Preparation Method and Application of a Ceramic-Polymer Quasi-Solid-State Electrolyte Based on a Vertical Array

Abstract

Preparation method and application of a ceramic-polymer quasi-solid-state electrolyte based on a vertical array, which relates to a preparation method and application of a quasi-solid-state electrolyte. The purpose of the present invention is to solve the problem that the introduction of existing zero-dimensional or one-dimensional inorganic fillers has a poor effect on improving the ionic conductivity of composite electrolytes. The present invention provides a preparation method of a ceramic-polymer quasi-solid-state electrolyte based on a vertical array, embedding an LATP ceramic framework with vertical array channels into a poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) / lithium bis(fluorosulfonyl)imide matrix and applying it in a lithium metal battery; the LATP ceramic framework has a stable self-supporting structure and a high specific surface area, enhancing the contact area between LATP and P(VDF-TrFE-CFE) / LiFSI, and there is no ceramic agglomeration phenomenon, which can significantly increase the electrochemical performance of the electrolyte and can also greatly improve the conductivity of the composite electrolyte.

Description

Technical Field

[0001] The invention relates to a preparation method and application of a quasi-solid electrolyte. Background Art

[0002] Lithium-ion batteries play an increasingly important role in our daily lives. They not only power our portable devices, but also drive vehicles (such as electric vehicles and hybrid vehicles), and even serve as a temporary storage system for excess peak energy delivered by renewable energy sources (such as solar, wind, nuclear, and hydroelectric power). However, the energy density of commercial lithium-ion batteries is gradually approaching its theoretical limit (300Wh kg -1 ), as people's requirements for lithium battery life continue to increase, the low energy density of commonly used negative electrode material graphite has become increasingly prominent. At the same time, as the overall specific capacity of the battery increases, the battery activity becomes higher and higher, and the overall safety of lithium-ion batteries has received more and more attention. In order to further improve the energy density of the battery and reduce the overall safety risk of the battery, researchers have turned their attention to solid-state lithium metal batteries. Lithium metal has a high capacity of up to 3860mAh g -1 The theoretical specific capacity can replace the traditional graphite negative electrode (372mAh g -1 ) improves the energy density of the battery. In addition, replacing the organic liquid electrolyte with a solid electrolyte (SSE) can not only inhibit the dendrite growth and penetration of the lithium metal anode, but also eliminate the safety issues caused by leakage, vaporization, and combustion of the organic liquid electrolyte.

[0003] Nowadays, obtaining solid-state electrolytes with high lithium ion conductivity at room temperature has become a key issue in the development of all-solid-state batteries. To overcome the problem of low ionic conductivity of solid-state electrolytes, scholars are striving to develop new solid-state electrolytes with higher ionic conductivity. The solid-state electrolytes used in solid-state lithium batteries can be divided into three categories: inorganic solid-state electrolytes, organic polymer solid-state electrolytes, and composite solid electrolytes (CSEs).

[0004] The reasons why a single solid electrolyte system is difficult to be applied in practice are: inorganic solid electrolytes are brittle and have poor contact with electrodes, resulting in high interface impedance; polymer electrolytes have poor mechanical strength and low room temperature ionic conductivity (10 –5 ~10 –4(S / cm). Combining the excellent room-temperature ionic conductivity of rigid inorganic solid electrolytes and the good flexibility of flexible organic polymer electrolytes, the preparation of a rigid-flexible organic-inorganic composite electrolyte is considered a wise choice to solve the above problems. The most commonly used preparation method at present is to add zero-dimensional inorganic particles or one-dimensional inorganic fibers to the polymer. It is generally believed that the introduction of inorganic fillers reduces the crystallinity of the polymer to a certain extent, thereby increasing the conductivity of the polymer matrix. However, the contribution of the introduction of zero- or one-dimensional inorganic fillers to improving the conductivity of composite electrolytes is limited, because further increasing the content of inorganic fillers will cause the particles or fibers to tend to agglomerate, resulting in the conductivity of the composite electrolyte being difficult to further increase or even decrease. At the same time, the inorganic fillers are isolated by the polymer and cannot form a continuous and fast ion transport channel, which further limits the improvement of the conductivity of the composite electrolyte. Therefore, an inorganic filler that does not agglomerate and has a continuous ion transport channel is crucial for further improving the performance of solid electrolytes. Summary of the Invention

[0005] The object of the present invention is to solve the problem that the introduction of existing zero-dimensional or one-dimensional inorganic fillers has poor effect on improving the ionic conductivity of composite electrolytes, and to provide a preparation method and application of a ceramic-polymer quasi-solid electrolyte based on a vertical array.

