An llnof-based solid-state electrolyte and a method of preparing the same

Abstract

The application discloses a kind of LLNOF-based solid electrolyte, it includes first electrolyte layer, polymer interface layer and second electrolyte layer being sequentially stacked;The first electrolyte layer includes lithium lanthanum niobium oxyfluoride solid electrolyte, the lithium lanthanum niobium oxyfluoride includes Li, La, Nb, O and F element, and has pyrochlore type crystal structure;The second electrolyte layer includes halide solid electrolyte;The polymer interface layer includes polymer matrix and lithium salt, and the polymer interface layer is arranged between the first electrolyte layer and the second electrolyte layer.The LLNOF-based solid electrolyte of the application can not only realize good compatibility with lithium metal negative electrode, inhibit lithium dendrite breeding, but also can adapt to high-voltage positive electrode;With the help of polymer interface layer, the contact between heterogeneous electrolyte layers is improved, the interface impedance is reduced, the structural stability of composite electrolyte is improved, and better cycle and safety performance of all-solid-state battery is obtained.

Description

Technical Field

[0001] This invention relates to the technical field of solid electrolytes, and more particularly to an LLNOF-based solid electrolyte and its preparation method. Background Technology

[0002] All-solid-state lithium batteries, with their advantages of high energy density and high safety, have become the core development direction of next-generation energy storage batteries. The performance of solid electrolytes is the key to their commercialization process. Inorganic solid electrolytes have attracted much attention due to their high ionic conductivity and high mechanical strength, but a single component cannot simultaneously achieve the stability of the negative electrode and the high voltage resistance of the positive electrode.

[0003] Pyrochlore-type lithium lanthanum niobium fluoride oxide (LLNOF) ceramic electrolytes exhibit intrinsic stability against lithium metal anodes and effectively suppress lithium dendrite nucleation and growth. However, their interfacial compatibility is poor when in direct contact with high-voltage cathode materials (such as NCM811), easily inducing space charge layers and side reactions, leading to rapid capacity decay. Halide solid electrolytes possess a wide electrochemical window and excellent compatibility with high-voltage cathodes, but their own reduction stability is poor, making them difficult to directly match with lithium metal anodes.

[0004] If LLNOF is directly composited with halides to leverage their respective strengths, both being rigid solids, atomic-level close contact is difficult to achieve during cold pressing. Numerous voids at the interface are unavoidable, causing a sharp increase in ion transport impedance and leading to localized current density concentration, severely deteriorating battery cycle life and critical current density. Furthermore, halides have poor thermal stability, making it impossible to eliminate interface defects through high-temperature co-sintering. Therefore, achieving low-impedance, high-stability heterogeneous integration of LLNOF and halides is a pressing technical challenge in the field of all-solid-state electrolytes. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the present invention provides an LLNOF-based solid electrolyte, which aims to solve the material compatibility contradiction that pyrochlore-type LLNOF ceramics are stable for lithium metal anodes but are difficult to adapt to high-voltage cathodes, and halide solid electrolytes are resistant to high voltages but cannot be directly matched with lithium metal anodes. At the same time, it solves the problems of significantly increased ion transport impedance, aggravated interfacial side reactions and uneven lithium dendrite deposition caused by the large number of interfacial voids due to the inability to tightly bond the layers when the two are directly cold-pressed as rigid solid electrolytes.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: An LLNOF-based solid electrolyte comprises a first electrolyte layer, a polymer interface layer, and a second electrolyte layer stacked sequentially; the first electrolyte layer comprises a lithium lanthanum niobium fluoride oxide solid electrolyte, wherein the lithium lanthanum niobium fluoride oxide contains Li, La, Nb, O, and F elements and has a pyrochlore-type crystal structure; the second electrolyte layer comprises a halide solid electrolyte; the polymer interface layer comprises a polymer matrix and a lithium salt, and the polymer interface layer is disposed between the first electrolyte layer and the second electrolyte layer.

[0007] As a preferred technical solution, the chemical formula of the lithium lanthanum niobium fluoride solid electrolyte satisfies Li 2- x La （1+x） / 3 Nb₂O₆F, where 0 < x ≤ 0.5; preferably, the chemical formula of the lithium lanthanum niobium fluoride oxide is Li₂O₆F. 1.8 La 0.4 Nb2O6F.

