Preparation method and preparation device of solid electrolyte

Abstract

The invention provides a preparation method and a preparation device of a solid electrolyte, and the preparation method comprises the following steps: obtaining raw materials including barium oxide, zirconium oxide, magnesium oxide and sodium fluoride with set contents; the raw materials are ground, an ethanol solution is added, and ground powder is obtained; applying a set pressure to the polishing powder to obtain an initial solid electrolyte; sintering the initial solid electrolyte at a set sintering temperature and a set heating rate to obtain a solid electrolyte; the problem that in the prior art, a solid electrolyte is low in ionic conductivity at normal temperature is solved.

Description

Technical Field

[0001] The present invention relates to the field of battery technology, and in particular to a method and device for preparing a solid electrolyte. Background Art

[0002] Solid electrolytes are an indispensable component of modern energy storage and conversion technologies, playing a key role in devices such as lithium-ion batteries, fuel cells and supercapacitors. Compared with traditional liquid electrolytes, solid electrolytes have attracted widespread attention due to their inherent safety, high temperature resistance, long life and wide range of applications. In solid electrolytes, the migration of ions is the basis of electrochemical reactions and directly affects the performance and efficiency of energy storage devices.

[0003] Solid electrolytes are mainly divided into two categories: inorganic solid electrolytes and organic polymer solid electrolytes. Inorganic solid electrolytes, such as Li3PO4, BaZrO3 and Li2S-P2S5 sulfide systems, generally have high stability and low flammability, but their ionic conductivity is limited by their crystal structure and ion migration paths. BaZrO3, as a typical inorganic solid electrolyte, has good chemical stability and high thermal stability, but due to the high formation energy of its inherent crystal defects (such as oxygen vacancies), its ionic conductivity is low at room temperature, limiting its application in energy storage devices. Summary of the Invention

[0004] The main purpose of the present invention is to provide a method and apparatus for preparing a solid electrolyte, so as to further solve the problem of low ionic conductivity of solid electrolytes at room temperature in the prior art.

[0005] In order to achieve the above object, according to one aspect of the present invention, a method for preparing a solid electrolyte is provided, comprising:

[0006] Obtaining raw materials, which include barium oxide, zirconium oxide, magnesium oxide, and sodium fluoride in predetermined amounts;

[0007] The raw materials are ground and an ethanol solution is added to obtain a ground powder;

[0008] applying a set pressure to the polished powder to obtain an initial solid electrolyte;

[0009] sintering the initial solid electrolyte at a set sintering temperature and a set heating rate to obtain a solid electrolyte;

[0010] Among them, the set content of barium oxide is 50g to 70g, the set content of zirconium oxide is 55g to 65g, the set content of magnesium oxide is 1.5g to 2.5g, the set content of sodium fluoride is 1.5g to 2.5g, the set pressure is 10Mpa to 20Mpa, the set sintering temperature is 1400℃ to 1600℃, and the set heating rate is 2℃ / min to 5℃ / min.

[0011] Furthermore, the sintering time of the initial solid electrolyte at the set sintering temperature and the set heating rate is 4 hours to 5 hours.

[0012] Further, the raw material is ground and an ethanol solution is added to obtain a ground powder, which includes:

[0013] Grind the raw material once and add 22.6 ml to 28.5 ml of ethanol solution to obtain a primary grinding powder;

[0014] Grinding the primary grinding powder for the second time to obtain polished powder;

[0015] The grinding time of the first grinding is 20 min to 30 min, the grinding time of the second grinding is 4 h to 6 h, and the ethanol content is 22.6 ml to 28.5 ml.

[0016] Furthermore, before the step of sintering the initial solid electrolyte at a set sintering temperature and a set heating rate, the method further includes:

[0017] Obtaining a preset temperature electrolyte database, the preset temperature electrolyte database including a plurality of initial sintering temperatures and the ionic conductivity of the solid electrolyte corresponding to each initial sintering temperature;

[0018] Traversing a preset temperature electrolyte database, determining a maximum value among a plurality of ion conductivities, and marking the maximum value among the plurality of ion conductivities as a target ion conductivity;

[0019] determining, according to the target ionic conductivity, a target sintering temperature corresponding to the target ionic conductivity among a plurality of initial sintering temperatures;

[0020] The target sintering temperature is used as the set sintering temperature to sinter the initial solid electrolyte.

[0021] Further, the content of barium oxide is 68.66g; and / or,

[0022] The content of zirconium oxide is 61.61 g; and / or,

[0023] The content of magnesium oxide is 2.02g; and / or,

[0024] The content of sodium fluoride is 2.10 g.

[0025] According to another aspect of the present invention, a solid electrolyte preparation device is provided, which is applied to the above-mentioned preparation method, and the preparation device comprises:

[0026] A raw material storage unit, which is used to store raw materials, including barium oxide, zirconium oxide, magnesium oxide and sodium fluoride in set contents;

[0027] A grinding unit, wherein the inlet of the grinding unit is connected to the outlet of the raw material storage unit to grind the raw material at a set content delivered from the raw material storage unit to obtain a ground powder;

[0028] A tablet pressing unit, wherein the inlet of the tablet pressing unit is connected to the outlet of the grinding unit to press the ground powder transported from the grinding unit to the tablet pressing unit at a set pressure to obtain an initial solid electrolyte;

[0029] a sintering unit, wherein the inlet of the sintering unit is connected to the outlet of the tableting unit, for sintering the initial solid electrolyte at a set sintering temperature and a set heating rate to obtain a solid electrolyte;

[0030] Among them, the set content of barium oxide is 50g to 70g, the set content of zirconium oxide is 55g to 65g, the set content of magnesium oxide is 1.5g to 2.5g, the set content of sodium fluoride is 1.5g to 2.5g, the set pressure is 10Mpa to 20Mpa, the set sintering temperature is 1400℃ to 1600℃, and the set heating rate is 2℃ / min to 5℃ / min.