[0006] A preparation method of a ceramic-polymer quasi-solid electrolyte based on a vertical array is specifically completed according to the following steps:

[0007] I. Preparation of a 3D LATP ceramic framework:

[0008] ①. Dissolve polyvinyl butyral in N,N-dimethylformamide, and stir magnetically until the polyvinyl butyral is completely dissolved. Then add Li 1.3 Al 0.3 Ti 1.7 (PO4)3, and continue to stir magnetically until a homogeneous solution is formed to obtain a mixed solution;

[0009] ②. Cast the mixed solution onto a dry and clean glass plate by vacuum defoaming and then use a scraper to scrape it into a film. Then transfer it to a deionized water bath for phase inversion for a period of time after standing in a fume hood to obtain an LATP-PVB film, and then transfer it to an oven for drying to obtain a dry LATP-PVB film;

[0010] ③. Cut the dry LATP-PVB film into discs and place it in an air atmosphere. First, heat it to 400°C to 450°C and calcine it at 400°C to 450°C for a period of time, then heat it to 850°C to 900°C and calcine it at 850°C to 900°C for a period of time, and then cool it to room temperature to obtain a 3D LATP ceramic framework;

[0011] II. Preparation of PI-LATP electrolyte:

[0012] ① Add P(VDF-TrFE-CFE) and LiFSI to DMF, and then stir magnetically for a period of time to obtain a uniform backfill solution.

[0013] ② Drop the backfill solution onto the surface of the 3D LATP ceramic framework, and then dry it under vacuum to obtain a ceramic-polymer quasi-solid-state electrolyte based on a vertical array.

[0014] A ceramic-polymer quasi-solid-state electrolyte based on a vertical array is used to assemble a lithium metal battery.

[0015] Principle of the present invention:

[0016] Three-dimensional structures have been increasingly widely used in lithium batteries. As an inorganic filler, due to its self-supporting structure, even when the proportion in the composite electrolyte exceeds 50 vol.%, the three-dimensional framework will not agglomerate.

[0017] The present invention prepares an organic-inorganic composite electrolyte by introducing an LATP framework as a mechanical support and a lithium-ion transport channel and combining it with a flexible polymer; the LATP framework is prepared by combining the phase inversion method and the sintering method to obtain a vertically connected pore structure with self-supporting properties and a high specific surface area; the existence of this structure optimizes the distribution of LATP particles in the polymer matrix, avoids the problem of ceramic powder agglomeration, then combines it with the polymer, and introduces a lithium salt to further reduce the crystallinity of the polymer; compared with 0D and 1D inorganic fillers, this quasi-solid-state electrolyte can further shorten the lithium-ion transport path, avoid side reactions between LATP and lithium metal, and has higher ionic conductivity and stable electrochemical performance.

[0018] Advantages of the present invention:

[0019] I. The present invention provides a preparation method of a ceramic-polymer quasi-solid-state electrolyte based on a vertical array, and Li with vertical array pores 1.3 Al 0.3 Ti 1.7(PO4)3(LATP) ceramic framework is embedded in a poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene / lithium bis(fluorosulfonyl)imide (P(VDF-TrFE-CFE) / LiFSI) matrix and applied in a lithium metal battery; the LATP ceramic framework has a stable self-supporting structure and a high specific surface area, enhancing the contact area between LATP and P(VDF-TrFE-CFE) / LiFSI, and there is no ceramic agglomeration phenomenon, which can significantly improve the electrochemical performance of the electrolyte; at the same time, the LATP ceramic framework can provide a vertically connected fast lithium-ion transport channel, greatly improving the conductivity of the composite electrolyte; in addition, the organic-inorganic composite electrolyte with a three-dimensional skeleton has good thermal stability and interfacial compatibility;

[0020] Second, the electrochemical performance of the vertically array-based ceramic-polymer quasi-solid electrolyte prepared in the present invention was tested. It has an ionic conductivity as high as 5.8×10 -4 S cm –1 , the lithium-ion transference number is 0.56, the electrochemical window is 4.7 V, and the assembled LiFePO4||CSE||Li full battery has an initial discharge specific capacity of 131 mAh g –1 at a rate of 1 C, and after 500 cycles, the capacity retention rate is still above 75%, indicating that the electrolyte material provided by the present invention has high cycle stability and service life. Description of the Drawings