[0008] As a preferred technical solution, the chemical formula of the halide solid electrolyte satisfies Li3MX6, where M is one or more of In, Y, Sc, Yb, and Er, and X is Cl and / or Br.

[0009] As a preferred technical solution, the polymer matrix is ​​one or more of the following: polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, and polycarbonate polymers.

[0010] As a preferred technical solution, the lithium salt is one or more of lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium hexafluorophosphate, and lithium perchlorate.

[0011] As a preferred technical solution, the thickness of the polymer interface layer is 0.5μm to 20μm; And / or, the thickness of the first electrolyte layer is 30 μm to 200 μm; And / or, the thickness of the second electrolyte layer is 5 μm to 100 μm.

[0012] Another aspect of the present invention is to provide a method for preparing an LLNOF-based solid electrolyte as described above, the method comprising the following steps: S1: A lithium-containing compound, a lanthanum-containing compound, a niobium-containing compound, and lithium fluoride are mixed, a dispersant and an alcohol solvent are added, and the mixture is wet-milled until homogeneous to obtain a mixture; the mixture is dried, shaped, and then sintered at high temperature to obtain a ceramic green body containing a first electrolyte layer; S2: A polymer interface layer is formed on the surface of the first electrolyte layer; S3: A second electrolyte layer is formed on the surface of the polymer interface layer opposite to the first electrolyte layer. The second electrolyte layer contains a halide solid electrolyte to obtain the LLNOF-based solid electrolyte.

[0013] As a preferred technical solution, the lithium-containing compound is at least one of lithium carbonate, lithium hydroxide, and lithium oxide; the lanthanum-containing compound is lanthanum oxide; and the niobium-containing compound is niobium pentoxide.

[0014] As a preferred technical solution, in step S2, the polymer interface layer is formed by dissolving the polymer matrix and lithium salt in an organic solvent to obtain a polymer slurry, coating the polymer slurry onto the surface of the first electrolyte layer, and drying it to obtain the polymer interface layer. Alternatively, a polymer interface layer can be formed on the surface of the first electrolyte layer by in-situ polymerization.

[0015] As a preferred technical solution, in step S3, the second electrolyte layer is formed by any of the following methods: (a) Disperse halide solid electrolyte powder in an aprotic solvent to obtain halide slurry, coat it on the surface of the polymer interface layer, and vacuum dry it at 50°C to 150°C; (b) The halide solid electrolyte powder is placed on the surface of the polymer interface layer and cold-pressed at 300MPa to 500MPa; (c) A halide solid electrolyte layer is precipitated in situ on the surface of the polymer interface layer by liquid-phase synthesis.

[0016] The beneficial effects of this invention are: This invention relates to an LLNOF-based solid-state electrolyte and its preparation method. By innovatively introducing a polymer interface layer composed of a polymer matrix and lithium salt between a pyrochlore-type lithium lanthanum niobium fluoride oxide first electrolyte layer (stabilizing the lithium metal anode) and a halide second electrolyte layer (stabilizing the high-voltage cathode), a three-layer composite structure is constructed, consisting of a first electrolyte layer, a polymer interface layer, and a second electrolyte layer stacked sequentially. This not only achieves a potential-matched design for lithium tolerance on the anode side and high-voltage tolerance on the cathode side, but also realizes a flexible interface transition between rigid inorganic electrolyte layers. This design not only enhances the overall structural stability and interlayer interface bonding of the composite solid-state electrolyte and significantly reduces interlayer interface impedance, but also maintains the excellent room-temperature ionic conductivity of the first electrolyte layer and the good interfacial compatibility between the second electrolyte layer and the high-voltage cathode active material. This helps to suppress lithium dendrite nucleation and penetration, inhibit interfacial side reactions during cycling, and improve the cycle life and safety performance of all-solid-state lithium batteries.

