CN109879316B - LLZO preparation method, quasi-solid electrolyte for thermal battery and preparation method of quasi-solid electrolyte - Google Patents
LLZO preparation method, quasi-solid electrolyte for thermal battery and preparation method of quasi-solid electrolyte Download PDFInfo
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Abstract
The invention relates to a LLZO preparation method, a quasi-solid electrolyte for a thermal battery and a preparation method thereof, wherein the preparation method of the quasi-solid electrolyte comprises the following steps: mixing Li2CO3、La2O3、ZrO2、H2C2O4Purifying the raw materials such as alkali metal halide and the like; weighing the required Li2CO3、La2O3、H2C2O4And ZrO2Grinding, calcining at 1200 deg.C in sealed stainless steel tank, naturally cooling, pulverizing, and ball milling to obtain Li-La-Zr-O solid electrolyte (Li)7La3Zr2O12LLZO); and (2) mixing the LLZO and the alkali metal halide eutectic salt again, rapidly heating to 400-500 ℃ under the protection of argon, infiltrating the eutectic salt into the porous LLZO by repeatedly vacuumizing and slowly pressurizing, naturally cooling, and performing ball milling and crushing on a product to obtain the quasi-solid electrolyte for the thermal battery. The quasi-solid electrolyte prepared by the invention has the advantages of small grain boundary resistance, high ion mobility, good thermal stability and the like.
Description
Technical Field
The invention relates to the field of material chemistry, and particularly relates to a LLZO preparation method, a quasi-solid electrolyte for a thermal battery and a preparation method of the quasi-solid electrolyte.
Background
At present, thermal batteries as missile-borne power sources employ alkali metal halide eutectic salts as electrolytes, which are flowable liquids above the eutectic point. Although the electrolyte is added with the MgO as the flow inhibitor to form the isolation powder when the thermal battery is prepared, the requirement on the resistance chemical environment of the battery is higher and higher along with the continuous improvement of the performance of a weapon system, and the traditional thermal battery still has the risk of electrolyte overflow under the severe mechanical environment, so that the short circuit of the battery is caused. The solid electrolyte material with strong thermal stability, wide electrochemical window and non-melting in the working temperature range of the thermal battery is adopted to replace the traditional thermal battery electrolyte material, which becomes a key measure for solving the problem, so the development of the solid electrolyte material for the thermal battery becomes a research work with great military significance.
In general, Li7La3Zr2O12(LLZO) is a solid electrolyte commonly used in Lithium-ion Batteries (LIBs), but cannot meet the requirement of high power output of thermal Batteries due to low ionic conductivity. In addition, when the LLZO for the LIBs is produced, in order to reduce the grain boundary internal resistance of the LLZO, a two-step solid phase method is generally adopted, wherein the square-phase LLZO (t-LLZO) is synthesized at 900 ℃, then the t-LLZO is crushed and pressed into tablets, and the tablets are roasted at more than 1000 ℃ for a long time to obtain the compact cubic-phase LLZO (c-LLZO).
In order to solve the above problems, various synthetic methods for improving the conductivity of the LLZO ion and reducing energy consumption become hot spots in LLZO research. "A method for preparing Al-doped LLZO by a citric acid-assisted polymerization sol-gel method" ("Power technology", Chenshu et Al, 2016, 140 (3): 529- "553") shortens the sintering time, but has a lower conductivity (4.5X 10)-5S/cm). Liu et al prepared F-doped LLZO by a solid phase reaction method (journal of inorganic materials 2015, 30(9):995-1001), which produced LLZO having high conductivity (5X 10)-4S/cm), but the method adopts the traditional two-step sintering (12 h at 900 ℃ and 36h at 1230 ℃), and the production cycle is long. Chinese patent CN105489930A adopts a molten salt method to prepare LLZO, the method has lower calcination temperature and shorter calcination time, and the prepared LLZO has higher conductivity (1.6 multiplied by 10)-4S/cm), but because LiCl-KCl eutectic salt is adopted, the corrosion to equipment is high at high temperature (700-.
Disclosure of Invention
The invention aims to provide a preparation method of LLZO, a quasi-solid electrolyte for a thermal battery and a preparation method thereof.
In order to achieve the above object, the present invention provides a LLZO preparation method comprising:
1) at the dew point of less than-40 ℃, adding La2O3Roasting at 800-1000 deg.c for 12-15 hr to eliminate La (OH)3Impurities of Li2CO3、ZrO2And H2C2O4Drying in a forced air drying oven;
2) according to the component content of LLZO, calculating and respectively weighing the required Li2CO3、La2O3And ZrO2Weighing appropriate amount of H2C2O4Mixing and grinding the four materials uniformly, roasting for 2-8 h at 1000-1200 ℃, then naturally cooling, and performing ball milling and uniform crushing to obtain LLZO; h2C2O4Accounting for 60-67% of the total mass of the four materials.
The LLZO preparation method, wherein in the step 1), Li2CO3、ZrO2And H2C2O4Drying the mixture in a forced air drying oven for 2 to 4 hours at the drying temperature of between 120 and 150 ℃.
The LLZO preparation method, wherein in the step 2), Li2CO3The excess is 10-20%.
The invention provides another technical scheme that the quasi-solid electrolyte for the thermal battery is composed of a porous loose-structure LLZO and alkali metal halide eutectic salt, wherein the mass percentage of the LLZO is 85-95%, and the mass percentage of the alkali metal halide eutectic salt is 5-15%.
The quasi-solid electrolyte for the thermal battery is characterized in that the LLZO with the porous loose structure is prepared by the LLZO preparation method.