[0021] Figure 1 are SEM images. In the figure, (a) is the surface magnified view of the 3D LATP ceramic framework prepared in Example 1, (b) is the low-magnification cross-sectional view of the 3D LATP ceramic framework prepared in Example 1, (c) is the high-magnification cross-sectional view of the 3D LATP ceramic framework prepared in Example 1, (d) is the surface magnified view of the PI-LATP electrolyte prepared in Example 1, (e) is the low-magnification cross-sectional view of the PI-LATP electrolyte prepared in Example 1, and (d) is the high-magnification cross-sectional view of the PI-LATP electrolyte prepared in Example 1;

[0022] Figure 2 is the ionic conductivity and lithium-ion transference number diagram of the PI-LATP electrolyte prepared in Example 1;

[0023] Figure 3 is the electrochemical stability window of the PI-LATP electrolyte prepared in Example 1;

[0024] Figure 4 is the limiting current density of the lithium symmetric battery assembled with the PI-LATP electrolyte prepared in Example 1;

[0025] Figure 5The lifespan of the lithium symmetric battery assembled with the PI-LATP electrolyte prepared in Example 1;

[0026] Figure 6 It is a cyclic performance curve graph of the LiFePO4||CSE||Li all-battery assembled with the PI-LATP electrolyte prepared in Example 1. Specific embodiments

[0027] Specific embodiment one: A preparation method of a ceramic-polymer quasi-solid electrolyte based on a vertical array is specifically completed according to the following steps:

[0028] I. Preparation of 3D LATP ceramic framework:

[0029] ①. Dissolve polyvinyl butyral in N,N-dimethylformamide, stir magnetically until polyvinyl butyral is completely dissolved, and then add Li 1.3 Al 0.3 Ti 1.7 (PO4)3, continue to stir magnetically until a homogeneous solution is formed to obtain a mixed solution;

[0030] ②. Cast the mixed solution onto a dry and clean glass plate by vacuum degassing and then use a scraper to scrape it into a film. Then, let it stand in a fume hood and transfer it to a deionized water bath for phase inversion for a period of time to obtain an LATP-PVB film, and then transfer it to an oven for drying to obtain a dry LATP-PVB film;

[0031] ③. Cut the dry LATP-PVB film into circular pieces and place them in an air atmosphere. First, heat it to 400 °C - 450 °C and calcine it at 400 °C - 450 °C for a period of time, then heat it to 850 °C - 900 °C and calcine it at 850 °C - 900 °C for a period of time, and then cool it to room temperature to obtain a 3D LATP ceramic framework;

[0032] II. Preparation of PI-LATP electrolyte:

[0033] ①. Add P(VDF-TrFE-CFE) and LiFSI to DMF, and then stir magnetically for a period of time to obtain a homogeneous backfill solution;

[0034] ②. Drop the backfill solution onto the surface of the 3D LATP ceramic framework and then dry it under vacuum to obtain a ceramic-polymer quasi-solid electrolyte based on a vertical array.

[0035] Specific embodiment two: The difference between this embodiment and specific embodiment one is that: in step I ①, the polyvinyl butyral, Li 1.3 Al 0.3 Ti 1.7(PO4)3 and N,N-dimethylformamide have a mass-volume ratio of (0.1 g to 0.2 g):(0.5 g to 1 g):(1 mL to 3 mL). Other steps are the same as those in the first specific implementation manner.

[0036] Specific implementation manner three: The difference between this implementation manner and one of the first or second specific implementation manners is that the vacuum degassing time described in step ①② is 20 min to 40 min. Other steps are the same as those in the first or second specific implementation manner.

[0037] Specific implementation manner four: The difference between this implementation manner and one of the first to third specific implementation manners is that in step ①②, a 1000 μm doctor blade is used to scrape it into a film, and then it is left to stand in a fume hood for 2 min to 3 min and then transferred to a deionized water bath for phase inversion for 1 h to 3 h. Other steps are the same as those in the first to third specific implementation manners.

[0038] Specific implementation manner five: The difference between this implementation manner and one of the first to fourth specific implementation manners is that in step ①②, the drying temperature of the LATP-PVB film is 40 °C to 60 °C, and the drying time is 12 h to 24 h. Other steps are the same as those in the first to fourth specific implementation manners.

