Oxidation halide electrolyte, preparation method thereof and solid-state battery

Abstract

The invention provides an oxyhalide electrolyte, a preparation method thereof and a solid-state battery. The oxyhalide electrolyte is a lithium tantalum oxychloride oxyhalide electrolyte with an amorphous structure; wherein the lithium tantalum oxychloride oxyhalide electrolyte with the amorphous structure is obtained by heating a precursor mixture through a microwave flash burning method to obtain a heating product, and cooling the heating product to room temperature; the precursor mixture is obtained by mixing raw materials of the oxyhalide electrolyte, and the raw materials comprise Li2O and TaCl5. The method is used for greatly improving the preparation efficiency and the ionic conductivity of the lithium tantalum oxychloride oxyhalide electrolyte.

Description

Technical Field

[0001] This application relates to the field of batteries, and more particularly to a halide oxide electrolyte and its preparation method, and a solid-state battery. Background Technology

[0002] All-solid-state lithium batteries are considered an ideal choice for next-generation energy storage devices due to their high safety and high energy density. Solid-state electrolytes, as one of the core materials of all-solid-state lithium batteries, need to possess high ionic conductivity, good chemical / electrochemical stability, and compatibility with electrode materials.

[0003] Currently, lithium tantalum oxychloride (LiTaOCl) is an emerging and promising solid-state halide electrolyte material. Theoretical predictions indicate that it possesses three-dimensional ion migration channels, enabling high lithium-ion conductivity, and exhibits excellent oxidation stability (oxidation potential > 4V).

[0004] However, due to the volatility of the raw material tantalum pentachloride (melting point 216°C, boiling point 242°C), the current LiTaOCl mainly relies on high-energy ball milling for preparation, which is time-consuming, energy-intensive and cannot be mass-produced. In addition, the ionic conductivity of LiTaOCl still needs to be further improved. Summary of the Invention

[0005] This invention provides a halogen oxide electrolyte and its preparation method, as well as a solid-state battery, to significantly improve the preparation efficiency and ionic conductivity of lithium tantalum oxychloride halogen oxide electrolyte.

[0006] In a first aspect, the present invention provides a halide electrolyte, wherein the halide electrolyte is a lithium tantalum oxychloride halide electrolyte having an amorphous structure;

[0007] The lithium tantalum oxychloride oxide electrolyte with an amorphous structure is obtained by heating a precursor mixture using a microwave flash calcination method to obtain a heated product, and then cooling the heated product to room temperature; the precursor mixture is obtained by mixing the raw materials of the oxyhalide electrolyte, and the raw materials include Li2O and TaCl5.

[0008] According to one embodiment of the present invention, the heated product is obtained by placing the precursor mixture in a microwave reactor for microwave irradiation treatment.

[0009] A second aspect of the present invention provides a method for preparing the aforementioned halide oxide electrolyte, the method comprising:

[0010] The raw materials for the halide oxide electrolyte are mixed to obtain a precursor mixture, wherein the raw materials include Li2O and TaCl5;

[0011] The precursor mixture was heated by microwave flash calcination to obtain the heated product;

[0012] The heated product was cooled to room temperature to obtain a lithium tantalum oxychloride oxide electrolyte with an amorphous structure.

[0013] According to one embodiment of the present invention, the heating treatment of the precursor mixture by microwave flash calcination to obtain the heated product includes:

[0014] The precursor mixture was placed in a microwave reactor for microwave irradiation treatment to obtain the heated product.

[0015] According to one embodiment of the present invention, the irradiation power of the microwave irradiation treatment is 500~2000W.

[0016] According to one embodiment of the present invention, the irradiation time of the microwave irradiation treatment is 1 to 10 minutes.

[0017] According to one embodiment of the present invention, the irradiation time of the microwave irradiation treatment is 3 to 5 minutes.

[0018] According to one embodiment of the present invention, the mixing of raw materials for the halide oxide electrolyte to obtain a precursor mixture includes:

[0019] Under an inert atmosphere, Li2O powder and TaCl5 powder weighed according to a preset stoichiometric ratio are uniformly mixed using a pulverizer to obtain the precursor mixture.