[0031] Furthermore, the grinding unit comprises:

[0032] A polishing tank body, wherein the polishing tank body has a polishing space;

[0033] A polishing platform is arranged in the polishing space, the polishing platform is an arc-shaped structure, and has an arc-shaped first polishing surface, and the arc-shaped opening of the polishing platform is arranged away from the bottom of the polishing tank body;

[0034] The grinding component is at least partially arranged in the grinding space. The grinding component has a grinding end, and the grinding end cooperates with the first grinding surface to grind the raw material in the first grinding surface to obtain initial grinding powder.

[0035] Furthermore, the grinding component includes:

[0036] A driving member is arranged on the top of the polishing tank body, and a driving end of the driving member is located in the polishing space;

[0037] a grinding rod, one end of which is connected to the driving end;

[0038] The grinding head is arranged at one end of the grinding rod away from the driving end. The grinding head has a grinding end, which is driven by the driving member to contact the first arc-shaped grinding surface to grind the raw material.

[0039] Furthermore, the grinding component also includes:

[0040] A photographing component is arranged in the polishing space and photographs the polishing pictures of the polishing powder at intervals of a preset time, wherein the polishing pictures are used to represent the powder particle size of the polishing powder;

[0041] The controller is connected to the shooting component and the grinding component to control the grinding component to start or stop grinding according to the powder particle size.

[0042] Furthermore, the grinding unit also includes:

[0043] The grinding component has an inlet connected to the outlet end of the grinding tank body to perform secondary grinding on the initial grinding powder to obtain grinding powder.

[0044] Furthermore, the raw material storage unit includes:

[0045] a first storage tank, the first storage tank being used to store barium oxide, the outlet of the first storage tank being connected to the inlet of the polishing unit; and / or,

[0046] a second storage tank, the second storage tank being used to store zirconium oxide, the outlet of the second storage tank being connected to the inlet of the polishing unit; and / or,

[0047] a third storage tank, the third storage tank is used to store magnesium oxide, and the outlet of the third storage tank is connected to the inlet of the polishing unit; and / or,

[0048] The fourth storage tank is used to store sodium fluoride, and the outlet of the fourth storage tank is connected to the inlet of the polishing unit.

[0049] Furthermore, grinding lines or protrusions are provided on at least one surface of the grinding platform and the grinding head.

[0050] Furthermore, the grinding unit also includes:

[0051] The discharge port is set at the bottom of the grinding platform;

[0052] A discharge pipe, the inlet end of which is connected to the discharge port;

[0053] The discharge valve is movably arranged at one end of the discharge pipe close to the discharge port to open or close the discharge pipe.

[0054] Applying the technical solution of the present invention, the barium oxide content is set to 50g to 70g, the zirconium oxide content is set to 55g to 65g, the magnesium oxide content is set to 1.5g to 2.5g, and the sodium fluoride content is also set to 1.5g to 2.5g. This precise ratio not only ensures the formation of the BaZrO3 matrix, but also the magnesium ion (Mg 2+ ) and fluoride ions (F - ) is controlled within the optimal range, which can effectively improve the ionic conductivity and avoid the degradation of electrochemical performance caused by improper raw material ratio;

[0055] Adding ethanol solution during the raw material grinding process can reduce powder agglomeration and improve powder fluidity. At the same time, the volatility of ethanol helps dry the powder, forming a more uniform solid electrolyte precursor. This mixed solvent grinding method improves the uniformity and purity of the powder, promotes ion diffusion and crystal growth during the subsequent tableting and sintering processes, and thus optimizes the microstructure of the solid electrolyte.

[0056] Applying a pressure of 10 to 20 MPa for tableting can tightly pack the powder without destroying the powder structure, forming a solid electrolyte body with a certain density. High-pressure tableting helps reduce the porosity within the body and increase the density of the solid electrolyte, thereby reducing the resistance to ion migration and improving ionic conductivity.

[0057] Sintering at a set sintering temperature of 1400°C to 1600°C and a set heating rate of 2°C / min to 5°C / min promotes close bonding between solid electrolyte particles, optimizes the material's crystal structure, reduces grain boundary defects, and improves the effectiveness of ion migration pathways. Proper control of the sintering temperature and heating rate ensures the material's microstructure and chemical stability, significantly improving the solid electrolyte's ionic conductivity and thermal stability.

[0058] This optimized preparation method significantly enhances the ionic conductivity of solid electrolyte materials, reduces interfacial impedance, and improves thermal stability, directly enhancing the performance and service life of electrochemical energy storage devices such as batteries and supercapacitors. Furthermore, the optimized material microstructure reduces ineffective energy loss during electrochemical reactions, improving energy conversion efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] The accompanying drawings, which constitute part of this application, are intended to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are intended to explain the present invention and do not constitute an undue limitation of the present invention. In the accompanying drawings:

[0060] Figure 1 A flow chart showing a method for preparing a solid electrolyte according to an embodiment of the present application is shown;

[0061] Figure 2 The figure shows a structural diagram of a solid electrolyte preparation device according to an embodiment of the present application.

