Viscoplastic solid electrolyte material and preparation method and application thereof

Abstract

The invention discloses a viscoplastic solid electrolyte material and a preparation method and application thereof, the general formula of the viscoplastic solid electrolyte material is x (AX)-y (MX3)-z (BX2), xgt; 0, ygt; z is greater than or equal to 0, and the macroscopic form of the viscoplastic solid electrolyte material is non-powdery. The preparation method comprises the following steps: under the protection of inert gas, weighing raw materials according to a stoichiometric ratio, uniformly mixing, sealing, carrying out solid-phase reaction, and obtaining the viscoplastic solid electrolyte material after the solid-phase reaction is finished. The viscoplastic solid electrolyte material provided by the invention has high ionic conductivity and good machinability, and can form a compact electrolyte sheet with high ionic conductivity under low pressure. The material has viscoplasticity, can reduce the assembly pressure of an all-solid-state battery, and is helpful for improving the energy density of the battery.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of solid electrolyte, in particular to a visco-plastic solid electrolyte material, a preparation method and application thereof. BACKGROUND

[0002] Lithium ion batteries have been widely used in consumer electronics and electric vehicles, but the energy density bottleneck and safety hazards of liquid electrolyte are becoming key factors restricting its further development. Under this background, all-solid-state battery technology shows breakthrough potential: the use of inorganic solid electrolyte is expected to fundamentally solve the risk of thermal runaway, and its wide electrochemical window also supports the matching of high-voltage positive electrodes and high-capacity negative electrodes, which can increase the energy density to more than 500 Wh / kg. This technical breakthrough will promote the development of energy storage systems to be safer and higher in energy density, providing key support for large-scale application of new energy.

[0003] Solid electrolyte material is the key to the success of solid-state battery technology. However, the existing solid-state battery system generally faces the problem of physical contact of electrode / electrolyte interface, especially rigid inorganic solid electrolyte usually needs to apply external pressure of several tens to hundreds of MPa to maintain stable interface contact. Such high-pressure operating conditions not only require additional pressure devices, increasing system complexity and cost, but also more seriously restrict the energy density improvement space of the battery. Because the bulky pressure structure will significantly offset the theoretical advantage of solid-state batteries in energy density. Therefore, how to reduce the working pressure of the battery while ensuring good interface contact has become a key scientific problem that must be overcome to promote the commercialization of solid-state batteries.

[0004] The visco-plastic solid electrolyte developed in recent years provides a new idea to solve these bottlenecks. Its unique rheological properties can form a dense structure under lower pressure, not only significantly improving the interface contact and reducing the interface impedance, but also maintaining a high ionic conductivity (>10 -3 S / cm). More importantly, the self-adaptability of this material can effectively alleviate the stress accumulation during the cycle process, and is expected to reduce the working pressure of the battery to below 2 MPa, providing an important technical path for the practical application of solid-state batteries. However, the ionic conductivity and interface contact performance of the existing visco-plastic solid electrolyte are still difficult to meet the increasing demand of lithium ion batteries. SUMMARY

[0005] The present application provides a visco-plastic solid electrolyte material, a preparation method and application thereof to solve the problems of low ionic conductivity and poor interface contact of inorganic solid electrolyte in the prior art.

[0006] The first aspect of the present application provides a viscoplastic solid-state electrolyte material: the chemical general formula of the viscoplastic solid-state electrolyte material is x(AX)-y(MX3)-z(BX2); Wherein, A is at least one of Li, Na, K and Ag, M is Ga, B is at least one of Mg, Ca, Sr, Ba and Zn, X is at least one of F, Cl, Br and I, x>0, y>0 and z≥0, and the macroscopic form of the viscoplastic solid-state electrolyte material is non-powder.

[0007] Compared with the prior art, the viscoplastic solid-state electrolyte material prepared from the raw materials in the above-mentioned proportions has high ion conductivity, is non-powder in macroscopic form, has high viscoplasticity, is compatible with various positive electrode materials and forms good interface contact, promotes the rapid conduction of ions between interfaces, and overcomes the problems of the traditional inorganic solid-state electrolyte, i.e. high pressure is required to obtain high ion conductivity and poor interface contact.