[0020] According to one embodiment of the present invention, cooling the heated product to room temperature to obtain a lithium tantalum oxychloride oxide electrolyte comprises:

[0021] The heated product was cooled to room temperature under an inert atmosphere to obtain a lithium tantalum oxychloride oxide electrolyte.

[0022] A third aspect of the present invention provides a solid-state battery comprising a halooxide electrolyte as described in the first aspect above, or comprising a halooxide electrolyte prepared by the preparation method described in the second aspect above.

[0023] A fourth aspect of the present invention provides an electrical device, including an electrical device body and a solid-state battery as described in the third aspect.

[0024] The present invention has at least the following beneficial effects:

[0025] Microwave flash calcination is used to heat-treat the raw material of lithium tantalum oxychloride. On the one hand, the rapid microwave non-equilibrium process can suppress the ordered growth of crystals, directly generating lithium tantalum oxychloride with an amorphous structure. Due to the characteristics of long-range disorder and short-range order in amorphous structures, this creates ion migration channels and activation sites far exceeding those of crystalline materials, significantly improving the ionic conductivity of lithium tantalum oxychloride. On the other hand, utilizing the bulk heating mechanism of microwaves reduces the reaction time from "several hours" in traditional methods to the "minutes" level, greatly improving the preparation efficiency of lithium tantalum oxychloride ions and giving it great potential for large-scale production. Attached Figure Description

[0026] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with this application and, together with the description, serve to explain the principles of this application.

[0027] Figure 1 This is a schematic flowchart of a method for preparing a halide oxide electrolyte according to Embodiment 2 of the present invention;

[0028] Figure 2 The image shows the XRD pattern of the LiTaOCl electrolyte corresponding to Example 1.

[0029] The accompanying drawings illustrate specific embodiments of this application, which will be described in more detail below. These drawings and descriptions are not intended to limit the scope of the concept in any way, but rather to illustrate the concept of this application to those skilled in the art through reference to particular embodiments. Detailed Implementation

[0030] To enable those skilled in the art to better understand the present invention, the present invention will be further described in detail below. The specific embodiments listed below are merely descriptions of the principles and features of the present invention, and the examples are only for explaining the present invention and are not intended to limit the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0031] To facilitate understanding of the technical content of this solution, the background technology is described in detail below:

[0032] Due to the volatility of the raw material tantalum pentachloride (TaCl5), current LiTaOCl preparations primarily rely on high-energy ball milling. Specifically, high-energy ball milling is a commonly used laboratory method for synthesizing materials. This method converts mechanical energy into chemical energy through the impact between the milling beads and the material, thereby promoting the reaction. Because it does not require heating, it is particularly suitable for the synthesis of LiTaOCl, whose raw material tantalum chloride is highly volatile. However, this method has limited production volumes, typically only achieving gram-level / batch preparation, and usually requires a reaction time of more than 8 hours, sometimes even up to 2 days. Moreover, the milling jar and milling beads account for a large portion of the mass (usually greater than 80%), resulting in a high energy consumption for rotating the jar and milling beads, leading to low energy efficiency.

[0033] In view of this, the current methods for preparing LiTaOCl are time-consuming and energy-intensive and cannot be mass-produced. In addition, there is room for further improvement in the ionic conductivity of LiTaOCl.

[0034] To address the problems mentioned above in the background art, Embodiment 1 of the present invention provides a halide oxide electrolyte, which is a lithium tantalum oxychloride halide oxide electrolyte with an amorphous structure.

[0035] The lithium tantalum oxychloride oxide electrolyte with an amorphous structure is obtained by heating a precursor mixture using a microwave flash calcination method to obtain a heated product, and then cooling the heated product to room temperature. The precursor mixture is obtained by mixing the raw materials of the oxyhalide electrolyte, including Li2O and TaCl5.

[0036] According to the inventors' research, on the one hand, traditional ball milling heating methods involve a slow heating process, with the material gradually reaching thermodynamic equilibrium, and the crystalline phase becoming a stable phase due to its low energy. On the other hand, microwave flash calcination allows for rapid heating of the material, resulting in atomic motion rates far lower than the heating rate. This prevents atoms from completing long-range ordered migration. Therefore, this microwave non-equilibrium process can suppress the ordered growth of crystals, directly resulting in an amorphous structure of LiTaOCl. Correspondingly, because this amorphous structure exhibits long-range disorder and short-range order, LiTaOCl prepared by microwave flash calcination provides more migration channels and activation sites for ions, thereby achieving a breakthrough in ionic conductivity.