[0017] In summary, the LLNOF-based solid electrolyte of this invention not only possesses excellent ionic conductivity, chemical stability to lithium metal anodes, electrochemical stability to high-voltage cathodes, and interlayer interface compatibility, but also features a simple and highly controllable preparation method. Each layer can be sequentially composited under mild conditions without high-temperature co-sintering, thus meeting the comprehensive performance requirements of high-energy-density, long-life all-solid-state lithium batteries for solid electrolytes. It has broad prospects for industrial application in electric vehicles, consumer electronics, and large-scale energy storage. Detailed Implementation

[0018] The following description is intended to disclose the invention and enable those skilled in the art to implement it. The preferred embodiments described below are merely examples, and other obvious variations will occur to those skilled in the art.

[0019] Example 1 This embodiment of the LLNOF-based solid electrolyte includes a first electrolyte layer, a polymer interface layer, and a second electrolyte layer stacked sequentially. The first electrolyte layer comprises a lithium lanthanum niobium fluoride oxide solid electrolyte, wherein the lithium lanthanum niobium fluoride oxide contains Li, La, Nb, O, and F elements and has a pyrochlore-type crystal structure. The second electrolyte layer comprises a halide solid electrolyte. The polymer interface layer comprises a polymer matrix and a lithium salt, and is disposed between the first electrolyte layer and the second electrolyte layer. The chemical formula of the lithium lanthanum niobium fluoride oxide solid electrolyte is Li. 1.8 La 0.4 Nb₂O₆F (i.e., x=0.2); the halide solid electrolyte is Li₃InCl₆; the polymer matrix is ​​polyethylene oxide (PEO); the lithium salt is lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The thickness of the polymer interface layer is 10 μm, the thickness of the first electrolyte layer is 100 μm, and the thickness of the second electrolyte layer is 50 μm.

[0020] Another aspect of the present invention is to provide a method for preparing an LLNOF-based solid electrolyte as described above, the method comprising the following steps: S1: Weigh lithium carbonate (Li2CO3), lanthanum oxide (La2O3), niobium pentoxide (Nb2O5), and lithium fluoride (LiF) according to a molar ratio of 0.4:0.2:1:1.05. Add 5% excess lithium fluoride to compensate for fluorine loss during sintering. Mix the above raw materials and add 1.5% polyethylene glycol dispersant (by weight of the total powder) and an appropriate amount of anhydrous ethanol as a solvent. Place the mixture in a planetary ball mill and wet-mill at 500 r / min for 120 min. After milling, place the mixture in an 80℃ forced-air drying oven and dry for 6 h. The powder was then ground and passed through a 200-mesh sieve to obtain a mixture. The mixture was then placed into a stainless steel mold with a diameter of 20 mm and pressed into a ceramic green body under a pressure of 100 MPa for 5 min. The ceramic green body was then placed in a tube furnace and heated to 120 °C at a heating rate of 2 °C / min and held for 2 h to remove residual solvent and dispersant. The temperature was then increased to 1150 °C at a heating rate of 2 °C / min and held for 6 h for high-temperature sintering. After sintering, the ceramic green body was naturally cooled to room temperature with the furnace to obtain a ceramic green body containing a first electrolyte layer with a thickness of 100 μm.

[0021] S2: A polymer interface layer is formed on the surface of the first electrolyte layer. Specifically, polyethylene oxide (PEO, molecular weight 600,000) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) are dissolved in acetonitrile (AN) solvent at a molar ratio of 70:5 (i.e., the molar ratio of PEO repeating units to LiTFSI) to prepare a polymer slurry with a concentration of 8wt% (i.e., each 100g slurry contains 8g of polymer and lithium salt mixture). The polymer slurry is uniformly coated onto the upper surface of the first electrolyte layer using an automatic coating machine. The coating gap is set to 800μm and the coating rate is 20mm / min. After coating, the coating is immediately transferred to a vacuum drying oven and dried under vacuum at 60℃ for 24h to obtain a polymer interface layer with a thickness of 10μm.

[0022] S3: A second electrolyte layer is formed on the surface of the polymer interface layer opposite to the first electrolyte layer. The second electrolyte layer contains a halide solid electrolyte. Specifically, Li3InCl6 solid electrolyte powder (average particle size D50 = 2 μm) is dispersed in N-methylpyrrolidone, and 2% polyvinylidene fluoride binder is added. The mixture is stirred thoroughly to form a halide slurry with a solid content of 30 wt%. The halide slurry is uniformly coated onto the upper surface of the polymer interface layer using a scraper. The wet film thickness is controlled to be 200 μm. The mixture is then placed in a vacuum oven at 80°C and dried for 12 h to completely remove the solvent, resulting in a second electrolyte layer with a thickness of 50 μm, thereby obtaining the three-layer LLNOF-based solid electrolyte.