[0008] In a possible implementation, the macroscopic form of the viscoplastic solid-state electrolyte material is clay-like. The clay-like means that the obtained solid-state electrolyte material is a kind of inorganic material with comprehensive physical properties such as plasticity, thixotropy and fine particle size.

[0009] In a possible implementation, the microstructure of the viscoplastic solid-state electrolyte material is crystalline phase, amorphous phase or coexistence of crystalline phase and amorphous phase. The variability of the microstructure is suitable for the solid-state electrolyte material of all component compositions.

[0010] The second aspect of the present application provides a preparation method of a viscoplastic solid-state electrolyte material, comprising the following steps: under the protection of inert gas, raw materials AX, MX3 and BX2 are weighed according to the stoichiometric ratio, mixed and sealed, and then solid-phase reaction is performed to obtain the viscoplastic solid-state electrolyte material.

[0011] In a possible implementation, the inert gas is one of helium, neon, argon and nitrogen, In a possible implementation, the sealing condition is that the oxygen content is less than 1 ppm and the water content is less than 1 ppm. Limiting the reaction conditions of the raw materials to the condition of complete sealing and air and water isolation can ensure that the macroscopic form of the obtained viscoplastic solid-state electrolyte material is non-powder.

[0012] In a possible implementation, the solid-phase reaction is performed in the form of ball milling, ball milling combined with heat treatment or sand milling.

[0013] In a possible implementation, the solid-phase reaction is performed by ball milling, the ball milling beads are made of zirconium oxide, the diameter of the ball milling beads is 0.1-50 mm, the ball-to-material ratio is (5-60):1, the ball milling time is 1-20 h, and the rotation speed is 100-600 rpm.

[0014] A third aspect of the present application provides a use of the viscoplastic solid-state electrolyte material in a solid-state battery, the solid-state battery comprising a positive electrode, a negative electrode, and an electrolyte interposed between the positive electrode and the negative electrode, at least one of the positive electrode, the negative electrode, and the electrolyte comprising the viscoplastic solid-state electrolyte material.

[0015] In a possible implementation, at least one of the positive electrode, the negative electrode, and the electrolyte further comprises an oxide solid-state electrolyte, a sulfide solid-state electrolyte, a halide solid-state electrolyte, a polymer electrolyte, or an electrolyte solution.

[0016] The present application has the following beneficial effects: (1) The viscoplastic solid-state electrolyte material obtained by the present application has a non-powder macroscopic morphology, high ionic conductivity, and high viscoplasticity, can be compatible with various positive electrode materials and form good interface contact, promotes the rapid conduction of ions between interfaces, and overcomes the problems of traditional inorganic solid-state electrolytes, i.e., high pressure is required to obtain high ionic conductivity and poor interface contact.

[0017] (2) The viscoplastic solid-state electrolyte material can be used to construct a low-voltage solid-state battery, which can greatly reduce the pressure during battery cycling and help develop low-voltage high-energy-density all-solid-state batteries.

[0018] (3) The viscoplastic solid-state electrolyte material has high ionic conductivity and viscoplasticity, and has a wide application prospect in solid-state batteries. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 FIG. 1 is an optical photograph of the viscoplastic solid-state electrolyte material prepared in Example 1 of the present application.

[0020] Figure 2 FIG. 2 is an XRD pattern of the viscoplastic solid-state electrolyte material prepared in Example 1 of the present application.

[0021] Figure 3 FIG. 3 is the first cycle charge-discharge curve of the solid-state battery prepared in Example 1 of the present application under a pressure of 2 MPa.

[0022] Figure 4 FIG. 4 is a long cycle graph of the solid-state battery prepared in Example 1 of the present application under a pressure of 2 MPa.

[0023] Figure 5 FIG. 5 is an XRD pattern of the viscoplastic solid-state electrolyte material prepared in Example 2 of the present application.

[0024] Figure 6 XRD pattern of the visco-plastic solid-state electrolyte material prepared in Example 3 of the present application.

