully. The mixture was then dried at 80 °C to obtain a white solid. 3 g of CoCl2·4H2O was dissolved in water and 100 ml of 38 wt% hydrochloric acid was added to dissolve it fully, resulting in a purple solution. The white solid obtained above was added to the purple solution and dissolved fully. 300 ml of 38 wt% hydrochloric acid was added and stirred at room temperature for 1 h to react fully. Finally, the mixture was dried at 70 °C for 15 hours to form a dense hybrid perovskite (PCP).

[0036] (2) Preparation of PEO mixed solution: Dissolve 600 mg of polyethylene oxide (PEO) with approximately 600,000 Mn in deionized water until homogeneous (PEO mass concentration is 6%), then add 80 mg of LiTFSI to the PEO solution and continue magnetic stirring for 20 h until homogeneous;

[0037] (3) Preparation of PEO-PCP composite electrolyte: 100 mg of the hybrid perovskite prepared in step (1) was dispersed in 5 ml of water and stirred evenly. This mixture was then added to the PEO solution and magnetically stirred at room temperature for 20 h. After sonication for 13 h (ultrasonic frequency 200 W), the mixture was dropped onto a mold and dried at 45 °C to obtain the hybrid perovskite composite solid electrolyte. The morphology of this hybrid perovskite composite solid electrolyte is shown in the figure below. Figure 1 As shown, the hybrid perovskite solid electrolyte appears as a uniformly dispersed, flat, and saturated blue film.

[0038] Example 2

[0039] This embodiment provides a method for preparing a hybrid perovskite composite solid electrolyte. The preparation process is basically the same as that in Example 1. The difference is that in this embodiment, the amount of hybrid perovskite added to the PEO mixed solution in step (3) is 20, 40, 60, 80 and 120 mg, respectively.

[0040] Example 3

[0041] This embodiment provides an application of a hybrid perovskite composite solid electrolyte. First, the crystallinity of the hybrid perovskite composite solid electrolyte material prepared in Example 1 is compared with that of a pure PEO polymer solid electrolyte without the addition of hybrid perovskite.

[0042] The pure PEO polymer solid electrolyte was prepared by using the same method as step (3) in Example 1, without the addition of hybrid perovskite.

[0043] The XRD patterns of the two are as follows Figure 2 As shown, the crystallinity of the solid electrolyte is significantly improved after the addition of hybrid perovskite, which can accelerate the dissociation of lithium salt and thus improve ionic conductivity.

[0044] The effect of varying the mass of hybrid perovskite material added to the PEO mixed solution on the battery's ionic conductivity was tested. Electrochemical impedance spectroscopy (EIS) was performed using an electrochemical workstation. A symmetrical battery was constructed based on a blocked electrode-electrolyte-blocked electrode configuration. The impedance spectrum of this battery was then measured using an EIS spectrometer. Analysis of the spectral data determined the total impedance contributed by the electrolyte itself. Finally, the lithium-ion conductivity of the sample was calculated based on the size of the electrolyte sample. The experimental results are as follows: Figure 3 As shown, the hybrid perovskite exhibits the highest ionic conductivity, reaching 3.12 x 10⁻⁶, when 100 mg of the mixture is added. -4 S / cm -1 Among them, the ionic conductivity of pure PEO polymer solid electrolyte without added hybrid perovskite is as follows: Figure 4 It is 4.4x10 -6 S / cm -1 This indicates that the addition of hybrid perovskite significantly improves the ionic conductivity of the solid electrolyte.

Claims

1. A method for preparing a hybrid perovskite composite solid electrolyte, characterized in that, Includes the following steps: A mixed solution of polyethylene oxide and lithium salt was mixed with a hybrid perovskite material and dried to obtain a hybrid perovskite composite solid electrolyte. The preparation method of the hybrid perovskite material includes: reacting organic raw materials with hydrochloric acid to obtain a first intermediate product; dissolving inorganic raw materials in water and adding hydrochloric acid to dissolve them to obtain a second intermediate product solution; dissolving the first intermediate product in the second intermediate product solution, adding hydrochloric acid to react, and then drying to obtain the hybrid perovskite material. The mass ratio of the hybrid perovskite material to polyethylene oxide is 1:5-30; The organic raw material is C 12 H 25 NH2, with CoCl2 as the inorganic raw material.

2. The method for preparing the hybrid perovskite composite solid electrolyte according to claim 1, characterized in that, The molecular weight of the polyethylene oxide is 100,000-600,000, and the mass ratio of polyethylene oxide to lithium salt is 10:1-1.

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3. The method for preparing the hybrid perovskite composite solid electrolyte according to claim 1, characterized in that, The drying temperature during the drying process to obtain the hybrid perovskite composite solid electrolyte is 40-50℃.

4. The method for preparing the hybrid perovskite composite solid electrolyte according to claim 1, characterized in that, During the drying process to obtain hybrid perovskite materials, the drying time is 12-15 hours and the temperature is 50-70℃.

5. The method for preparing the hybrid perovskite composite solid electrolyte according to claim 1, characterized in that, The mass ratio of the organic raw material to the inorganic raw material is 1:1 to 1:1.

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6. The method for preparing the hybrid perovskite composite solid electrolyte according to claim 1, characterized in that, When dissolving the first intermediate product in the solution of the second intermediate product and adding hydrochloric acid, the volume of hydrochloric acid added is 200-300 ml.

7. A hybrid perovskite composite solid electrolyte, characterized in that, It is prepared by the method described in any one of claims 1 to 6.

8. The application of the hybrid perovskite composite solid electrolyte as described in claim 7, characterized in that... This hybrid perovskite composite solid electrolyte is used in lithium-ion batteries or supercapacitors.

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