[0039] Specific implementation manner six: The difference between this implementation manner and one of the first to fifth specific implementation manners is that the heating rate described in step ①③ is 2 °C / min to 5 °C / min; the cooling rate described in step ①③ is 2 °C / min to 5 °C / min. Other steps are the same as those in the first to fifth specific implementation manners.

[0040] Specific implementation manner seven: The difference between this implementation manner and one of the first to sixth specific implementation manners is that in step ①③, it is calcined at 400 °C to 450 °C for 1 h to 3 h; in step ①③, it is calcined at 850 °C to 900 °C for 5 h to 7 h. Other steps are the same as those in the first to sixth specific implementation manners.

[0041] Specific implementation manner eight: The difference between this implementation manner and one of the first to seventh specific implementation manners is that in step ①③, the dried LATP-PVB film is cut into circular pieces with a diameter of 16 mm; in step ②①, the mass-volume ratio of P(VDF-TrFE-CFE), LiFSI, and DMF is (0.2 g to 0.4 g):(0.1 g to 0.3 g):(2 mL to 4 mL); the magnetic stirring time described in step ②① is 10 h to 12 h. Other steps are the same as those in the first to seventh specific implementation manners.

[0042] Specific implementation manner nine: The difference between this implementation manner and one of the first to eighth specific implementation manners is that in step ②②, the volume ratio of the backfill solution to the surface area of the 3D LATP ceramic framework is (300 μL to 500 μL):(150 mm 2~300 mm 2 );The temperature of the vacuum drying described in Step ② is 50°C to 60°C, and the time of the vacuum drying is 10 h to 12 h. Other steps are the same as those in the first to eighth specific embodiments.

[0043] Specific Embodiment Ten: This embodiment is a ceramic-polymer quasi-solid electrolyte based on a vertical array for assembling a lithium metal battery.

[0044] The following examples are used to verify the beneficial effects of the present invention:

[0045] Example 1: A preparation method of a ceramic-polymer quasi-solid electrolyte based on a vertical array is specifically completed according to the following steps:

[0046] I. Preparation of a 3D LATP ceramic framework:

[0047] ①. Dissolve 0.2 g of polyvinyl butyral (PVB) in N,N-dimethylformamide (DMF), magnetically stir until the polyvinyl butyral is completely dissolved, and then add 1 g of Li 1.3 Al 0.3 Ti 1.7 (PO4)3 (LATP), continue magnetic stirring until a homogeneous solution is formed to obtain a mixed solution;

[0048] ②. After vacuum degassing the mixed solution for 20 min, cast the liquid onto a dry and clean glass plate by tape casting, then use a 1000-μm doctor blade to scrape it into a film, and then transfer it to a deionized water bath for phase inversion for 2 h after standing in a fume hood for 2 min to obtain a LATP-PVB film, and then transfer it to an oven at 55°C for drying for 15 h to obtain a dried LATP-PVB film;

[0049] ③. Cut the dried LATP-PVB film into circular pieces with a diameter of 16 mm, and place them in an air atmosphere. First, heat up to 400°C and calcine at ~400°C for 2 h, then heat up to 850°C and calcine at 850°C for 6 h, and then cool down to room temperature to obtain a 3D LATP ceramic framework;

[0050] The heating rate described in Step ①③ is 2°C / min;

[0051] The cooling rate described in Step ①③ is 2°C / min;

[0052] II. Preparation of a PI-LATP electrolyte:

[0053] ①. Add 0.3 g of P(VDF-TrFE-CFE) and 0.2 g of LiFSI to 3 mL of DMF, and then magnetically stir at 25°C for 12 h to obtain a homogeneous backfill solution;

[0054] ②. Drop 400 μL of the backfill solution onto the surface of the 3D LATP ceramic framework, and then vacuum dry it in a vacuum drying oven at 55 °C for 12 h to obtain a ceramic-polymer quasi-solid-state electrolyte (PI-LATP electrolyte) based on a vertical array.