[0023] Example 2 The preparation method of the LLNOF-based solid electrolyte in this embodiment is basically the same as that in Example 1 in terms of raw material composition and preparation steps. The difference is that in the preparation method of this embodiment, the chemical formula of the lithium lanthanum niobium fluoride solid electrolyte is Li. 1.5 La 0.5 Nb₂O₆F (i.e., x=0.5); accordingly, lithium carbonate, lanthanum oxide, niobium pentoxide and lithium fluoride are weighed in a molar ratio of 0.25:0.25:1:1.05.

[0024] Example 3 The preparation method of the LLNOF-based solid electrolyte in this embodiment is basically the same as that in Example 1 in terms of raw material composition and preparation steps. The difference is that in the preparation method of this embodiment, the chemical formula of the lithium lanthanum niobium fluoride solid electrolyte is Li. 1.6 La 0.47 Nb₂O₆F (i.e., x=0.4); accordingly, lithium carbonate, lanthanum oxide, niobium pentoxide and lithium fluoride are weighed in a molar ratio of 0.3:0.23:1:1.05.

[0025] Example 4 The preparation method of the LLNOF-based solid electrolyte in this embodiment is basically the same as that in Example 1 in terms of raw material composition and preparation steps. The difference is that in the preparation method of this embodiment, the chemical formula of the lithium lanthanum niobium fluoride solid electrolyte is Li. 1.7 La 0.43 Nb₂O₆F (i.e., x=0.3); accordingly, lithium carbonate, lanthanum oxide, niobium pentoxide and lithium fluoride are weighed in a molar ratio of 0.35:0.22:1:1.05.

[0026] Example 5 The preparation method of the LLNOF-based solid electrolyte in this embodiment is basically the same as that in Example 1 in terms of raw material composition and preparation steps. The difference is that in the preparation method of this embodiment, the chemical formula of the lithium lanthanum niobium fluoride solid electrolyte is Li. 1.9 La 0.37 Nb₂O₆F (i.e., x=0.1); accordingly, lithium carbonate, lanthanum oxide, niobium pentoxide and lithium fluoride are weighed in a molar ratio of 0.45:0.18:1:1.05.

[0027] Example 6 The preparation method of the LLNOF-based solid electrolyte in this embodiment is basically the same as that in Example 1 in terms of raw material composition and preparation steps. The difference is that in the preparation method of this embodiment, the halide solid electrolyte is Li3YCl6 instead of Li3InCl6.

[0028] Example 7 The preparation method of the LLNOF-based solid electrolyte in this embodiment is basically the same as that in Example 1 in terms of raw material composition and preparation steps. The difference is that in the preparation method of this embodiment, the halide solid electrolyte is Li3ScCl6 instead of Li3InCl6.

[0029] Example 8 The preparation method of the LLNOF-based solid electrolyte in this embodiment is basically the same as that in Example 1 in terms of raw material composition and preparation steps. The difference is that in the preparation method of this embodiment, the halide solid electrolyte is Li3YbBr6 instead of Li3InCl6.

[0030] Example 9 The preparation method of the LLNOF-based solid electrolyte in this embodiment is basically the same as that in Example 1 in terms of raw material composition and preparation steps. The difference is that in the preparation method of this embodiment, the halide solid electrolyte is Li3ErBr6 instead of Li3InCl6.

[0031] Example 10 The preparation method of the LLNOF-based solid electrolyte in this embodiment is basically the same as that in Example 1 in terms of raw material composition and preparation steps. The difference is that in the preparation method of this embodiment, polyvinylidene fluoride is used instead of polyethylene oxide as the polymer matrix; and lithium bis(fluorosulfonyl)imide is used instead of lithium bis(trifluoromethanesulfonyl)imide as the lithium salt.