[0037] Meanwhile, the instantaneous nature (extremely high heating rate) and consistent bulk heating characteristics of microwave flash calcination result in an ultra-short preparation process for LiTaOCl, allowing TaCl5 to react completely and be fixed in the product microlattice before reaching the point of significant volatilization. The advantages of this strategy include: (1) effectively ensuring the purity of the prepared product, thereby ensuring that the performance of the product is not affected by impurities; (2) avoiding waste of raw materials and reducing raw material costs; and (3) solving the core pain point of difficulty in controlling the stoichiometry.

[0038] On the other hand, traditional ball milling heating methods have long heating times, usually requiring more than 8 hours of reaction time. However, the microwave bulk heating mechanism can shorten the reaction time from "several hours" to "minutes" using traditional methods, achieving an order-of-magnitude improvement in efficiency and a significant reduction in energy consumption, giving LiTaOCl great potential for large-scale production.

[0039] Therefore, by processing LiTaOCl raw materials using a microwave flash calcination method, LiTaOCl with higher ionic conductivity can be prepared rapidly and efficiently.

[0040] In one possible implementation, the heated product is obtained by microwave irradiation of a precursor mixture in a microwave reactor.

[0041] In other words, the raw materials can be microwave flash-burned by placing the precursor mixture in a microwave reactor for microwave irradiation treatment, thereby obtaining the heated product.

[0042] It should be understood that this implementation method uses a microwave flash calcination process via a microwave reactor. The volumetric instantaneous heating characteristic of the microwave reactor can further ensure that the material is heated synchronously inside and out, thereby ensuring that the effect of microwave flash calcination is fully utilized to obtain lithium tantalum oxychloride oxide electrolyte with higher purity and superior ionic conductivity.

[0043] The halide electrolyte provided in this invention has higher ionic conductivity because it is a lithium tantalum oxychloride halide electrolyte with an amorphous structure obtained by heating the raw materials using a microwave flash calcination method. In addition, due to the rapid heating method in microwave heating and the uniformity of the internal and external phases, the reaction process is rapid, which can effectively avoid the volatilization and escape of TaCl5 during the heating process. As a result, the lithium tantalum oxychloride halide electrolyte prepared by this method also has higher purity.

[0044] Furthermore, Figure 1 This is a schematic flowchart of a method for preparing a halide oxide electrolyte according to Embodiment 2 of the present invention, used to prepare the halide oxide electrolyte in the aforementioned embodiments, comprising:

[0045] S101. The raw materials of the halide oxide electrolyte are mixed to obtain a precursor mixture, wherein the raw materials include Li2O and TaCl5.

[0046] In this step, the raw materials required for preparing lithium tantalum oxychloride oxide electrolyte need to be mixed to obtain a precursor mixture, which is used in the subsequent heating reaction process.

[0047] In one possible implementation, Li2O powder and TaCl5 powder weighed according to a preset stoichiometric ratio can be uniformly mixed using a pulverizer under an inert atmosphere to obtain a precursor mixture.

[0048] The preset stoichiometric ratio can be determined based on the actual economic benefits of the target electrolyte and the desired performance. This invention does not impose a specific limitation on the ratio of Li₂O to TaCl₅. For example, the ratio of Li₂O to TaCl₅ may be 1:1, 1:2, or 2:1.

[0049] An inert atmosphere, for example, is at least one of nitrogen, argon, helium, or neon.

[0050] In this implementation, mixing the raw materials under an inert atmosphere prevents Li2O from contacting moisture or oxygen in the air, avoiding the formation of byproducts (such as LiOH) and ensuring the purity of the raw materials. At the same time, a pulverizer is used to break down the physical barriers between particles through mechanical force, achieving uniform mixing of the raw materials at the molecular level. The combined use of the inert atmosphere and the pulverizer improves the uniformity of the raw material mixing, thereby allowing the raw materials to fully contact and react in the subsequent microwave flash calcination stage, reducing performance fluctuations caused by uneven local reactions, and ensuring the consistency of product performance.

[0051] S102. The precursor mixture is heated by microwave flash calcination to obtain the heated product.