[0062] The above drawings include the following reference numerals:

[0063] 10. Raw material storage unit; 101. First storage tank; 102. Second storage tank; 103. Third storage tank; 104. Fourth storage tank; 20. Grinding unit; 2011. Grinding tank body; 2012. Grinding platform; 2013. Grinding components; 2014. Driving part; 2015. Grinding rod; 2016. Grinding head; 2017. Feeding tube; 30. Tablet pressing unit; 40. Sintering unit. DETAILED DESCRIPTION

[0064] It should be noted that, in the absence of conflict, the embodiments and features of the embodiments in this application can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0065] Solid electrolytes are an indispensable component of modern energy storage and conversion technologies, playing a key role in devices such as lithium-ion batteries, fuel cells and supercapacitors. Compared with traditional liquid electrolytes, solid electrolytes have attracted widespread attention due to their inherent safety, high temperature resistance, long life and wide range of applications. In solid electrolytes, the migration of ions is the basis of electrochemical reactions and directly affects the performance and efficiency of energy storage devices.

[0066] Solid electrolytes are mainly divided into two categories: inorganic solid electrolytes and organic polymer solid electrolytes. Inorganic solid electrolytes, such as Li3PO4, BaZrO3 and Li2S-P2S5 sulfide systems, generally have high stability and low flammability, but their ionic conductivity is limited by their crystal structure and ion migration paths. BaZrO3, as a typical inorganic solid electrolyte, has good chemical stability and high thermal stability, but due to the high formation energy of its inherent crystal defects (such as oxygen vacancies), its ionic conductivity is low at room temperature, limiting its application in energy storage devices.

[0067] The main purpose of the present invention is to provide a method and apparatus for preparing a solid electrolyte, so as to further solve the problem of low ionic conductivity of solid electrolytes at room temperature in the prior art.

[0068] First, if Figure 1 As shown, the embodiment of the present application discloses a method for preparing a solid electrolyte, comprising:

[0069] S1. Obtaining raw materials, which include barium oxide, zirconium oxide, magnesium oxide, and sodium fluoride at set contents;

[0070] S2. grinding the raw materials and adding ethanol solution to obtain grinding powder;

[0071] Grind the raw material once and add 22.6 ml to 28.5 ml of ethanol solution to obtain a primary grinding powder;

[0072] Grinding the primary grinding powder for the second time to obtain polished powder;

[0073] The grinding time of the first grinding is 20 min to 30 min, the grinding time of the second grinding is 4 h to 6 h, and the ethanol content is 22.6 ml to 28.5 ml.

[0074] S3, applying a set pressure to the polished powder to obtain an initial solid electrolyte;

[0075] S4, sintering the initial solid electrolyte at a set sintering temperature and a set heating rate to obtain a solid electrolyte;

[0076] The sintering time of the initial solid electrolyte at the set sintering temperature and the set heating rate is 4 to 5 hours;

[0077] The step of sintering the initial solid electrolyte at a set sintering temperature and a set heating rate also includes:

[0078] Obtaining a preset temperature electrolyte database, the preset temperature electrolyte database including a plurality of initial sintering temperatures and the ionic conductivity of the solid electrolyte corresponding to each initial sintering temperature;

[0079] Traversing a preset temperature electrolyte database, determining a maximum value among a plurality of ion conductivities, and marking the maximum value among the plurality of ion conductivities as a target ion conductivity;

[0080] determining, according to the target ionic conductivity, a target sintering temperature corresponding to the target ionic conductivity among a plurality of initial sintering temperatures;

[0081] The target sintering temperature is used as the set sintering temperature to sinter the initial solid electrolyte.

[0082] The barium oxide content is set to 50 g to 70 g, the zirconium oxide content is set to 55 g to 65 g, the magnesium oxide content is set to 1.5 g to 2.5 g, the sodium fluoride content is set to 1.5 g to 2.5 g, the pressure is set to 10 MPa to 20 MPa, the sintering temperature is set to 1400° C. to 1600° C., and the heating rate is set to 2° C. / min to 5° C. / min.

[0083] The content of barium oxide in this embodiment is 68.66 g; the content of zirconium oxide is 61.61 g; the content of magnesium oxide is 2.02 g; and the content of sodium fluoride is 2.10 g.

[0084] Specifically, if Figure 1 As shown, in the process of preparing the solid electrolyte, it is first necessary to obtain raw materials, which include 50g to 70g of barium oxide, preferably 68.66g, 55g to 65g of zirconium oxide, preferably 61.61g, 1.5g to 2.5g of magnesium oxide, preferably 2.02g, and 1.5g to 2.5g of sodium fluoride, preferably 2.10g;

[0085] After the above raw materials are selected, the raw materials need to be polished. The polishing process is divided into primary polishing and secondary polishing. During the primary polishing of the above raw materials, 22.6ml to 28.5ml of ethanol solution needs to be added, and the polishing time should be 20min to 30min, which can avoid the agglomeration of the raw materials during the polishing process to obtain a primary polished powder. The primary polished powder is then subjected to a secondary polishing, and the secondary polishing time should be 4h to 6h. After uniform polishing, a polished powder is obtained. A pressure of 10Mpa to 20Mpa is applied to the polished powder to press the polished powder to obtain an initial solid electrolyte, and the initial solid electrolyte is sintered at a set temperature. The heating rate from 0 degrees to the set temperature is 2℃ / min to 5℃ / min. The set temperature is preferably 1500℃ in this embodiment to obtain a solid electrolyte.