[0025] Figure 7 XRD pattern of the visco-plastic solid-state electrolyte material prepared in Example 4 of the present application.

[0026] Figure 8 XRD pattern of the visco-plastic solid-state electrolyte material prepared in Example 5 of the present application.

[0027] Figure 9 Statistical diagram of the ion conductivity of the visco-plastic solid-state electrolyte materials prepared in Examples 1-5 of the present application. DETAILED DESCRIPTION

[0028] In order to make the above objectives, features and advantages of the present application more obvious and easy to understand, the specific embodiments of the present application are described in detail below. It should be noted that the following embodiments are only used to illustrate the implementation method and typical parameters of the present application, and are not used to limit the parameter range described in the present application, and the reasonable changes derived therefrom are still within the protection scope of the claims of the present application.

[0029] It should be noted that the endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The ranges and values should be interpreted as approximately between the stated values. For ranges, the endpoints are included between each respective range; the endpoints are included in the respective range or ranges; and each respective range is a continuation of the preceding range(s) and the succeeding range(s), if any. The same rule applies for the separate points.

[0030] Unless otherwise defined, all terms, symbols and other scientific terminology used herein are intended to have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. In some cases, terms with commonly understood meanings are defined herein for clarity and / or for ready reference, and the inclusion of such definitions herein should not necessarily be construed to mean that the terms are in any way being redefined in such definition in relation to common usage of such terms. The techniques described or referenced herein are generally well known in the art and are practiced in a conventional manner, as is appreciated by those skilled in the art. The kits and reagents, instruments of the present application are commercially available.

[0031] The present application is mainly directed to the lack of high ion conductivity, visco-plastic solid-state electrolyte in the prior art, and provides a kind of super ionic conductor-visco-plastic solid-state electrolyte material with the advantages of inorganic and organic solid-state electrolyte.The invention realizes the breakthrough of the comprehensive performance of solid-state electrolyte while improving processability, enhancing interface contact and maintaining high ion migration rate, and is suitable for high energy density solid-state energy storage devices.

[0032] The chemical general formula of the viscoplastic solid-state electrolyte material is x(AX)-y(MX3)-z(BX2); wherein, A is at least one of Li, Na, K, and Ag, M is Ga, B is at least one of Mg, Ca, Sr, Ba, and Zn, X is at least one of F, Cl, Br, and I, x>0, y>0, and z≥0. The macroscopic morphology of the viscoplastic solid-state electrolyte material is non-powder, and is preferably clay-like. The micro-morphology is a crystalline phase, an amorphous phase, or a coexistence of a crystalline phase and an amorphous phase.

[0033] The viscoplastic solid-state electrolyte material can be prepared by a ball milling method, a ball milling combined with heat treatment method, or a sand milling method, and has a wide application in solid-state batteries. The solid-state battery comprises: a positive electrode comprising positive electrode active material particles and electrolyte particles; a negative electrode comprising negative electrode active material particles and electrolyte particles; and an electrolyte layer interposed between the positive electrode and the negative electrode; wherein at least one of the positive electrode, the negative electrode, and the electrolyte layer comprises the viscoplastic solid-state electrolyte material obtained by the application.

[0034] The positive electrode active material refers to a material capable of absorbing and releasing metal ions, such as a layered metal oxide material, a polyanion material, a spinel material, a Prussian blue material, etc. The negative electrode active material refers to a material capable of absorbing and releasing metal ions, such as a metal material, a carbon material, a silicon material, a nitrogen material, etc. The metal material can be metal lithium or sodium, or an alloy such as a Li-In or Na-Sn alloy, etc.

[0035] To ensure the electrochemical cycle stability and ion conductivity, at least one of the positive electrode, the negative electrode, and the electrolyte layer of the solid-state battery can further contain another electrolyte material. The other electrolyte material is not required, and can be an oxide solid-state electrolyte, a sulfide solid-state electrolyte, a halide solid-state electrolyte, a polymer electrolyte, an electrolyte, etc.