[0052] In this step, the precursor mixture will be directly heated. The mixture will rapidly heat up by absorbing microwave energy, quickly completing the solid-phase reaction to obtain the heated product.

[0053] It should be understood that microwave flash burning, a rapid microwave non-equilibrium process, can suppress the ordered growth of crystals, resulting in an amorphous structure in the heated product. This structure can further improve the ionic conductivity of the product.

[0054] In one possible implementation, the precursor mixture can be placed in a microwave reactor for microwave irradiation treatment to obtain the heated product.

[0055] Specifically, the precursor mixture can be transferred to an alumina crucible and placed in the center of a microwave reactor; the power and time of microwave irradiation in the microwave reactor can be set; the reaction program can be started so that the microwave reactor can irradiate the precursor mixture under the set power and time conditions; after the reaction is completed, the heated product is obtained.

[0056] Optionally, the irradiation power of the microwave irradiation treatment is 500~2000W. Specifically, the irradiation power of the microwave irradiation treatment is, for example, 500W, 600W, 700W, 800W, 900W, 1000W, 1100W, 1200W, 1300W, 1400W, 1500W, 1600W, 1700W, 1800W, 1900W, 2000W, or any two of the aforementioned values ​​can be selected to form a new range, and the values ​​taken within the new range can be used.

[0057] It should be understood that if the power setting of microwave irradiation is too high, it may lead to excessively vigorous reactions of the raw materials, triggering side reactions and affecting the purity of the product. If the power setting is too low, it will be difficult to meet the instantaneous requirements of microwave flash calcination, affecting the process cycle and product purity (excessive escape and volatilization of TaCl5). Within the range of 500~2000W, the precursor reaction can be driven gently and efficiently, thereby preparing a heated product with high purity and high ionic conductivity.

[0058] Optionally, the irradiation time for microwave irradiation treatment is 1 to 10 minutes. Specifically, the irradiation time for microwave irradiation treatment can be, for example, 1 minute, 1.5 minutes, 2 minutes, 2.5 minutes, 3 minutes, 3.5 minutes, 4 minutes, 4.5 minutes, 5 minutes, 5.5 minutes, 6 minutes, 6.5 minutes, 7 minutes, 7.5 minutes, 8 minutes, 8.5 minutes, 9 minutes, 9.5 minutes, or 10 minutes, or any two of the aforementioned values ​​can be selected to form a new range, and the values ​​taken within the new range can be used.

[0059] It should be understood that an irradiation time of 1 to 10 minutes can ensure both the completion of the solid-phase reaction of the raw materials and the timeliness of product preparation.

[0060] Optionally, the microwave irradiation treatment time is 3-5 minutes. It should be understood that setting the time within this range can further achieve the effect of efficiently preparing high-performance products in a short time, further balancing timeliness and product structural advantages.

[0061] This method involves directly placing the precursor mixture into a microwave reactor for microwave irradiation treatment to achieve microwave flash heating of the raw materials and obtain the heated products. By leveraging the volumetric instantaneous heating characteristic of the microwave reactor, it further ensures that the material is heated synchronously inside and out, thereby ensuring that the effect of microwave flash heating is fully utilized and achieving the effect of obtaining lithium tantalum oxychloride oxide electrolyte with higher purity and superior ionic conductivity.

[0062] S103. Cool the heated product to room temperature to obtain a lithium tantalum oxychloride oxide electrolyte with an amorphous structure.

[0063] In this step, the heated product needs to be cooled to room temperature to permanently fix its long-range disordered and short-range ordered amorphous structure, ensuring that the final product has an amorphous structure. Simultaneously, this transforms the product from a high-temperature reactive state to a room-temperature stable state, facilitating its direct use in subsequent storage and processing.

[0064] In one possible implementation, the heated product is cooled to room temperature under an inert atmosphere to obtain a lithium tantalum oxychloride oxide electrolyte.

[0065] The inert atmosphere includes at least one of nitrogen, argon, helium, and neon.

[0066] In this implementation, cooling the heated product under an inert atmosphere prevents the product from coming into contact with moisture or oxygen in the air, avoids the formation of byproducts, and ensures the purity of the final product.