[0086] Before the step of sintering the initial solid electrolyte at the set sintering temperature, it is also necessary to determine the sintering temperature. The step of determining the sintering temperature is to obtain a preset temperature electrolyte database. The preset temperature electrolyte database includes multiple initial sintering temperatures. The temperature gradient between each two adjacent initial sintering temperatures is 50°C. Each initial sintering temperature corresponds to the ionic conductivity of a solid electrolyte. The preset temperature electrolyte database is traversed, and the ionic conductivity at the maximum value is determined from the multiple ionic conductivities. The ionic conductivity at the maximum value is marked as the target ionic conductivity. According to the correspondence between each ionic conductivity and the initial sintering temperature, the target sintering temperature corresponding to the target ionic conductivity is determined, and the target sintering temperature is used as the set sintering temperature to sinter the initial solid electrolyte.

[0087] Using the preparation method of the present invention, the ionic conductivity of the solid electrolyte can reach 10^-4 S / cm at room temperature, which is several times higher than that of undoped BaZrO3 material. Especially under high temperature conditions, the ionic conductivity can reach 10^-2 S / cm, which is significantly better than traditional liquid electrolytes. In addition, the solid electrolyte prepared by this method remains stable and does not easily decompose even in high temperature environments.

[0088] The electrolyte prepared in this application does not contain flammable organic solvents and will not leak during use, greatly improving the safety performance of energy storage devices;

[0089] At the same time, the optimized sintering temperature and doping process effectively reduce the interface impedance between the solid electrolyte and the electrode, and improve the efficiency of the electrochemical reaction;

[0090] The structural stability of solid electrolytes allows for extended cycle life of energy storage devices.

[0091] As shown in the following table, the various properties of the solid electrolyte prepared by the preparation method of the present application are compared with the various properties of the conventional liquid electrolyte;

[0092]

[0093]

[0094] like Figure 2 As shown, the embodiment of the present application further provides a solid electrolyte preparation device, which is applied to the above-mentioned preparation method, and the preparation device includes:

[0095] A raw material storage unit 10 is used to store raw materials, including barium oxide, zirconium oxide, magnesium oxide, and sodium fluoride in predetermined amounts;

[0096] A grinding unit 20, the inlet of which is connected to the outlet of the raw material storage unit 10, so as to grind the raw material at a set content delivered from the raw material storage unit 10 and obtain a ground powder;

[0097] The tablet pressing unit 30 has an inlet connected to the outlet of the polishing unit 20 to press the polished powder transported from the polishing unit 20 to the tablet pressing unit 30 at a set pressure to obtain an initial solid electrolyte;

[0098] a sintering unit 40 , wherein the inlet of the sintering unit 40 is connected to the outlet of the tableting unit 30 , for sintering the initial solid electrolyte at a set sintering temperature and a set heating rate to obtain a solid electrolyte;

[0099] Among them, the set content of barium oxide is 50g to 70g, the set content of zirconium oxide is 55g to 65g, the set content of magnesium oxide is 1.5g to 2.5g, the set content of sodium fluoride is 1.5g to 2.5g, the set pressure is 10Mpa to 20Mpa, the set sintering temperature is 1400℃ to 1600℃, and the set heating rate is 2℃ / min to 5℃ / min.

[0100] Specifically, the preparation of the solid electrolyte provided in the embodiment of the present application includes a raw material storage unit 10 for storing raw materials, and the outlet end of the raw material storage unit 10 is connected to the inlet end of the grinding unit 20 to transport the raw materials in the raw material storage unit 10 to the grinding unit 20 for grinding, and obtain a ground powder, and transport the ground powder to the tableting unit 30 connected thereto for pressing at a set pressure to obtain an initial solid electrolyte, and transport the initial solid electrolyte to the sintering unit 40 connected to the tableting unit 30, so that the initial solid electrolyte is sintered by the sintering unit 40 at a set sintering temperature and heating rate to obtain a solid electrolyte.

[0101] The seamless connection between the raw material storage unit 10 and the grinding unit 20 realizes the automatic transportation and rapid grinding of raw materials. This design avoids the instability and time consumption of manual transfer and mixing of raw materials in traditional preparation, ensures the uniformity and high processing capacity of raw materials, and lays a solid foundation for subsequent tableting and sintering.

[0102] By precisely controlling the ratio of barium oxide, zirconium oxide, magnesium oxide, and sodium fluoride, and applying optimized sintering temperature and heating rate, this embodiment significantly improves the ionic conductivity of the solid electrolyte. At room temperature, the conductivity can be stabilized at 10^-4S / cm, and at high temperature, the conductivity can be further increased to 10^-2S / cm. Compared with undoped BaZrO3, the conductivity is significantly improved, and compared with traditional liquid electrolytes, it exhibits superior performance.

[0103] The integrated connection between the tableting unit 30 and the sintering unit 40 ensures precise control of the material's microstructure during the preparation process. By applying a pressure of 10 to 20 MPa and combining it with a high-temperature sintering process at approximately 1500°C, the density of the solid electrolyte is effectively increased, while the porosity is reduced. This enhances the structural and thermal stability of the material, ensuring consistent performance over a wide temperature range.

[0104] Because of the use of a solid electrolyte, the material prepared by this method does not leak during use and does not pose the risk of flammable or toxic substances, greatly improving the safety of energy storage and conversion equipment. Furthermore, the stability and environmental friendliness of the solid electrolyte also reduce potential environmental hazards.