[0036] The application will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0037] Embodiment 1

[0038] This embodiment provides a viscoplastic solid-state electrolyte material, and the general formula of the viscoplastic solid-state electrolyte material is LiCl-0.5GaF3-0.5CaCl2, wherein x=1, y=0.5, and z=0.5.

[0039] The preparation method of the viscoplastic solid-state electrolyte material comprises the following steps: The raw materials LiCl, GaF3 and CaCl2 are weighed in a glove box under argon protection in a molar ratio of 1:0.5:0.5, and the sealed environment of the glove box has a water content of less than 1 ppm and an oxygen content of less than 1 ppm, so as to effectively ensure the dryness of the solid-phase reaction.

[0040] The weighed raw materials are placed in a 100 ml zirconia ball mill jar under argon protection, the ball milling beads have a diameter of 5 mm, and the ball-to-material ratio is 20:1, then the ball mill jar is sealed and placed in a planetary high-energy ball mill, and the ball milling is carried out at a speed of 350 revolutions / minute for 5 hours. After the ball milling is completed, the obtained viscous plastic solid-state electrolyte material is obtained, Figure 1 It is an optical photograph of the obtained ball-milled product viscous plastic solid-state electrolyte material, and the photograph is taken in the glove box. The white strip or disc-shaped substance in the figure is the viscous plastic solid-state electrolyte material prepared in this embodiment, and the white substance can be pulled arbitrarily and can be restored under a small force.

[0041] The viscous plastic solid-state electrolyte sealed in an inert atmosphere is subjected to XRD testing by using a Cu target X-ray source, and the scanning range is 10-80° (2θ), and the X-ray diffraction pattern is obtained. The viscous plastic solid-state electrolyte sealed in an inert atmosphere is obtained by placing the obtained viscous plastic solid-state electrolyte material on a non-diffraction peak glass and flattening it in the glove box, and then sealing it with a Kapton film.

[0042] Figure 2 It is the XRD pattern of the viscous plastic solid-state electrolyte material prepared in embodiment 1, and it can be seen that the sample in this embodiment is a solid-state electrolyte material coexisting in amorphous phase-crystalline phase. The wide diffraction peak before 20° in the figure corresponds to the amorphous diffraction peak of the Kapton film.

[0043] In this embodiment, the prepared viscous plastic solid-state electrolyte material is assembled into a solid-state battery, and the ionic conductivity is tested. The viscous plastic solid-state electrolyte material of embodiment 1 is loaded into a general mold battery in the glove box, and a pressure of 10 MPa is applied to obtain a solid electrolyte sheet. The electrochemical impedance spectrum of the battery is tested, and the ionic conductivity of the viscous plastic solid-state electrolyte at 25°C is 24.84 mS cm -1 , as shown in Figure 9 .

[0044] The electrochemical cycle performance of the viscous plastic solid-state electrolyte material of embodiment 1 after being assembled into a solid-state battery is tested. First, Li 2.4 YCl 5.4 powder 40 mg is weighed in the glove box, loaded into a general mold battery, and manually flattened. Then 40 mg of Li3InCl6 is placed on the above-mentioned electrolyte sheet and a pressure of 2 t is applied to obtain a solid electrolyte sheet Li 2.4 YCl5.4 / Li3InCl6.

[0045] Secondly, LiFePO4, the plastic-viscous solid-state electrolyte material with the component of LiCl-0.5GaF3-0.5CaCl2 and CNT are mixed and ground in a molar ratio of 5:4.5:0.5, 8 mg of the ground product is taken as the positive electrode layer material, placed on the Li3InCl6 side of the solid electrolyte sheet, and 3t pressure is applied. Finally, Li-In alloy is placed on the Li3InCl6 side of the solid electrolyte sheet of the solid-state battery, and 2t pressure is applied. The stacking pressure of the battery is set to 2MPa to complete the assembly of the solid-state battery, and the first cycle charge-discharge curve of the solid-state battery is tested at 0.1C and 25℃. 2.4 YCl 5.4 The side, and 2t pressure is applied. Finally, the stacking pressure of the battery is set to 2MPa to complete the assembly of the solid-state battery, and the first cycle charge-discharge curve of the solid-state battery is tested at 0.1C and 25℃.