[0067] The method for preparing the halide oxide electrolyte provided in this embodiment uses microwave flash calcination to heat the raw materials of lithium tantalum oxychloride halide electrolyte, reducing the reaction time from several hours in traditional methods to minutes, significantly improving production efficiency. Furthermore, this method achieves synthesis in one step, requiring no pretreatment, and the overall process is simple, easy to operate, and has good reproducibility, making it suitable for industrial production. Simultaneously, the bulk heating characteristics of microwaves ensure uniform heating within the material, preventing the volatilization of TaCl5 due to localized high temperatures during traditional heating, thus ensuring the stability of the product's stoichiometry. In addition, the rapid microwave non-equilibrium process suppresses the ordered growth of crystals, resulting in an amorphous structure in the prepared lithium tantalum oxychloride halide electrolyte, which improves the product's ionic conductivity.

[0068] Embodiment 3 of the present invention also provides a solid-state battery, including a halooxide electrolyte.

[0069] Wherein, the halogen oxide electrolyte is the halogen oxide electrolyte in the aforementioned product examples, or the halogen oxide electrolyte is the halogen oxide electrolyte prepared by the preparation method in the aforementioned method examples.

[0070] As a specific example, a solid-state battery includes a positive electrode layer, a solid electrolyte layer, and a negative electrode layer.

[0071] The solid electrolyte layer is prepared from the aforementioned halide oxide electrolyte.

[0072] In practical applications, the positive electrode layer specifically includes a positive electrode current collector and a positive electrode active layer formed of a positive electrode active material disposed on the surface of the positive electrode current collector. The negative electrode layer specifically includes a negative electrode current collector and a negative electrode active layer formed of a negative electrode active material disposed on the surface of the negative electrode current collector. This invention does not impose specific limitations on the selection and preparation of the positive and negative electrode layers in solid-state batteries.

[0073] Optionally, the positive or negative active layer may also include the halide electrolyte to further improve the performance of the solid-state battery (e.g., ionic conductivity).

[0074] The solid-state battery provided by this invention exhibits superior cycle performance due to the inclusion of the halooxide electrolyte. Furthermore, because the halooxide electrolyte used in this solid-state battery has high production efficiency, the solid-state battery also possesses high production efficiency, meeting the requirements for industrial-scale manufacturing.

[0075] Embodiment 4 of the present invention also provides an electrical device, including a main body of the electrical device and a solid-state battery provided by the present invention.

[0076] It should be noted that the present invention does not particularly limit the type of electrical device, which can be any electrical device including the battery, including but not limited to electric vehicles, mobile phones, portable devices, laptops, electric bicycles, electric toys, energy storage devices, etc.

[0077] The present invention will be further described below through specific embodiments.

[0078] Example 1

[0079] In an argon-filled glove box, Li₂O powder and TaCl₅ powder were weighed at a stoichiometric ratio of 1:1 and mixed evenly in a pulverizer to obtain a precursor mixture. The precursor mixture was transferred to an alumina crucible and placed in the center of a microwave reactor with a rated power of 0~1500W. The irradiation power of the microwave reactor was set to 1000W and the irradiation time was 5min. The reaction program was started. After the reaction was completed, the heated product was obtained and allowed to cool naturally to room temperature in the reactor to obtain the final product (LiTaOCl electrolyte).

[0080] Example 2

[0081] The only difference from Example 1 is that the stoichiometric ratio of Li2O powder to TaCl5 powder is 0.5:1.

[0082] Example 3

[0083] The only difference from Example 1 is that the stoichiometric ratio of Li2O powder to TaCl5 powder is 2:1.

[0084] Example 4

[0085] The only difference from Example 1 is that the irradiation time is 1 minute.

[0086] Example 5

[0087] The only difference from Example 1 is that the irradiation time is 3 minutes.

[0088] Example 6

[0089] The only difference from Example 1 is that the irradiation time is 10 minutes.

[0090] Comparative Example 1

[0091] In an argon-filled glove box, Li₂O powder and TaCl₅ powder were weighed at a stoichiometric ratio of 1:1 and mixed evenly in a pulverizer to obtain a precursor mixture. The precursor mixture was then ball-milled to obtain LiTaOCl electrolyte. The ball milling speed was 700 rpm and the milling time was 8 hours to obtain the final product.

[0092] Comparative Example 2

[0093] The only difference from Comparative Example 1 is that the ball milling time was 5 minutes.