[0032] Comparative Example 1 The preparation method of the LLNOF-based solid electrolyte in this comparative example is basically the same as that in Example 1 in terms of raw material composition and preparation steps. The difference is that step S2 is omitted in the preparation method of this comparative example, that is, no polymer interface layer is set.

[0033] Comparative Example 2 The preparation method of the LLNOF-based solid electrolyte in this comparative example is basically the same as that in Example 1 in terms of raw material composition and preparation steps. The difference is that step S3 is omitted in the preparation method of this comparative example, that is, the second electrolyte layer containing halide solid electrolyte is not set.

[0034] The LLNOF-based solid electrolytes prepared in Examples 1-10 and Comparative Examples 1-2 were subjected to performance tests, and the performance results are shown in Table 1. The test method for room temperature ionic conductivity is as follows: gold electrodes are sputtered on the upper and lower surfaces of a solid electrolyte sheet as blocking electrodes to assemble a blocking battery system. The test is conducted using AC impedance spectroscopy in the frequency range of 1Hz to 1MHz and the amplitude of 10mV. The ionic conductivity is calculated based on the sum of the bulk resistance and grain boundary resistance in the Nyquist plot (i.e., the intersection of the semicircle in the high-frequency region and the real axis) and the formula σ=L / (R·S), where L is the thickness of the electrolyte sheet, S is the electrode area, and the test temperature is 25℃.

[0035] The interface impedance test method is as follows: the solid electrolyte sheet and the stainless steel blocking electrodes on both sides are assembled into a symmetrical blocking battery. The AC impedance spectroscopy method is used to test the interface impedance value under the conditions of frequency range of 1Hz to 1MHz and amplitude of 10mV. The interface impedance value is read from the diameter of the semicircle in the high-frequency region of the Nyquist diagram. This value reflects the total interface resistance between the solid electrolyte layers and between the electrolyte and the electrode. The test temperature is 25℃.

[0036] The critical current density (CCD) test method is as follows: Solid electrolyte sheets are assembled into a Li / electrolyte / Li symmetric battery, and the battery is charged and discharged at a constant current of 0.05 mA / cm². 2 The current density was gradually increased in step size, and constant current charging and discharging were performed for 30 minutes at each current density until the battery voltage dropped sharply (polarization voltage dropped sharply by more than 50mV) or a short circuit occurred. The maximum stable current density value before the short circuit occurred was recorded as the critical current density. The test temperature was 60℃.

[0037] The test method for 100-cycle capacity retention is as follows: A solid electrolyte sheet and an NCM811 positive electrode (containing active material NCM811, conductive agent SuperP, and binder PVDF, with a mass ratio of 80:10:10 and an areal loading of 3.5 mg / cm³) are used. 2 The lithium metal anode and lithium metal were assembled into an all-solid-state coin cell. After 3 weeks of formation at a 0.1C rate, it was subjected to 100 cycles of constant current charge and discharge at a 0.5C / 0.5C rate. The cycle cutoff voltage was 2.8V to 4.3V. The discharge capacity of the 100th cycle divided by the discharge capacity of the 1st cycle (excluding the formation cycle, taking the 0.5C cycle start cycle as the 1st cycle) is the 100-cycle capacity retention rate. The test temperature was 60℃.

[0038] Table 1

[0039] As shown in Table 1, the LLNOF-based solid electrolytes of Examples 1-10 all exhibited good overall electrochemical performance. Comparative Example 2, due to the omission of the halide second electrolyte layer, exhibited the highest room-temperature ionic conductivity (4.0 mS / cm) due to its shortest path, but lacking a high-voltage cathode protection layer, its cycle retention rate dropped sharply to 65.8% when matched with NCM811. Comparative Example 1, lacking a polymer interface layer, suffered from poor rigid interlayer contact, resulting in an interface impedance as high as 195 Ω·cm. 2 The CCD has an A / cm² speed of only 0.5 mA. 2 In contrast, although the three-layer composite structure of Example 1 has a slightly lower ionic conductivity (3.1 mS / cm) than Comparative Example 2 due to the series connection of halide layers, its interfacial impedance is reduced to 32 Ω·cm. 2 The CCD was improved to 2.0 mA / cm². 2 With a cycle retention rate as high as 93.6%, the overall electrochemical performance is significantly better than that of any single structure comparison, fully demonstrating the synergistic advantages of the present invention.

