An anion-adsorbing composite solid-state electrolyte for a sodium-ion solid-state battery and a preparation method thereof
Anion-adsorption composite solid electrolyte with a three-dimensional inorganic ceramic fiber framework was prepared by electrospinning and calcination, which solved the problems of low ion transference number and poor long-cycle performance of composite solid electrolytes, and achieved high ionic conductivity and long-cycle stability.
Patent Information
- Application Number
- CN202211178489.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-09-26
- Publication Date
- 2025-12-09
- Estimated Expiration
- 2042-09-26
AI Technical Summary
Existing composite solid electrolytes have low ion transference numbers, exhibit significant electroplating stripping polarization, and have poor long-cycle performance.
An inorganic ceramic spun membrane was prepared by electrospinning and then calcined to form a three-dimensional inorganic ceramic fiber framework. Then, a mixed solution of polyethylene oxide and sodium salt was cast onto the framework to prepare an anion adsorption type composite solid electrolyte.
It improves ionic conductivity and ion transference number, reduces concentration polarization, and enhances the long-cycle stability of the battery. The ionic conductivity is 3.52×10-4~4.43×10-4S/cm, the ion transference number is 0.55~0.61, and the battery can maintain a capacity retention of 80.1%~89.2% after 1000~1500 cycles.
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Figure CN115621561B_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of ion batteries, in particular to an anion-adsorbing composite solid-state electrolyte for sodium ion solid-state batteries and a preparation method thereof. BACKGROUND
[0002] Most of the current commercial ion batteries use traditional liquid electrolytes, which have safety hazards because organic solvents are volatile, flammable and easy to leak. In contrast, solid-state batteries using all-solid-state electrolytes have a larger electrochemical stability window, good thermal stability, excellent mechanical properties, effectively solving the problems of electrolyte leakage, flammability and poor chemical stability, and improving safety. Sodium metal has a high theoretical specific capacity (1166 mAh g –1 ) and a low potential (relative to the standard hydrogen electrode, -2.71 V), and metal sodium has the advantages of abundant natural reserves and low cost. However, sodium ions have a larger ionic radius, making it more difficult to migrate and transport in electrolytes, and sodium metal anodes have higher chemical reactivity, which can cause adverse side effects when matched with traditional organic liquid electrolytes, leading to reduced battery performance. Therefore, the development of sodium ion solid-state electrolyte technology has very important strategic significance.
[0003] Composite solid-state electrolytes combine the advantages of organic polymer solid-state electrolytes and inorganic solid-state electrolytes by adding inorganic ceramics to polymer electrolytes, which can effectively inhibit polymer crystallization, promote the dissociation of alkali metal salts, and the mechanical strength and puncture resistance of inorganic ceramics can effectively inhibit the growth of dendrites during battery operation, thereby improving the cycle stability and coulombic efficiency of the battery. Most existing composite solid-state electrolyte technologies simply mechanically stir and mix inorganic ceramic particles and polymers without structural design, and the inorganic ceramic particles randomly distributed are very easy to agglomerate, which can block the continuous ion transport path and reduce the ionic conductivity. Inorganic ceramics have a significant impact on the ionic conductivity of composite solid-state electrolytes. To solve the problem of uniform dispersion of inorganic ceramic particles in composite solid-state electrolytes, on the one hand, the inorganic ceramic particles can be designed into one-dimensional nanowire structures to minimize particle connections and create longer continuous ion transport paths; on the other hand, the inorganic ceramic particles can be spun with the polymer matrix to form a continuous three-dimensional composite solid-state electrolyte. The above technologies successfully solve the dispersion problem of inorganic ceramic particles in composite solid-state electrolytes and improve the ionic conductivity, but such composite solid-state electrolytes still have problems such as low ion transference number, uneven ion deposition, large concentration difference, obvious plating stripping polarization, and poor long cycle performance.
[0004] Therefore, the prior art still needs to be improved and developed. SUMMARY
[0005] In view of the deficiencies of the prior art described above, the purpose of the present application is to provide an anion-adsorbing composite solid electrolyte for sodium ion solid-state batteries and a preparation method thereof, aiming to solve the problems of low ion transference number, obvious electroplating peeling polarization and poor long cycle performance of the existing composite solid electrolyte.