[0094] Comparative Example 3

[0095] In an argon-filled glove box, Li2O powder and TaCl5 powder were weighed at a stoichiometric ratio of 1:1 and mixed evenly in a pulverizer to obtain a precursor mixture. The precursor mixture was then transferred to a muffle furnace and sintered at 250°C for 5 minutes to obtain the final product.

[0096] The final products prepared in the above embodiments and comparative examples were subjected to performance tests, and the specific test contents are as follows:

[0097] 1) Calculation of weight loss rate

[0098] Weigh the mass (M1) of the precursor mixture before the reaction and the mass (M2) of the final product obtained after the reaction. Calculate the weight loss rate using the formula (M1-M2) / M1 to assess the volatilization loss of the raw materials during the reaction.

[0099] 2) Ion conductivity test

[0100] In a specific mold, a certain quantity of the final product is pressurized to form an electrolyte sheet with a diameter of 10 mm and a certain thickness, at a pressure of 800 MPa. The electrolyte sheet is subjected to electrochemical impedance spectroscopy (EIS) testing using an electrochemical workstation (Solartron 1260+1287) to obtain its impedance value. The test frequency range for electrochemical impedance spectroscopy is 6 MHz to 1 Hz, with a sine wave amplitude of 50 mV. Impedance analysis and fitting are performed using Zview software. The thickness of the electrolyte sheet is measured. Based on the impedance value, thickness, and area of ​​the electrolyte sheet, the ionic conductivity of the electrolyte sheet is calculated using the formula σ = L / RS, where σ is the ionic conductivity of the electrolyte sheet (ms / cm), L is the thickness of the electrolyte sheet (cm), R is the impedance value of the electrolyte sheet measured by EIS (Ω), and S is the cross-sectional area of ​​the electrolyte sheet (cm²). 2 .

[0101] The test results are shown in Table 1.

[0102] Table 1: Performance test results of the final products of each embodiment and comparative example

[0103]

[0104] As can be seen from Examples 1, 4 to 6, and Comparative Example 1, when the raw material ratio is 1:1, the electrolyte prepared by microwave flash calcination has the highest ionic conductivity of 9.2 mS / cm, while the electrolyte prepared by ball milling has a conductivity of 4.8 mS / cm. Furthermore, the electrolyte product cannot be obtained by solid-state sintering, therefore, the ionic conductivity cannot be measured. It is evident that the LiTaOCl electrolyte prepared by microwave sintering has a higher ionic conductivity.

[0105] In addition, the invention also performed X-ray diffraction (XRD) crystal phase analysis on the LiTaOCl electrolyte prepared in Example 1. Specifically, the electrolyte powder sample was sealed using a Kapton film, and the crystal phase structure of the intermediate and electrolyte product was analyzed using a powder X-ray diffractometer (XRD, Bruker, D2 Phaser), yielding the following results: Figure 2 The XRD pattern shown is a Cu target (λ = 1.54 Å) used in the XRD instrument. The scanning range 2θ is 10–60°. (Refer to...) Figure 2It can be seen that the electrolyte of Example 1 has only one broadened intensity peak in the entire 2θ range, without any sharp characteristic diffraction peaks, which is completely consistent with the XRD characterization characteristics of amorphous materials. Therefore, the electrolyte corresponding to Example 1 has an amorphous structure. Accordingly, this further confirms the technical essence of the flash calcination method in improving the internal structure of the electrolyte, thereby enhancing the electrolyte's ionic conductivity.

[0106] As can be seen from Examples 1, 2, and 3, when the reaction time is 5 minutes, the microwave flash heating method in Example 1 can prepare an electrolyte with high ionic conductivity with a low weight loss rate. In contrast, ball milling and solid-state sintering methods cannot produce the corresponding products in a short time (and consequently, the ionic conductivity of the products cannot be measured). Therefore, the method provided in this scheme can significantly improve the production efficiency of LiTaOCl electrolyte while ensuring product performance. Furthermore, the solid-state sintering method in Comparative Example 3 not only fails to complete product preparation in a short time, but its weight loss rate also far exceeds that of other methods, failing to meet the product preparation requirements.