[0046] The results are as follows Figure 3 The first cycle charge-discharge curve of the solid-state battery obtained in Example 1 at 25℃, the charge-discharge voltage window is 2.1-3.8V(vs. Li+ / Li), it can be seen that under the condition of 0.1C, the charge specific capacity of the obtained solid-state battery is 172.3mAh / g, the discharge specific capacity is 152.8 mAh / g, and the first cycle coulombic efficiency is 88.67%. As shown in Figure 2, the charge-discharge curve of the solid-state battery obtained in Example 1 at 25℃, the charge-discharge voltage window is 2.1-3.8V(vs. Li+ / Li), it can be seen that under the condition of 0.1C, the charge specific capacity of the obtained solid-state battery is 172.3mAh / g, the discharge specific capacity is 152.8 mAh / g, and the first cycle coulombic efficiency is 88.67%. Figure 4 The long cycle curve of the solid-state battery at 2MPa pressure shows that after 100 cycles at 0.5C, the capacity retention rate is 78.25% and the capacity is 110.9 mAh / g. It shows that the plastic-viscous solid-state electrolyte has good application effect in the solid-state battery.

[0047] Example 2

[0048] The plastic-viscous solid-state electrolyte material provided in the embodiment has a general formula of 0.5LiCl-0.5GaF3-0.5CaCl2, wherein x=0.5, y=0.5, and z=0.5.

[0049] The preparation method of the plastic-viscous solid-state electrolyte material includes the following steps: Under helium protection, LiCl, GaF3 and CaCl2 raw materials are weighed in a molar ratio of 0.5:0.5:0.5 in a glove box, the sealed environment of the glove box is less than 1ppm in water content and less than 1ppm in oxygen content, so as to effectively ensure the dryness during ball milling. Under helium protection, the weighed raw materials are placed in a 100ml zirconia ball mill jar, the ball milling beads have a diameter of 2mm, and the ball-to-material ratio is 60:1. The sealed ball mill jar is placed in a planetary high-energy ball mill, and ball milling is carried out at a speed of 450r / min for 3 hours. The plastic-viscous solid-state electrolyte material is obtained after ball milling.

[0050] The Cu target X-ray source is used to test the XRD of the viscous plastic solid electrolyte material sealed in inert atmosphere, the scanning range is 10-80° (2θ), and the X-ray diffraction pattern is obtained as shown in Figure 5 It can be seen from the figure that the prepared viscous plastic solid electrolyte material has no obvious diffraction peak except the diffraction peak of part of LiCl raw material, which indicates that the microstructure of the viscous plastic solid electrolyte material is mainly amorphous.

[0051] The viscous plastic solid electrolyte material synthesized is assembled into a solid-state battery. The viscous plastic solid electrolyte material of the embodiment is loaded into a general mold battery inside the glove box, and a solid electrolyte sheet is obtained by applying a pressure of 10 MPa. The electrochemical impedance spectrum of the battery is tested, and the ionic conductivity of the viscous plastic solid electrolyte material at 25°C is 20.93 mScm -1 , as shown in Figure 9 .

[0052] Example 3

[0053] The embodiment provides a viscous plastic solid electrolyte material, the general formula of the viscous plastic solid electrolyte material is LiCl-0.5GaF3-0.5MgCl2, at this time x=1, y=0.5, and z=0.5.

[0054] The preparation method of the viscous plastic solid electrolyte material comprises the following steps. Under helium protection, LiCl, GaF3 and MgCl2 raw materials are weighed in a glove box in a molar ratio of 1:0.5:0.5. The sealing environment of the glove box is less than 1 ppm in water content and less than 1 ppm in oxygen content, so as to effectively ensure the dryness during ball milling. The weighed raw materials are placed in a 100 mL zirconia ball milling tank, the ball milling beads have a diameter of 3 mm, and the ball-to-material ratio is 40:1. The sealed ball milling tank is placed in a planetary high-energy ball mill, and ball milling is performed at a speed of 400 revolutions / minute for 9 hours. After ball milling, the viscous plastic solid electrolyte material is obtained.