[0105] Furthermore, the grinding unit 20 includes:

[0106] A polishing tank body 2011, wherein the polishing tank body 2011 has a polishing space;

[0107] The polishing platform 2012 is disposed in the polishing space. The polishing platform 2012 is an arc-shaped structure having an arc-shaped first polishing surface. The arc-shaped opening of the polishing platform 2012 is disposed away from the bottom of the polishing tank body 2011.

[0108] The grinding component 2013 is at least partially disposed in the grinding space. The grinding component 2013 has a grinding end, which cooperates with the first grinding surface to grind the raw material in the first grinding surface to obtain initial grinding powder.

[0109] Specifically, the polishing unit 20 includes a polishing tank body 2011, a polishing space is formed in the polishing tank body 2011, and a polishing platform 2012 is provided in the polishing space. Figure 1 As shown, the grinding platform 2012 is an arc-shaped structure in this embodiment, and the grinding platform 2012 has an arc-shaped first grinding surface, and the opening of the grinding platform 2012 is set away from the bottom of the grinding tank body 2011. A grinding component 2013 is also provided in the grinding space, which has a grinding end, and the grinding end can be used in conjunction with the first grinding surface. During use, the raw materials are transported to the grinding platform 2012 in the grinding tank body 2011. Since the grinding platform 2012 is an arc-shaped structure, the raw materials will almost accumulate at the bottom center of the grinding platform 2012. The grinding component 2013 can continuously cooperate with the first grinding surface to grind the raw materials on the grinding platform 2012 to obtain initial grinding powder.

[0110] The grinding platform 2012 adopts an arc-shaped structure. The arc-shaped design of its first grinding surface can ensure that the raw materials are evenly distributed during the grinding process, especially concentrated at the center of the bottom, so that all raw materials can fully contact the grinding component 2013, thereby obtaining a highly uniform initial grinding powder, which provides favorable conditions for subsequent mixing and sintering.

[0111] During the grinding process, the raw materials are subjected to repeated impact and friction by the grinding component 2013, which not only achieves the refinement of the powder, but also optimizes the microstructure of the material through appropriate force and contact mode, laying the foundation for the formation of a solid electrolyte with high density and good ionic conductivity.

[0112] By controlling the grinding time and force, this embodiment effectively reduces powder agglomeration and improves the fluidity of the powder, which is crucial for the subsequent tableting and sintering steps and can ensure the uniformity and density of the solid electrolyte during the molding process.

[0113] Furthermore, the grinding component 2013 includes:

[0114] The driving member 2014 is provided on the top of the polishing tank body 2011, and the driving end of the driving member 2014 is located in the polishing space;

[0115] A polishing rod 2015, one end of which is connected to the driving end;

[0116] The grinding head 2016 is arranged at an end of the grinding rod 2015 away from the driving end. The grinding head 2016 has a grinding end, which is driven by the driving member 2014 to contact the first arc-shaped grinding surface to grind the raw material.

[0117] Specifically, the grinding component 2013 includes a driving member 2014 disposed on the top of the grinding tank body 2011. The driving member 2014 is a driving motor in this embodiment. A grinding rod 2015 is provided at the driving end of the driving member 2014. The grinding rod 2015 is arranged along the grinding wheel. Figure 1 The grinding rod 2015 extends in the vertical direction thereof, and a grinding head 2016 is provided at one end away from the driving member 2014. The grinding head 2016 is a prototype in this embodiment. The grinding head 2016 has the above-mentioned grinding end. When grinding, the driving member 2014 drives the grinding rod 2015 to rotate. Driven by the grinding rod 2015, the grinding head 2016 also rotates, continuously grinding the raw materials on the grinding platform 2012.

[0118] The drive motor 2014 provides stable and adjustable rotational power, ensuring efficient grinding of the grinding head 2016 on the grinding platform 2012. The vertical extension of the grinding rod 2015 allows the grinding head 2016 to act perpendicularly on the raw material, increasing the grinding force and contact area, thereby improving grinding efficiency and the refinement of the powder.

[0119] By precisely controlling the speed of the drive motor, the grinding frequency and intensity of the grinding head 2016 can be adjusted, making the grinding process more controllable. This precise control capability helps ensure the grinding effect while avoiding over-grinding that causes powder to be too fine or structural damage, thereby maintaining the optimal performance of the material.

[0120] The prototype design of the grinding head 2016, combined with its rotation on the grinding platform 2012, effectively disperses and evenly grinds the raw materials, reducing powder agglomeration and improving powder flowability. Uniform powder distribution is crucial for the subsequent mixing and sintering processes, ensuring microstructural uniformity in the solid electrolyte material, thereby improving ionic conductivity.

[0121] Due to the continuous rotation and grinding of the grinding head 216 on the grinding platform 212, the raw materials are deeply mixed in the grinding tank body 211. This deep mixing helps to ensure that the magnesium ions (Mg 2+ ) and fluoride ion (F - ) is evenly distributed in the BaZrO3 matrix, creating favorable conditions for the formation of a solid electrolyte with high ionic conductivity.

[0122] Furthermore, the grinding component also includes:

[0123] A photographing component is arranged in the polishing space and photographs the polishing pictures of the polishing powder at intervals of a preset time, wherein the polishing pictures are used to represent the powder particle size of the polishing powder;

[0124] The controller is connected to the shooting component and the grinding component to control the grinding component 2013 to start or stop grinding according to the powder particle size.