[0107] Comparing Examples 1 and 4 to 6, it can be seen that as the reaction time increases from 1 min to 3 min, the ionic conductivity increases from 3.2 mS / cm to 8.0 mS / cm; then, increasing to 5 min, the ionic conductivity increases from 8.0 mS / cm to 9.2 mS / cm; further increasing to 10 min, the ionic conductivity increases slightly to 9.3 mS / cm. This shows that the microwave flash calcination method is rapid, achieving the desired reaction effect within 5 min. Furthermore, the LiTaOCl electrolyte prepared with a time of 3-5 min exhibits even higher ionic conductivity.

[0108] By comparing Examples 1 to 3, it can be seen that LiTaOCl electrolytes prepared by microwave flash calcination with different raw material ratios all exhibit good ionic conductivity. Furthermore, as the Li₂O:TaCl₅ ratio increases from 0.5:1 to 1:1, and then to 2:1, the ionic conductivity increases from 6.3 mS / cm to 9.2 mS / cm, and then decreases to 7.0 mS / cm. This shows that adjusting the raw material ratio also affects the ionic conductivity of the product to some extent, with a 1:1 ratio resulting in better performance.

[0109] In summary, the microwave flash calcination method employed in this scheme can prepare LiTaOCl with excellent ionic conductivity in a very short time (3-5 min). Furthermore, the rapid reaction and the special heating method avoid raw material volatilization loss, ensuring a low weight loss rate for the product.

[0110] Finally, it should be noted that other embodiments of the invention will readily occur to those skilled in the art upon consideration of the specification and practice of the invention disclosed herein. This invention is intended to cover any variations, uses, or adaptations of the invention that follow the general principles of the invention and include common knowledge or customary techniques in the art not disclosed herein, and is not limited to the precise structures described above and shown in the accompanying drawings, and various modifications and changes can be made without departing from its scope. The scope of the invention is limited only by the appended claims.

Claims

1. A halide oxide electrolyte, characterized in that, The halide electrolyte is a lithium tantalum oxychloride halide electrolyte with an amorphous structure. The lithium tantalum oxychloride oxide electrolyte with an amorphous structure is obtained by heating a precursor mixture using a microwave flash calcination method to obtain a heated product, and then cooling the heated product to room temperature; the precursor mixture is obtained by mixing the raw materials of the oxide electrolyte, and the raw materials include Li2O and TaCl5.

2. The halide oxide electrolyte according to claim 1, characterized in that, The heated product is obtained by microwave irradiation treatment of the precursor mixture in a microwave reactor.

3. A method for preparing a halide oxide electrolyte as described in claim 1 or 2, characterized in that, The preparation method includes: The raw materials for the halide oxide electrolyte are mixed to obtain a precursor mixture, wherein the raw materials include Li2O and TaCl5; The precursor mixture was heated by microwave flash calcination to obtain the heated product; The heated product was cooled to room temperature to obtain a lithium tantalum oxychloride oxide electrolyte with an amorphous structure.

4. The preparation method according to claim 3, characterized in that, The heating treatment of the precursor mixture by microwave flash calcination to obtain the heated product includes: The precursor mixture was placed in a microwave reactor for microwave irradiation treatment to obtain the heated product.

5. The method according to claim 4, characterized in that, The irradiation power of the microwave irradiation treatment is 500~2000W.

6. The method according to claim 4 or 5, characterized in that, The irradiation time for the microwave irradiation treatment is 1 to 10 minutes.

7. The method according to claim 6, characterized in that, The irradiation time for the microwave irradiation treatment is 3-5 minutes.

8. The method according to any one of claims 3 to 5, characterized in that, The process of mixing the raw materials of the halide oxide electrolyte to obtain a precursor mixture includes: Under an inert atmosphere, Li2O powder and TaCl5 powder weighed according to a preset stoichiometric ratio are uniformly mixed using a pulverizer to obtain the precursor mixture.

9. The method according to any one of claims 3 to 5, characterized in that, The step of cooling the heated product to room temperature to obtain a lithium tantalum oxychloride oxide electrolyte includes: The heated product was cooled to room temperature under an inert atmosphere to obtain a lithium tantalum oxychloride oxide electrolyte.

10. A solid-state battery, characterized in that, The solid-state battery includes the halide oxide electrolyte as described in claim 1 or 2, or the solid-state battery includes the halide oxide electrolyte prepared by the preparation method described in any one of claims 3 to 9.

Images