[0055] Figure 1 is an SEM image. In the figure, (a) is a magnified view of the surface of the 3D LATP ceramic framework prepared in Example 1, (b) is a low-magnification cross-sectional view of the 3D LATP ceramic framework prepared in Example 1, (c) is a high-magnification cross-sectional view of the 3D LATP ceramic framework prepared in Example 1, (d) is a magnified view of the surface of the PI-LATP electrolyte prepared in Example 1, (e) is a low-magnification cross-sectional view of the PI-LATP electrolyte prepared in Example 1, and (f) is a high-magnification cross-sectional view of the PI-LATP electrolyte prepared in Example 1;

[0056] From Figure 1 (a) and (b) of, it can be seen that the surface of the sintered LATP ceramic framework is dense and has vertical finger-like voids inside; from Figure 1 (c) of, it can be known that the LATP particles are closely connected and there is no agglomeration phenomenon, and interconnected ceramic channels are formed. From Figure 1 (d), (e), and (f) of, it can be known that the polymer uniformly covers the surface layer of the LATP framework and there is no additional polymer coating.

[0057] Figure 2 is the ionic conductivity and lithium ion transference number diagram of the PI-LATP electrolyte prepared in Example 1;

[0058] From Figure 2 it can be known that at 25 °C, the ionic conductivity of PI-LATP is 5.8×10 –4 S cm –1 , and the lithium ion transference number is 0.56, indicating that the continuous LATP ceramic framework provides a fast migration path for lithium ions and promotes the dissociation of lithium salts.

[0059] The electrochemical stability window of the quasi-solid-state electrolyte was tested by linear sweep voltammetry, as shown in Figure 3 ;

[0060] Figure 3 is the electrochemical stability window of the PI-LATP electrolyte prepared in Example 1;

[0061] From Figure 3It can be known that the oxidation potential of PI-LATP is 4.7V, which can meet the working requirements of the cathode material of lithium batteries. At the same time, the PI-LATP electrolyte with a vertical continuous array does not show an obvious reduction peak at 0V, indicating that PI-LATP has good anti-reduction properties.

[0062] The lithium symmetric battery was assembled using the PI-LATP electrolyte prepared in Example 1, and the specific steps are as follows:

[0063] Lithium symmetric batteries were assembled with lithium foils with a diameter of 12 mm as electrodes on both sides of the PI-LATP electrolyte prepared in Example 1, and the battery assembly was carried out in a glove box filled with argon.

[0064] Figure 4 is the limiting current density of the lithium symmetric battery assembled with the PI-LATP electrolyte prepared in Example 1;

[0065] From Figure 4 It can be known that: due to the high ionic conductivity of PI-LATP and good internal filling, the quasi-solid-state electrolyte can also inhibit the growth of lithium dendrites at high current densities, and the limiting current density is 1.2 mA cm -2 .

[0066] At a current density of 0.1 mA cm –2 and a areal capacity of 0.1 mAh cm -2 , the lifespan of the lithium symmetric battery was tested, as shown in Figure 5 shown;

[0067] Figure 5 is the lifespan of the lithium symmetric battery assembled with the PI-LATP electrolyte prepared in Example 1;

[0068] From Figure 5 It can be known that: the lithium symmetric battery assembled with the PI-LATP electrolyte prepared in Example 1 has a lower overpotential, and when the battery operates for 800 h, the overpotential does not increase significantly. This indicates that there is good interfacial contact between the PI-LATP quasi-solid-state electrolyte and lithium metal, which can significantly improve the non-uniform deposition of lithium ions in the solid electrolyte.

[0069] The LiFePO4||CSE||Li all-battery assembled with the PI-LATP electrolyte prepared in Example 1 was completed according to the following steps:

[0070] Mix lithium iron phosphate, super conductive carbon black and polyvinylidene fluoride in a mass ratio of 80:10:10 to obtain the positive electrode; use a metallic lithium sheet with a diameter of 14 mm as the negative electrode, and assemble a quasi-solid-state lithium metal battery using the PI-LATP electrolyte prepared in Example 1. Drop 4 μL of lithium hexafluorophosphate electrolyte on each side of the PI-LATP electrolyte prepared in Example 1. The battery assembly is carried out in a glove box filled with argon to obtain the LiFePO4||CSE||Li full cell.

[0071] Figure 6 It is a cyclic performance curve graph of the LiFePO4||CSE||Li full cell assembled using the PI-LATP electrolyte prepared in Example 1.

[0072] Figure 6 It shows the cyclic performance of the quasi-solid-state battery at a rate of 1C. PI-LATP has a high discharge specific capacity of 131 mAh g –1 at a rate of 1C, and after 500 cycles, the discharge specific capacity is 99 mAh g -1 , the capacity retention rate is greater than 75%, and the charge-discharge efficiency is close to 100%. It shows that the quasi-solid-state electrolyte based on the LATP framework has excellent cyclic stability.