[0055] The Cu target X-ray source is used to test the XRD of the viscous plastic solid electrolyte material sealed in inert atmosphere, the scanning range is 10-80° (2θ), and the X-ray diffraction pattern is obtained as shown in Figure 6 It can be seen from the figure that the prepared viscous plastic solid electrolyte material has no obvious diffraction peak except the diffraction peak of part of LiCl raw material, which indicates that the microstructure of the viscous plastic solid electrolyte material is mainly amorphous.

[0056] The viscous plastic solid electrolyte material synthesized is assembled into a solid-state battery. The viscous plastic solid electrolyte material of the embodiment is loaded into a general mold battery inside the glove box, and a solid electrolyte sheet is obtained by applying a pressure of 10 MPa. The electrochemical impedance spectrum of the battery is tested, and the ionic conductivity of the viscous plastic solid electrolyte material at 25°C is 20.93 mScm-1 As shown in Figure 9

[0057] Example 4

[0058] The present embodiment provides a viscoplastic solid-state electrolyte material, the general formula of which is LiCl-0.5GaF3-0.5SrCl2, where x = 1, y = 0.5, and z = 0.5.

[0059] The preparation method of the viscoplastic solid-state electrolyte material includes the following steps: Under argon protection, LiCl, GaF3, and SrCl2raw materials are weighed in a glove box in a molar ratio of 1:0.5:0.5, the sealed environment of the glove box has a water content of less than 1 ppm and an oxygen content of less than 1 ppm, so as to effectively ensure dryness during ball milling. The weighed raw materials are placed in a 100 mL zirconia ball milling tank under an argon atmosphere, the ball milling beads have a diameter of 2 mm, and the ball-to-material ratio is 30:1. The sealed ball milling tank is placed in a planetary high-energy ball mill, and ball milling is carried out at a speed of 500 revolutions per minute for 12 hours. After ball milling, the viscoplastic solid-state electrolyte material is obtained.

[0060] The synthesized viscoplastic solid-state electrolyte material is subjected to X-ray diffraction testing, the viscoplastic solid-state electrolyte material is sealed in an inert atmosphere, and the X-ray diffraction pattern of the viscoplastic solid-state electrolyte material is tested under a Cu target X-ray source at 10°-80°, as shown in Figure 7 The microstructure of the obtained viscoplastic solid-state electrolyte material is mainly crystalline.

[0061] The synthesized viscoplastic solid-state electrolyte material is assembled into a solid-state battery, the viscoplastic solid-state electrolyte material of the present embodiment is loaded into a general mold battery inside a glove box, and a pressure of 10 MPa is applied to obtain a solid electrolyte sheet. The electrochemical impedance spectrum of the battery is tested, and the ionic conductivity of the viscoplastic solid-state electrolyte material at 25°C is 33.21 mS cm -1 As shown in Figure 9

[0062] Example 5

[0063] The present embodiment provides a viscoplastic solid-state electrolyte material, the general formula of which is LiCl-0.5GaF3-0.5BaCl2, where x = 1, y = 0.5, and z = 0.5.

[0064] The preparation method of the viscoplastic solid-state electrolyte material includes the following steps: ​​The LiCl, GaF3 and BaCl2 raw materials are weighed in a glove box in a molar ratio of 1:0.5:0.5 under neon protection, the sealing environment of the glove box is less than 1 ppm in water content and less than 1 ppm in oxygen content, so as to effectively ensure dryness during ball milling. The weighed raw materials are sealed in a 100 mL zirconia ball milling tank under a neon atmosphere, the ball milling beads have a diameter of 3 mm, and the ball-to-material ratio is 30:1. The sealed ball milling tank is placed in a planetary high-energy ball mill, and ball milling is performed at a speed of 550 revolutions / minute for 4 hours. The plastic-viscous solid electrolyte material is obtained after ball milling.