[0006] The technical scheme adopted by the present application to solve the above technical problems is as follows:
[0007] A preparation method of an anion-adsorbing composite solid electrolyte for sodium ion solid-state batteries, comprising the following steps:
[0008] An inorganic ceramic spinning film is prepared by electrospinning method;
[0009] The inorganic ceramic spinning film is calcined to obtain a three-dimensional inorganic ceramic fiber framework;
[0010] Polyethylene oxide and sodium salt are mixed in a solvent to obtain a first solution;
[0011] The first solution is cast onto the three-dimensional inorganic ceramic fiber framework and dried to obtain the anion-adsorbing composite solid electrolyte for sodium ion solid-state batteries.
[0012] The preparation method of the anion-adsorbing composite solid electrolyte for sodium ion solid-state batteries, wherein the inorganic ceramic is Na3Zr2Si2PO 12 The step of preparing the inorganic ceramic spinning film by electrospinning method specifically comprises:
[0013] Tetraethyl orthosilicate and zirconium acetate are dissolved in anhydrous ethanol and stirred to obtain a second solution;
[0014] Anhydrous sodium acetate and ammonium dihydrogen phosphate are dissolved in water to obtain a third solution;
[0015] The second solution and the third solution are mixed and polyvinylpyrrolidone is added and stirred to obtain a homogeneous slurry;
[0016] The homogeneous slurry is electrospun by an electrospinning device, and the inorganic ceramic spinning film is collected.
[0017] The preparation method of the anion-adsorbing composite solid electrolyte for sodium ion solid-state batteries, wherein the molar ratio of tetraethyl orthosilicate to zirconium acetate is 1:1.
[0018] The preparation method of the anion-adsorbing composite solid electrolyte for sodium ion solid-state batteries, wherein the addition amount of polyvinylpyrrolidone is 14% of the volume sum of the water and the anhydrous ethanol.
[0019] The preparation method of the anion-adsorbing type composite solid electrolyte for sodium ion solid-state batteries, wherein the electrostatic spinning parameters are: an injector with a needle hole diameter of 0.5 mm is used, the distance between the needle of the injector and the collector is 10-15 cm, the spinning voltage is 20-23 kV, the push slurry speed is 1-2 mL / h, the spinning temperature is 35-39 DEG C, and the humidity of the electrostatic spinning device is 38-42%.
[0020] The preparation method of the anion-adsorbing type composite solid electrolyte for sodium ion solid-state batteries, wherein the calcination treatment is specifically: the inorganic ceramic spinning film is calcined at 500 DEG C for 5 h, then heated to 900 DEG C at a heating rate of 1 DEG C / min and calcined for 12 h.
[0021] The preparation method of the anion-adsorbing type composite solid electrolyte for sodium ion solid-state batteries, wherein the sodium salt is NaClO4, and the solvent is acetonitrile.
[0022] The preparation method of the anion-adsorbing type composite solid electrolyte for sodium ion solid-state batteries, wherein the molar ratio of ethylene oxide to sodium ions in the first solution is 8:1.
[0023] The preparation method of the anion-adsorbing type composite solid electrolyte for sodium ion solid-state batteries, wherein the temperature of the drying treatment is 55-65 DEG C.
[0024] An anion-adsorbing type composite solid electrolyte for sodium ion solid-state batteries, wherein the method described in the above scheme of the application is used.
[0025] Beneficial effects: The application discloses an anion-adsorbing type composite solid electrolyte for sodium ion solid-state batteries and a preparation method thereof, the sodium ion solid-state battery anion-adsorbing type composite solid electrolyte is prepared by using an electrostatic spinning and calcination process and a hot percolation method, in the electrolyte, three-dimensional inorganic ceramic fiber framework gaps are completely filled with polymer slurry, anions are effectively adsorbed on the inorganic ceramic fiber network, a high content of inorganic ceramic framework provides more contact area to fix anions, can provide a continuous ion transmission path, improves the ion conductivity and ion transference number of the solid electrolyte, reduces the concentration difference polarization phenomenon caused by the low ion transference number, successfully solves the problems of poor long cycle performance and gradually increasing plating stripping polarization of the sodium ion composite solid electrolyte, and improves the long cycle stability of the battery. -4 ~4.43*10 -4The sodium ion solid-state battery has high ion conductivity of 0.1 S / cm and high ion transference number of 0.55-0.61, can maintain polarization stability for more than 1000 hours, can maintain long cycle for 1000-1500 cycles or more in the charge-discharge cycle test, and has a capacity retention rate of 80.1%-89.2%. BRIEF DESCRIPTION OF DRAWINGS
[0026] Figure 1 The flow chart of the preferred embodiment of the preparation method of the anion adsorption type composite solid electrolyte for the sodium ion solid-state battery provided in the embodiment of the present application.