[0125] Specifically, the polishing component also includes a shooting component arranged in the polishing space. The shooting component can be a camera. The shooting component can take a polishing picture of the polishing powder in the polishing space once at a preset time interval. The polishing picture can represent the powder particle size of the polishing powder. It also includes a controller. The controller is connected to the shooting component and the polishing component respectively. The controller can control the polishing component 2013 to start or stop polishing, or increase or decrease the polishing rate of the polishing component 2013 according to the size of the powder particle size.

[0126] A camera installed within the grinding chamber automatically captures images of the powder being ground at preset intervals, providing a visual representation of the powder's particle size distribution. This real-time monitoring capability allows the operator or controller to promptly understand the powder's state during the grinding process and dynamically adjust grinding conditions.

[0127] The controller is connected to the imaging and grinding components, allowing real-time feedback on the powder particle size to adjust the grinding rate or stop grinding. When the powder particle size reaches the preset ideal range, the controller automatically reduces the grinding speed or stops grinding, avoiding over-grinding that may result in too small a particle size or structural damage, ensuring optimal material properties.

[0128] Real-time powder particle size monitoring and control helps ensure that all raw materials are evenly ground to the preset particle size, reducing material inhomogeneity caused by particle size differences and improving the electrochemical performance reliability and consistency of the finished solid electrolyte product.

[0129] Furthermore, the polishing unit 20 further includes:

[0130] The grinding component has an inlet connected to the outlet of the grinding tank body 2011 to perform secondary grinding on the initial grinding powder to obtain grinding powder.

[0131] Specifically, the grinding component can perform secondary grinding on the initial grinding powder to obtain the grinding powder.

[0132] Furthermore, the raw material storage unit 10 includes:

[0133] A first storage tank 101, the first storage tank 101 is used to store barium oxide, and the outlet of the first storage tank 101 is connected to the inlet of the polishing unit 20; and / or,

[0134] A second storage tank 102, the second storage tank 102 is used to store zirconium oxide, and the outlet of the second storage tank 102 is connected to the inlet of the polishing unit 20; and / or,

[0135] A third storage tank 103, the third storage tank 103 is used to store magnesium oxide, and the outlet of the third storage tank 103 is connected to the inlet of the grinding unit 20; and / or,

[0136] The fourth storage tank 104 is used to store sodium fluoride. The outlet of the fourth storage tank 104 is connected to the inlet of the polishing unit 20.

[0137] The design of each storage tank (first storage tank 101, second storage tank 102, third storage tank 103, and fourth storage tank 104) enables the raw materials to be precisely metered and continuously fed into the grinding unit 20. This precise metering and continuous supply method ensures the consistency of the mixing ratio and avoids fluctuations in material properties caused by uneven raw material supply or metering errors.

[0138] The interconnected design between the storage tank and the polishing unit 20 enables automated raw material delivery, reducing manual steps and time, significantly improving production efficiency. This interconnection also reduces dust leakage, improves the working environment, and enhances production safety.

[0139] The direct connection between the storage tank and the polishing unit 20 reduces waste and potential contamination during the transfer process. The raw materials are enclosed within the system during transfer from the storage tank to the polishing unit 20, preventing contact with the external environment and maintaining the purity of the raw materials.

[0140] Before entering the grinding unit 20, the raw materials directly enter the grinding space through the outlet of the storage tank, which reduces the separation or agglomeration of the raw materials during the mixing process, ensures the initial uniform mixing of the raw materials at the beginning of grinding, and provides advantages for subsequent deep grinding.

[0141] The direct connection between each storage tank and the polishing unit 20, in conjunction with the use of a controller, can record and control the delivery volume and speed of raw materials, making the entire preparation process more traceable and controllable, and contributing to the management of product quality and the optimization of process parameters.

[0142] Furthermore, grinding lines or protrusions are provided on at least one surface of the grinding platform 2012 and the grinding head 2016 .

[0143] The grinding lines or raised surface design increases friction between the raw material and the grinding platform 2012 or grinding head 2016, helping to more effectively break up and refine the raw material particles. This makes the grinding process more thorough, achieving a smaller powder particle size, thereby optimizing the microstructure of the solid electrolyte and improving ionic conductivity.

[0144] The grinding lines or bumps on the surface can guide the movement path of the raw material within the grinding space, reducing the ineffective movement of the raw material during the grinding process and ensuring effective contact between the raw material and the grinding component. This improves grinding efficiency and reduces the grinding time required to achieve the desired powder particle size.

[0145] The special surface structure helps improve the uniformity of the powder. The grinding lines or protrusions can promote the uniform distribution of raw materials on the grinding platform 2012, avoiding local over-grinding or under-grinding, and ensuring that all raw materials achieve the desired particle size and morphology.

[0146] By providing grinding lines or protrusions on the surface of the grinding platform 2012 or the grinding head 2016, powder agglomeration can be reduced during the grinding process. These structural changes help separate powder particles, improve powder flowability, and provide a better raw material state for subsequent mixing and tableting steps.

[0147] Furthermore, the polishing unit 20 further includes:

[0148] The material discharge port is arranged at the bottom end of the grinding platform 2012;

[0149] A discharge pipe 2017, wherein the inlet end of the discharge pipe 2017 is connected to the discharge port;

[0150] The discharge valve is movably arranged at one end of the discharge pipe 2017 near the discharge port to open or close the discharge pipe 2017.

[0151] Specifically, the grinding unit 20 also includes a discharge port arranged at the bottom end of the grinding platform 2012. When the powder particle size of the raw material is at the set particle size, the discharge valve provided on the discharge pipe 2017 will open, thereby transporting the ground powder to the tablet pressing unit 30 for pressing.