[0040] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.

Claims

1. An LLNOF-based solid electrolyte, characterized in that, The solid electrolyte comprises a first electrolyte layer, a polymer interface layer, and a second electrolyte layer stacked sequentially; the first electrolyte layer comprises a lithium lanthanum niobium fluoride oxide solid electrolyte, wherein the lithium lanthanum niobium fluoride oxide contains Li, La, Nb, O, and F elements and has a pyrochlore-type crystal structure; the second electrolyte layer comprises a halide solid electrolyte; the polymer interface layer comprises a polymer matrix and a lithium salt, and the polymer interface layer is disposed between the first electrolyte layer and the second electrolyte layer.

2. The LLNOF-based solid electrolyte as described in claim 1, characterized in that, The chemical formula of the lithium lanthanum niobium fluoride solid electrolyte satisfies Li 2-x La （1+x） / 3 Nb₂O₆F, where 0 < x ≤ 0.5; preferably, the chemical formula of the lithium lanthanum niobium fluoride oxide is Li₂O₆F. 1.8 La 0.4 Nb2O6F.

3. The LLNOF-based solid electrolyte as described in claim 1, characterized in that, The chemical formula of the halide solid electrolyte satisfies Li3MX6, where M is one or more of In, Y, Sc, Yb, and Er, and X is Cl and / or Br.

4. The LLNOF-based solid electrolyte as described in claim 1, characterized in that, The polymer matrix is ​​one or more of the following: polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, and polycarbonate polymers.

5. The LLNOF-based solid electrolyte as described in claim 1, characterized in that, The lithium salt is one or more of lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium hexafluorophosphate, and lithium perchlorate.

6. The LLNOF-based solid electrolyte as described in claim 1, characterized in that, The thickness of the polymer interface layer is 0.5 μm to 20 μm; And / or, the thickness of the first electrolyte layer is 30 μm to 200 μm; And / or, the thickness of the second electrolyte layer is 5 μm to 100 μm.

7. A method for preparing an LLNOF-based solid electrolyte as described in any one of claims 1-6, characterized in that, The preparation method includes the following steps: S1: A lithium-containing compound, a lanthanum-containing compound, a niobium-containing compound, and lithium fluoride are mixed, a dispersant and an alcohol solvent are added, and the mixture is wet-milled until homogeneous to obtain a mixture; the mixture is dried, shaped, and then sintered at high temperature to obtain a ceramic green body containing a first electrolyte layer; S2: A polymer interface layer is formed on the surface of the first electrolyte layer; S3: A second electrolyte layer is formed on the surface of the polymer interface layer opposite to the first electrolyte layer. The second electrolyte layer contains a halide solid electrolyte to obtain the LLNOF-based solid electrolyte.

8. The method for preparing the LLNOF-based solid electrolyte as described in claim 7, characterized in that, The lithium-containing compound is at least one of lithium carbonate, lithium hydroxide, and lithium oxide; the lanthanum-containing compound is lanthanum oxide; and the niobium-containing compound is niobium pentoxide.

9. The method for preparing the LLNOF-based solid electrolyte as described in claim 7, characterized in that, In step S2, the polymer interface layer is formed by dissolving the polymer matrix and lithium salt in an organic solvent to obtain a polymer slurry, coating the polymer slurry onto the surface of the first electrolyte layer, and drying it to obtain the polymer interface layer. Alternatively, a polymer interface layer can be formed on the surface of the first electrolyte layer by in-situ polymerization.

10. The method for preparing the LLNOF-based solid electrolyte as described in claim 7, characterized in that, In step S3, the second electrolyte layer is formed by any of the following methods: (a) Disperse halide solid electrolyte powder in an aprotic solvent to obtain halide slurry, coat it on the surface of the polymer interface layer, and vacuum dry it at 50°C to 150°C; (b) The halide solid electrolyte powder is placed on the surface of the polymer interface layer and cold-pressed at 300MPa to 500MPa; (c) A halide solid electrolyte layer is precipitated in situ on the surface of the polymer interface layer by liquid-phase synthesis.

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