[0027] Figure 2 The SEM diagram of the NZSP ceramic framework in the embodiment of the present application.
[0028] Figure 3 The ion transference number diagram of the anion adsorption type 3D NZSP / PEO composite solid electrolyte in the embodiment of the present application.
[0029] Figure 4 The ion conductivity diagram of the anion adsorption type 3D NZSP / PEO composite solid electrolyte in the embodiment of the present application.
[0030] Figure 5 The ClO 4- adsorption energy diagram of the 3D NZSP surface in the embodiment of the present application.
[0031] Figure 6 The polarization diagram of the sodium symmetric battery matched with the anion adsorption type 3D NZSP / PEO composite solid electrolyte in the embodiment of the present application.
[0032] Figure 7 The long cycle diagram of the battery matched with the anion adsorption type 3D NZSP / PEO composite solid electrolyte in the embodiment of the present application. DETAILED DESCRIPTION
[0033] The present application provides an anion adsorption type composite solid electrolyte for a sodium ion solid-state battery and a preparation method thereof. To make the purpose, technical scheme and effects of the present application more clear and explicit, the present application is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present application and not to limit the present application.
[0034] In the description of the present application, it should be understood that the terms "center", "longitudinal", "transverse", "length", "width", "thickness", "upper", "lower", "front", "rear" and the like indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation of the present application.
[0035] Furthermore, the terms "first", "second", etc. are used herein for descriptive purposes only and should not be construed as indicating or implying relative importance or a quantity of indicated technical features. Thus, features defined with "first", "second" can explicitly or implicitly include one or more of the features. Those skilled in the art can understand that, unless otherwise defined, all terms (including technical terms and scientific terms) used herein have the same meaning as that generally understood by those skilled in the art to which the present application belongs. It should also be understood that terms such as those defined in a general dictionary should be understood as having meanings consistent with those in the context of the prior art, and should not be interpreted in an idealized or overly formal sense unless specifically defined as such herein.
[0036] Inorganic ceramic has a significant impact on the ionic conductivity of composite solid electrolyte. In order to solve the technical problem of uniform dispersion of inorganic ceramic microparticles in composite solid electrolyte, on the one hand, the inorganic ceramic microparticles can be designed into one-dimensional nanowire structure to minimize the connection between particles and create a longer continuous ion transport path; on the other hand, the inorganic ceramic microparticles are spun with the polymer matrix to form a continuous three-dimensional composite solid electrolyte. The above technology successfully solves the dispersion problem of inorganic ceramic microparticles in composite solid electrolyte and improves the ionic conductivity, but such composite solid electrolyte still has the problems of low ion transference number, uneven ion deposition, large concentration difference, obvious electroplating peeling polarization phenomenon and poor long cycle performance.
[0037] Based on this, the present application provides a preparation method of an anion adsorption type composite solid electrolyte for a sodium ion solid-state battery, referring to Figure 1 which comprises the steps of:
[0038] S10, preparing an inorganic ceramic spinning film by electrospinning method;
[0039] S20, calcining the inorganic ceramic spinning film to obtain a three-dimensional inorganic ceramic fiber framework;
[0040] S30, mixing polyethylene oxide and sodium salt in a solvent to obtain a first solution;
[0041] S40, casting the first solution onto the three-dimensional inorganic ceramic fiber framework and performing drying treatment to obtain the anion adsorption type composite solid electrolyte for the sodium ion solid-state battery.
[0042] Specifically, the application adopts an electrostatic spinning and calcination process and a thermal infiltration method to prepare an anion-adsorbing composite solid electrolyte for a sodium ion solid-state battery, in which a three-dimensional inorganic ceramic fiber framework gap is completely filled with a polymer slurry, anions are effectively adsorbed on the inorganic ceramic fiber network, a high content of inorganic ceramic framework provides more contact area to fix anions, can provide a continuous ion transmission path, improves the ion conductivity and ion transference number of the solid electrolyte, reduces the concentration polarization phenomenon caused by the low ion transference number, successfully solves the problems of poor long cycle performance and gradually increasing plating stripping polarization of the sodium ion composite solid electrolyte, and improves the long cycle stability of the battery. The novel electrolyte prepared by the method of the application shows a high ion conductivity of 3.52 x 10 -4 ~ 4.43 x 10 -4 S / cm and a high ion transference number of 0.55~0.61, can maintain a polarization stability of more than 1000 hours, can maintain more than 1000~1500 cycles in the charge and discharge cycle test, and has a capacity retention rate as high as 80.1%~89.2%.