[0152] When the discharge port opens when the raw material powder particle size reaches the desired set size, the controller monitors the powder particle size through the camera component. Once the particle size meets the requirement, the discharge valve is automatically opened, ensuring the consistency of the powder particle size delivered to the tableting unit 30. This precise control method avoids tableting and sintering problems caused by excessively large or small particle size, thereby improving the preparation quality of solid electrolytes.

[0153] Through the automatic control of the discharge valve, the ground powder can be smoothly transported from the bottom of the grinding unit 20 through the discharge pipe 2017 directly to the tableting unit 30, realizing the automated and continuous transportation of materials, reducing the stagnation time during the material transfer process, and improving the overall production efficiency.

[0154] The discharge port, located at the bottom of the grinding platform 2012, ensures complete discharge of the powder after grinding, preventing residual material from accumulating within the grinding tank body 2011 and minimizing material loss and potential contamination. Furthermore, the enclosed discharge tube 2017 prevents the powder from coming into contact with the outside world during transportation, maintaining its purity.

[0155] Since the grinding unit 20 can automatically convey powder according to the set powder particle size, the tableting unit 30 can receive powder with uniform particle size, which helps to optimize the tableting process parameters, such as pressure and time, and ensure the consistency of the tableting process and the uniformity of the tableted products.

[0156] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present application. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this specification, they indicate the presence of features, steps, operations, devices, components and / or combinations thereof.

[0157] Unless otherwise specifically stated, the relative arrangement of the parts and steps, numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention. At the same time, it should be understood that, for ease of description, the sizes of the various parts shown in the accompanying drawings are not drawn according to actual proportional relationships. The technology, methods and equipment known to those of ordinary skill in the relevant art may not be discussed in detail, but in appropriate cases, the technology, methods and equipment should be considered as a part of the specification. In all examples shown and discussed here, any specific value should be interpreted as being merely exemplary, rather than as a limitation. Therefore, other examples of the exemplary embodiments can have different values. It should be noted that similar numbers and letters represent similar items in the following drawings, and therefore, once an item is defined in an accompanying drawing, it does not need to be further discussed in subsequent drawings.

[0158] In the description of the present invention, it should be understood that the directions or positional relationships indicated by directional words such as "front, back, up, down, left, right", "horizontal, vertical, perpendicular, horizontal" and "top, bottom" are usually based on the directions or positional relationships shown in the accompanying drawings. They are only for the convenience of describing the present invention and simplifying the description. Unless otherwise specified, these directional words do not indicate or imply that the device or element referred to must have a specific direction or be constructed and operated in a specific direction. Therefore, they cannot be understood as limiting the scope of protection of the present invention; the directional words "inside and outside" refer to the inside and outside relative to the outline of each component itself.

[0159] For ease of description, spatially relative terms such as "above", "above", "on the upper surface of", "above", etc. may be used herein to describe the spatial positional relationship of a device or feature to other devices or features as shown in the figures. It should be understood that spatially relative terms are intended to include different orientations of the device in use or operation in addition to the orientation described in the figures. For example, if the device in the drawings is inverted, the device described as "above other devices or structures" or "above other devices or structures" will be positioned as "below other devices or structures" or "below other devices or structures". Thus, the exemplary term "above" can include both "above" and "below". The device can also be positioned in other different ways (rotated 90 degrees or in other orientations), and the spatially relative descriptions used here are interpreted accordingly.

[0160] In addition, it should be noted that the use of terms such as "first" and "second" to limit components is only for the convenience of distinguishing the corresponding components. Unless otherwise stated, the above terms have no special meaning and therefore cannot be understood as limiting the scope of protection of the present invention.

[0161] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A method for preparing a solid electrolyte, characterized in that: include: Obtaining raw materials, wherein the raw materials include barium oxide, zirconium oxide, magnesium oxide and sodium fluoride in set contents; Grinding the raw material and adding ethanol solution to obtain a ground powder; applying a set pressure to the polished powder to obtain an initial solid electrolyte; sintering the initial solid electrolyte at a set sintering temperature and a set heating rate to obtain the solid electrolyte; Among them, the set content of the barium oxide is 50g to 70g, the set content of the zirconium oxide is 55g to 65g, the set content of the magnesium oxide is 1.5g to 2.5g, the set content of the sodium fluoride is 1.5g to 2.5g, the set pressure is 10Mpa to 20Mpa, the set sintering temperature is 1400℃ to 1600℃, and the set heating rate is 2℃ / min to 5℃ / min.

2. The method for preparing a solid electrolyte according to claim 1, wherein: The sintering time of the initial solid electrolyte at the set sintering temperature and the set heating rate is 4 hours to 5 hours.

3. The method for preparing a solid electrolyte according to claim 1, wherein: The step of grinding the raw material and adding an ethanol solution to obtain a ground powder comprises: Grinding the raw material once, and adding 22.6 ml to 28.5 ml of the ethanol solution to obtain a primary grinding powder; performing secondary grinding on the primary grinding powder to obtain the polished powder; The grinding time of the first grinding is 20 min to 30 min, the grinding time of the second grinding is 4 h to 6 h, and the content of ethanol is 22.6 ml to 28.5 ml.