[0065] The obtained plastic-viscous solid electrolyte material is subjected to X-ray diffraction test, the solid electrolyte is sealed under inert atmosphere, and the X-ray diffraction pattern of the solid electrolyte is tested under Cu target X-ray source at 10°-80°, as shown in Figure 8 The microstructure of the obtained plastic-viscous solid electrolyte material is mainly crystalline phase.

[0066] The synthesized plastic-viscous solid electrolyte material is assembled into a solid-state battery, the plastic-viscous solid electrolyte material of the embodiment is loaded into a general mold battery inside the glove box, and a solid electrolyte sheet is obtained by applying a pressure of 10 MPa. The electrochemical impedance spectrum of the battery is tested, and the ionic conductivity of the plastic-viscous solid electrolyte material at 25°C is 16.77 mScm -1 , as shown in Figure 9 .

[0067] In summary, the present application provides a plastic-viscous solid electrolyte material, which has plastic-viscous and high ionic conduction characteristics, can form a stable interface with a variety of positive electrode materials and realize stable cycling. In addition, the plastic-viscous solid electrolyte material of the present application can realize the operation of the solid-state battery under low pressure, and is expected to improve the energy density of the solid-state battery. The preparation method of the present application is simple and practical, and the plastic-viscous solid electrolyte material prepared by the present application can be used to construct a low-pressure high-energy density all-solid-state battery.

[0068] The above is only a specific embodiment of the present application, but the protection scope of the present application is not limited thereto, any person skilled in the art can easily think of changes or replacements within the technical range disclosed in the present application, which should be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A viscoplastic solid electrolyte material, characterized in that, The general chemical formula of the viscoplastic solid electrolyte material is x(AX)-y(MX3)-z(BX2); Wherein, A is at least one of Li, Na, K, and Ag, M is Ga, B is at least one of Mg, Ca, Sr, Ba, and Zn, X is at least one of F, Cl, Br, and I, x>0, y>0, z≥0, and the macroscopic morphology of the viscoplastic solid electrolyte material is non-powder.

2. The viscoplastic solid electrolyte material according to claim 1, characterized in that, The macroscopic morphology of the viscoplastic solid electrolyte material is clay-like.

3. The viscoplastic solid electrolyte material according to claim 1, characterized in that, The microstructure of the viscoplastic solid electrolyte material is a crystalline phase, an amorphous phase, or a coexistence of crystalline and amorphous phases.

4. A method for preparing a viscoplastic solid electrolyte material according to any one of claims 1 to 3, characterized in that, The process includes the following steps: Under inert gas protection, raw materials AX, MX3 and BX2 are weighed according to stoichiometric ratio, mixed and sealed, and then subjected to a solid-phase reaction to obtain the viscoplastic solid electrolyte material.

5. The preparation method according to claim 4, characterized in that, The inert gas is one of helium, neon, argon, and nitrogen.

6. The preparation method according to claim 4, characterized in that, The sealing conditions are: oxygen content less than 1 ppm and water content less than 1 ppm.

7. The preparation method according to claim 4, characterized in that, The solid-phase reaction is carried out by ball milling, ball milling combined with heat treatment, or sand milling.

8. The preparation method according to claim 7, characterized in that, The solid-phase reaction is carried out by ball milling, with the milling beads made of zirconium oxide, the diameter of the milling beads being 0.1~50 mm, the ball-to-material ratio being (5~60):1, the milling time being 1~20 h, and the rotation speed being 100~600 rpm.

9. The application of a viscoplastic solid electrolyte material according to any one of claims 1 to 3 in a solid-state battery, characterized in that, The solid-state battery includes a positive electrode, a negative electrode, and an electrolyte spaced between the positive and negative electrodes, wherein at least one of the positive electrode, the negative electrode, and the electrolyte comprises the viscoplastic solid electrolyte material.

10. The application according to claim 9, characterized in that, At least one of the positive electrode, the negative electrode, and the electrolyte further comprises an oxide solid electrolyte, a sulfide solid electrolyte, a halide solid electrolyte, a polymer electrolyte, or an electrolyte solution.

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