[0043] In some embodiments, the inorganic ceramic is Na3Zr2Si2PO 12 (NZSP), the step of preparing an inorganic ceramic spinning film by electrostatic spinning method specifically includes:
[0044] S101, dissolving tetraethyl orthosilicate (C8H 20 O4Si) and zirconium acetate (C8H 12 O4Zr) in anhydrous ethanol, stirring to obtain a second solution;
[0045] S102, dissolving anhydrous sodium acetate (CH3COONa) and ammonium dihydrogen phosphate (NH4H2PO4) in water to obtain a third solution;
[0046] S103, mixing the second solution and the third solution and adding polyvinylpyrrolidone (PVP), stirring to obtain a homogeneous slurry;
[0047] S104, electrostatic spinning of the homogeneous slurry by using an electrostatic spinning device, and collecting the inorganic ceramic spinning film.
[0048] Specifically, the porous 3D inorganic ceramic framework (3DNZSP) structure prepared by adopting the electrostatic spinning method can make PEO well penetrate to form a composite solid electrolyte, and effectively solve the problems of uneven dispersion of existing technology ceramic particles, low ion conductivity and the like; the present application can prepare a porous 3D inorganic ceramic framework structure by adopting electrostatic spinning combined with a calcination process, the three-dimensional inorganic ceramic fiber framework is only suitable for a sodium ion solid-state battery, the structure can provide a continuous ion transmission path in the composite electrolyte on the one hand, and the 3D inorganic ceramic framework structure provides more anion ClO4 - The adsorption sites form anion adsorption type, so as to improve ion migration number and reduce polarization.
[0049] In some embodiments, the molar ratio of the tetraethyl orthosilicate to the zirconium acetate is 1:1.
[0050] In some embodiments, the addition amount of the polyvinylpyrrolidone is 10% to 14% of the volume sum of the water and the anhydrous ethanol, preferably, the molecular weight of the polyvinylpyrrolidone is 800000 to 1300000.
[0051] In some embodiments, the parameters of the electrostatic spinning are as follows: a syringe with a needle hole diameter of 0.5mm is adopted, the distance between the needle of the syringe and the collector is 10 to 15cm, the spinning voltage is 20 to 23kV, the pushing speed is 1 to 2mL / h, the spinning temperature is 35 to 39℃, and the humidity of the electrostatic spinning device is 38% to 42%.
[0052] In some embodiments, the calcination treatment is specifically as follows: the inorganic ceramic spinning film is calcined at 500℃ for 5h, then the temperature is increased to 900℃ at a temperature increasing rate of 1℃ / min and calcined for 12h.
[0053] Specifically, the segmented calcination can remove the solvent PVP in the inorganic ceramic spinning film in the first segment of calcination, and form the three-dimensional inorganic ceramic fiber framework in the second segment of calcination.
[0054] In some embodiments, the molecular weight of the polyethylene oxide is 500000 to 800000, the sodium salt is NaClO4, and the solvent is acetonitrile.
[0055] In some embodiments, in the first solution, the molar ratio of ethylene oxide to sodium ion is 8:1, and at this molar ratio, the content of the carrier Na ion in the electrolyte is higher.
[0056] In some embodiments, the temperature of the drying treatment is 55-65℃, at which temperature the PEO and sodium salt dissolved in acetonitrile completely infiltrate into the 3DNZSP framework with the flowability of the hot solution, and after the solvent is completely volatilized, a composite solid electrolyte in the form of 3DNZSP / PEO is formed.
[0057] The application also provides an anion-adsorbing composite solid electrolyte for a sodium-ion solid-state battery, which is prepared by the method described in the above scheme of the application.
[0058] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the drawings in the embodiments of the application. Obviously, the described embodiments are only some of the embodiments of the application, rather than all the embodiments of the application, and are only used to explain the application but not to limit the application. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative efforts fall within the protection scope of the application.