Claims

1. A preparation method of a ceramic-polymer quasi-solid electrolyte based on a vertical array, characterized in that The preparation method is specifically completed according to the following steps: I. Preparation of 3D LATP ceramic framework: ①. Dissolve polyvinyl butyral in N,N-dimethylformamide, and stir magnetically until polyvinyl butyral is completely dissolved. Then add Li 1.3 Al 0.3 Ti 1.7 (PO4)3, and continue to stir magnetically until a homogeneous solution is formed to obtain a mixed solution; ②. The mixed solution is deaerated under vacuum and then cast and flow-casted on a dry and clean glass plate. Then, it is scraped into a film using a doctor blade, and then left standing in a fume hood and transferred to a deionized water bath for phase inversion for a period of time to obtain an LATP-PVB film, which is then transferred to an oven for drying to obtain a dried LATP-PVB film; In step I②, a 1000 μm doctor blade is used to scrape it into a film, and then left standing in a fume hood for 2 min to 3 min and then transferred to a deionized water bath for phase inversion for 2 h; ③. The dried LATP-PVB film is cut into circular pieces and placed in an air atmosphere. First, it is heated to 400 °C to 450 °C and calcined at 400 °C to 450 °C for a period of time, then heated to 850 °C to 900 °C and calcined at 850 °C to 900 °C for a period of time, and then cooled to room temperature to obtain a 3D LATP ceramic framework; In step I③, it is calcined at 400 °C to 450 °C for 1 h to 3 h; in step I③, it is calcined at 850 °C to 900 °C for 5 h to 7 h; II. Preparation of PI-LATP electrolyte: ①. P(VDF-TrFE-CFE) and LiFSI are added to DMF, and then magnetically stirred for a period of time to obtain a uniform backfill solution; In step II①, the mass-volume ratio of P(VDF-TrFE-CFE), LiFSI, and DMF is (0.2 g to 0.4 g):(0.1 g to 0.3 g):(2 mL to 4 mL); ②. The backfill solution is dripped onto the surface of the 3D LATP ceramic framework and then vacuum dried to obtain a ceramic-polymer quasi-solid-state electrolyte based on a vertical array; The volume ratio of the backfill solution described in Step 2② to the surface area of the 3D LATP ceramic framework is (300 μL - 500 μL):(150 mm 2 - 300 mm 2 ).

2. The preparation method of a ceramic-polymer quasi-solid electrolyte based on a vertical array according to claim 1, characterized in that The polyvinyl butyral and Li described in Step 1① 1.3 Al 0.3 Ti 1.7 (PO4)3 and N,N-dimethylformamide have a mass-to-volume ratio of (0.1 g to 0.2 g):(0.5 g to 1 g):(1 mL to 3 mL).

3. The preparation method of a ceramic-polymer quasi-solid electrolyte based on a vertical array according to claim 1, wherein In step I②, the time for vacuum deaeration is 20 min to 40 min.

4. The preparation method of a ceramic-polymer quasi-solid electrolyte based on a vertical array according to claim 1, characterized in that In step I②, the drying temperature of the LATP-PVB film is 40 °C to 60 °C, and the drying time is 12 h to 24 h.

5. The preparation method of a ceramic-polymer quasi-solid electrolyte based on a vertical array according to claim 1, characterized in that In step I③, the heating rate is 2 °C / min to 5 °C / min; in step I③, the cooling rate is 2 °C / min to 5 °C / min.

6. The preparation method of a ceramic-polymer quasi-solid electrolyte based on a vertical array according to claim 1, wherein In step I③, the dried LATP-PVB film is cut into circular pieces with a diameter of 16 mm; in step II①, the time for magnetic stirring is 10 h to 12 h.

7. The preparation method of a ceramic-polymer quasi-solid electrolyte based on a vertical array according to claim 1, characterized in that In step II②, the vacuum drying temperature is 50 °C to 60 °C, and the vacuum drying time is 10 h to 12 h.

8. Application of a ceramic-polymer quasi-solid electrolyte based on a vertical array prepared by the preparation method according to claim 1, characterized in that A ceramic-polymer quasi-solid-state electrolyte based on a vertical array is used to assemble a lithium metal battery.

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