4. The method for preparing a solid electrolyte according to claim 1, wherein: Before the step of sintering the initial solid electrolyte at a set sintering temperature and a set heating rate, the step further includes: Acquire a preset temperature electrolyte database, wherein the preset temperature electrolyte database includes a plurality of initial sintering temperatures and the ionic conductivity of the solid electrolyte corresponding to each of the initial sintering temperatures; Traversing the preset temperature electrolyte database, determining a maximum value among a plurality of the ionic conductivities, and marking the maximum value among the plurality of the ionic conductivities as a target ionic conductivity; determining, according to the target ionic conductivity, a target sintering temperature corresponding to the target ionic conductivity among the plurality of initial sintering temperatures; The initial solid electrolyte is sintered using the target sintering temperature as the set sintering temperature.

5. The method for preparing a solid electrolyte according to claim 1, wherein: The content of the barium oxide is 68.66 g; and / or, The content of the zirconium oxide is 61.61 g; and / or, The content of the magnesium oxide is 2.02g; and / or, The content of the sodium fluoride is 2.10 g.

6. A solid electrolyte preparation device, characterized in that: The preparation device is applied to the preparation method of the solid electrolyte according to any one of claims 1 to 5, and the preparation device comprises: A raw material storage unit (10), wherein the raw material storage unit (10) is used to store raw materials, wherein the raw materials include barium oxide, zirconium oxide, magnesium oxide and sodium fluoride in set contents; a grinding unit (20), wherein the inlet of the grinding unit (20) is connected to the outlet of the raw material storage unit (10) to grind the raw material at the set content delivered from the raw material storage unit (10) to obtain a ground powder; a tablet pressing unit (30), wherein the inlet of the tablet pressing unit (30) is used to communicate with the outlet of the polishing unit (20) so as to press the polished powder transported from the polishing unit (20) to the tablet pressing unit (30) at a set pressure to obtain an initial solid electrolyte; a sintering unit (40), wherein the inlet of the sintering unit (40) is connected to the outlet of the tableting unit (30), so as to sinter the initial solid electrolyte at a set sintering temperature and a set heating rate to obtain the solid electrolyte; Among them, the set content of the barium oxide is 50g to 70g, the set content of the zirconium oxide is 55g to 65g, the set content of the magnesium oxide is 1.5g to 2.5g, the set content of the sodium fluoride is 1.5g to 2.5g, the set pressure is 10Mpa to 20Mpa, the set sintering temperature is 1400℃ to 1600℃, and the set heating rate is 2℃ / min to 5℃ / min.

7. The solid electrolyte preparation device according to claim 6, characterized in that: The polishing unit (20) comprises: A polishing tank body (2011), wherein the polishing tank body (2011) has a polishing space therein; A polishing platform (2012) is disposed in the polishing space, wherein the polishing platform (2012) is an arc-shaped structure having an arc-shaped first polishing surface, and an arc-shaped opening of the polishing platform (2012) is disposed away from the bottom of the polishing tank body (2011); A grinding component (2013) is at least partially arranged in the grinding space, and the grinding component (2013) has a grinding end, and the grinding end cooperates with the first grinding surface to grind the raw material in the first grinding surface to obtain initial grinding powder.

8. The solid electrolyte preparation device according to claim 7, characterized in that: The polishing component (2013) comprises: A driving member (2014) is arranged on the top of the polishing tank body (2011), and a driving end of the driving member (2014) is located in the polishing space; a polishing rod (2015), one end of which is connected to the driving end; A grinding head (2016) is arranged at an end of the grinding rod (2015) away from the driving end. The grinding head (2016) has the grinding end so as to contact the first arc-shaped grinding surface under the drive of the driving member (2014) to grind the raw material.

9. The solid electrolyte preparation device according to claim 7, characterized in that: The grinding component also includes: a photographing component, disposed in the polishing space, for photographing a polishing picture of the polishing powder at intervals of a preset time, wherein the polishing picture is used to represent the powder particle size of the polishing powder; A controller is connected to the shooting component and the grinding component to control the grinding component (2013) to start or stop grinding according to the powder particle size.

10. The solid electrolyte preparation device according to claim 7, characterized in that: The polishing unit (20) further comprises: A grinding component, the inlet of which is connected to the outlet end of the grinding tank body (2011), so as to perform secondary grinding on the initial grinding powder to obtain the grinding powder.

11. The solid electrolyte preparation device according to claim 6, characterized in that: The raw material storage unit (10) comprises: a first storage tank (101), the first storage tank (101) being used to store the barium oxide, the outlet of the first storage tank (101) being connected to the inlet of the polishing unit (20); and / or, a second storage tank (102), the second storage tank (102) being used to store the zirconium oxide, the outlet of the second storage tank (102) being in communication with the inlet of the polishing unit (20); and / or, a third storage tank (103), the third storage tank (103) being used to store the magnesium oxide, the outlet of the third storage tank (103) being in communication with the inlet of the grinding unit (20); and / or, A fourth storage tank (104), the fourth storage tank (104) is used to store the sodium fluoride, and the outlet of the fourth storage tank (104) is connected to the inlet of the polishing unit (20).

12. The solid electrolyte preparation device according to claim 8, characterized in that: At least one surface of the grinding platform (2012) and the grinding head (2016) is provided with grinding lines or protrusions.

13. The solid electrolyte preparation device according to claim 7, characterized in that: The polishing unit (20) further comprises: A feeding port is provided at the bottom end of the polishing platform (2012); A feeding pipe (2017), wherein the inlet end of the feeding pipe (2017) is connected to the feeding port; A discharge valve is movably arranged at one end of the discharge pipe (2017) close to the discharge port to open or close the discharge pipe (2017).

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