[0059] Embodiment 1
[0060] A preparation method of an anion-adsorbing composite solid electrolyte for a sodium-ion solid-state battery, comprising the steps of:
[0061] S101, dissolving 1198 μL of tetraethyl orthosilicate and 1284 μL of zirconium acetate in anhydrous ethanol, and magnetically stirring at room temperature for 1 h to obtain a homogeneous solution A;
[0062] S102, dissolving anhydrous sodium acetate and ammonium dihydrogen phosphate in water to obtain a solution B;
[0063] S103, mixing the homogeneous solution A and the solution B, stirring for 30 min, and then adding 14% of polyvinylpyrrolidone (PVP, Mw=1300000) relative to the solvent, continuously stirring overnight to obtain a white homogeneous slurry;
[0064] S104, electrospinning the homogeneous slurry by using an electrospinning device, pouring the white homogeneous solution into a syringe equipped with a 0.5 mm needle hole under a high voltage of 20-23 kV, wherein the distance between the needle and the collector is fixed at 15 cm, the slurry pushing speed is 1.5 mL / h, the rotation speed of the collector is kept at 100 rpm, the humidity of the electrospinning device is maintained at 40%, and the temperature is 37℃, and the NZSP spinning film is collected;
[0065] S20, calcining the NZSP spinning film at 500℃ for 5 h, and then increasing the temperature to 900℃ at a temperature increasing rate of 1℃ / min and calcining for 12 h to obtain a three-dimensional NZSP inorganic fiber framework;
[0066] S30, mixing polyethylene oxide (PEO, Mw=600000) with NaClO4 in acetonitrile to obtain a homogeneous solution of EO:Na + molar ratio of 8:1;
[0067] S40, casting the homogeneous solution onto the three-dimensional NZSP inorganic fiber framework and drying at 60°C to obtain the anion-adsorbed composite solid-state electrolyte for sodium ion solid-state batteries.
[0068] It has been confirmed by means of SEM and other means that the three-dimensional NZSP inorganic fiber framework has been successfully prepared by electrospinning, as shown in Figure 2 , which shows that the continuous structure of the three-dimensional inorganic fiber framework provides a continuous transmission path for sodium ions.
[0069] After confirming the feasibility of the 3D NZSP / PEO composite solid-state electrolyte, a model was established by means of Materialstudio software, and the AIMD method was used for calculation, followed by long-time dynamic simulation under the NVT system to analyze the characteristics and advantages of this 3D structure. In the calculation, a 3D NZSP / PEO / NaClO4 composite model was established, the structure was optimized by means of the OPLS force field, the polarization effect of anions and cations was corrected by means of the charge scaling factor of ions, and then the stable structure was obtained by means of the conjugate gradient algorithm and energy minimization method, followed by MD dynamic simulation. The results show that the diffusion rate of sodium ions is the largest (D interface = 9.341 x 10 -5 m 2 S -1 ) on the interface between the 3D NZSP skeleton and PEO, and the diffusion rate in the PEO polymer is the smallest (D PEO = 0.312 x 10 -5 m 2 S -1 ). In order to verify this anion-adsorbed structure, the adsorption energy of the anions in the model was calculated, as shown in Figure 5 , the adsorption energy (Eads): Eads = Ead / sub-Ead-Esub, wherein Ead / sub, Ead and Esub are the total energy of the optimized adsorbate / substrate system, the total energy of the adsorbate and clean substrate in the structure. Finally, the ionic conductivity of the composite electrolyte was calculated to be 4.43 x 10 -4 S / cm, and the ion transference number was 0.61. This high ionic conductivity and high ion transference number are due to the design of the anion-adsorbed 3D NZSP inorganic fiber framework.
[0070] The anion-adsorbed composite solid-state electrolyte for sodium ion solid-state batteries proposed in this embodiment has excellent performance, as shown inFigure 3 and Figure 4 The composite electrolyte has high ionic conductivity and high ion transference number, as shown in Figure 6 The sodium symmetric battery can maintain polarization stability for more than 1000 hours, as shown in Figure 7 The battery with the anion-adsorbing composite solid-state electrolyte can perform long cycle for 1500 cycles at a certain rate current, and the capacity retention rate is as high as 80.1%.
[0071] In summary, the application discloses an anion-adsorbing composite solid-state electrolyte for a sodium ion solid-state battery and a preparation method thereof, wherein the method comprises the following steps: preparing an inorganic ceramic spinning film by using an electrostatic spinning method; performing calcination treatment on the inorganic ceramic spinning film to obtain a three-dimensional inorganic ceramic fiber framework; mixing polyethylene oxide and a sodium salt in a solvent to obtain a first solution; and casting the first solution on the three-dimensional inorganic ceramic fiber framework and performing drying treatment to obtain the anion-adsorbing composite solid-state electrolyte for the sodium ion solid-state battery. The anion-adsorbing composite solid-state electrolyte is prepared by using an electrostatic spinning and calcination process and a thermal infiltration method. In the electrolyte, the three-dimensional inorganic ceramic fiber framework gap is completely filled with a polymer slurry, anions are effectively adsorbed on the inorganic ceramic fiber network, a high content of inorganic ceramic framework provides more contact area to fix anions, can provide a continuous ion transmission path, improves the ionic conductivity and ion transference number of the solid-state electrolyte, reduces the concentration polarization phenomenon caused by the low ion transference number, successfully solves the problems of poor long cycle performance and gradually increasing plating stripping polarization of the sodium ion composite solid-state electrolyte, and improves the long cycle stability of the battery. The novel electrolyte prepared by using the method of the application has a high ionic conductivity of 3.52*10 -4 ~4.43*10 -4 S / cm and a high ion transference number of 0.55~0.61, can maintain polarization stability for more than 1000 hours, can maintain long cycle for more than 1000~1500 cycles in the charge and discharge cycle test, and has a capacity retention rate as high as 80.1%~89.2%.
[0072] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the application, but not to limit them; although the application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that they can modify the technical solutions recorded in the foregoing examples, or make equivalent replacement for part of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the application.
Claims
1. A method for producing an anion-absorbing composite solid electrolyte for a sodium-ion solid-state battery, characterized by, The method comprises the steps of: preparing an inorganic ceramic spinning membrane by using an electrospinning method; performing calcination treatment on the inorganic ceramic spinning membrane to obtain a three-dimensional inorganic ceramic fiber framework; mixing polyethylene oxide and a sodium salt in a solvent to obtain a first solution; casting the first solution on the three-dimensional inorganic ceramic fiber framework and performing drying treatment to obtain an anion-adsorbing composite solid-state electrolyte for a sodium-ion solid-state battery; The inorganic ceramic is Na3Zr2Si2PO 12 The step of preparing the inorganic ceramic spinning membrane by the electrostatic spinning method specifically comprises: dissolving tetraethyl orthosilicate and zirconium acetate in anhydrous ethanol, stirring to obtain a second solution; dissolving anhydrous sodium acetate and ammonium dihydrogen phosphate in water to obtain a third solution; mixing the second solution and the third solution and adding polyvinylpyrrolidone, stirring to obtain a homogeneous slurry; performing electrospinning on the homogeneous slurry by using an electrospinning device to collect the inorganic ceramic spinning membrane; the addition amount of the polyvinylpyrrolidone is 14% of the volume sum of the water and the anhydrous ethanol; the parameters of the electrospinning are as follows: an injector with a needle hole diameter of 0.5 mm is used, the distance between the needle of the injector and the collector is 10-15 cm, the spinning voltage is 20-23 kV, the slurry pushing speed is 1-2 mL / h, the spinning temperature is 35-39 ℃, and the humidity of the electrospinning device is 38%-42%; the calcination treatment is specifically as follows: the inorganic ceramic spinning membrane is calcined at 500 ℃ for 5 h, then the temperature is increased to 900 ℃ at a temperature increasing rate of 1 ℃ / min and calcined for 12 h.
2. The preparation method of the anion-adsorbing type composite solid electrolyte for a sodium-ion solid-state battery according to claim 1, characterized by, the molar ratio of the tetraethyl orthosilicate to the zirconium acetate is 1:
1.
3. The preparation method of the anion-adsorbing type composite solid electrolyte for a sodium-ion solid-state battery according to claim 1, characterized by, the sodium salt is NaClO4, and the solvent is acetonitrile.
4. The preparation method of the anion-adsorbing composite solid-state electrolyte for a sodium-ion solid-state battery according to claim 1, characterized by, in the first solution, the molar ratio of the polyethylene oxide to the sodium ion is 8:
1.
5. The preparation method of the anion-adsorbing composite solid-state electrolyte for a sodium-ion solid-state battery according to claim 1, characterized by, the temperature of the drying treatment is 55-65 ℃.
6. An anion-adsorbing composite solid-state electrolyte for a sodium-ion solid-state battery, characterized by obtained by using the method according to any one of claims 1-5.