The invention provides another technical scheme which is a preparation method of a quasi-solid electrolyte for a thermal battery, comprising the following steps:
step one, La is added under the environment with the dew point less than minus 40 DEG C2O3Roasting at 800-1000 deg.c for 12-15 hr to eliminate La (OH)3Impurities of Li2CO3、ZrO2、H2C2O4Co-molten salt with alkali metal halide is placed in a forced air drying oven for drying;
step two, calculating and respectively weighing the required Li according to the component content of the LLZO2CO3、La2O3And ZrO2Weighing appropriate amount of H2C2O4Mixing and grinding the four materials uniformly, roasting for 2-8 h at 1000-1200 ℃, then naturally cooling, and performing ball milling and uniform crushing to obtain LLZO; h2C2O4Accounting for 60-67% of the total mass of the four materials;
weighing the LLZO and alkali metal halide eutectic salt, wherein the mass percentage of the LLZO is 85-95%, and the mass percentage of the alkali metal halide eutectic salt is 5-15%; mixing and grinding LLZO and alkali metal halide eutectic salt uniformly, heating to 400-500 ℃ under the protection of argon, maintaining the temperature unchanged, vacuumizing until the reading of a pressure gauge is less than-0.9 MPa, slowly introducing argon until the reading of the pressure gauge reaches 0.1-0.3MPa, and repeating the operations of vacuumizing and introducing argon for pressurizing for 3-5 times; and repeating the operations of vacuumizing and argon introducing for 3-5 times every 1h, cooling and recovering to normal pressure after 2-4 h, naturally cooling to room temperature, and performing ball milling and crushing on the blocky product to obtain the quasi-solid electrolyte for the thermal battery.
In the first step, the alkali metal halide eutectic salt is a LiF-LiCl-LiBr system, a LiCl-LiBr-KBr system or a LiCl-KCl system.
The preparation method of the quasi-solid electrolyte for the thermal battery comprises the step two, wherein in the step two, Li is added2CO3、ZrO2、H2C2O4And putting the eutectic salt and alkali metal halide into a forced air drying oven to dry for 2 to 4 hours at the drying temperature of between 120 and 150 ℃.
The thermal battery is fixed by the standardA method for preparing the electrolyte, wherein, in the second step, Li2CO3The excess is 10-20%.
Compared with the prior art, the invention has the beneficial technical effects that:
aiming at the problems that the existing thermal battery electrolyte material has the flowing risk in a severe mechanical environment and the conventional LLZO solid electrolyte for LIBs has low conductivity and a complex preparation method, the invention firstly provides a quasi-solid electrolyte with simple preparation method and high ionic conductivity, wherein the quasi-solid electrolyte takes LLZO as a matrix and is a non-flowing solid in the thermal battery working temperature range (400-<100 ℃ C.), and the ion conductivity of LLZO increases with the increase of temperature, therefore, the thermal battery is not required to be sintered at high temperature for a long time, and on the contrary, in order to infiltrate the doped eutectic salt of high conductivity (ion conductivity at melting point is 1-3S/cm) into LLZO, the sintering time of LLZO should be reduced and a gas generating agent (H) is used2C2O4) In conclusion, the preparation method provided by the invention is simple, has short sintering time, and has the potential of engineering application in thermal battery type products;
the quasi-solid electrolyte prepared by the invention has the advantages of small grain boundary resistance, high ion mobility, good thermal stability and the like.
Drawings
The LLZO preparation method, quasi-solid electrolyte for thermal battery and preparation method thereof of the present invention are given by the following examples and drawings.
Fig. 1 is an electrical schematic diagram of a single cell using a quasi-solid electrolyte as an electrolyte according to a preferred embodiment of the present invention.
Fig. 2 is an electrical schematic diagram of a single cell using a quasi-solid electrolyte as an electrolyte according to another preferred embodiment of the present invention.
Detailed Description
The LLZO preparation method, the quasi-solid electrolyte for a thermal battery and the preparation method thereof according to the present invention will be described in further detail with reference to FIGS. 1 to 2.
The quasi-solid electrolyte for the thermal battery is composed of LLZO and alkali metal halide eutectic salt with a porous loose structure, wherein the mass percentage of the LLZO is 85-95%, and the mass percentage of the alkali metal halide eutectic salt is 5-15%.
The preparation method of the quasi-solid electrolyte for the thermal battery comprises the following steps:
step one, La is added under the environment with the dew point less than minus 40 DEG C2O3Roasting at 800-1000 deg.c for 12-15 hr to eliminate La (OH)3Impurities of Li2CO3、ZrO2、H2C2O4Putting the eutectic salt and alkali metal halide in a blast drying oven, and drying for 2-4 h at 120-150 ℃;
preferably, the alkali metal halide eutectic salt is a LiF-LiCl-LiBr system (the mass percentage of LiF in the system is 8-11%, the mass percentage of LiCl is 21-23%, and the mass percentage of LiBr is 67-70%), a LiCl-LiBr-KBr system (the mass percentage of LiCl in the system is 11-13%, the mass percentage of LiBr in the system is 35-38%, and the mass percentage of KBr in the system is 50-53%), or a LiCl-KCl system (the mass percentage of LiCl in the system is 44-46%, and the mass percentage of KCl in the system is 54-56%);
step two, calculating and respectively weighing the required Li according to the component content of the LLZO2CO3、La2O3And ZrO2Weighing appropriate amount of H2C2O4Mixing and grinding the four materials uniformly, putting the four materials after being ground uniformly into a stainless steel tank, roasting for 2-8 h at 1000-1200 ℃, naturally cooling, ball-milling and grinding uniformly to obtain LLZO, wherein the LLZO is LLZO with a porous loose structure;
H2C2O4accounts for the total mass of four materials60-67% of the amount;
preferably, since lithium ions are volatile at high temperature, Li2CO3The excess amount needs to be 10-20%, namely 1.1-1.2 times of the required amount is weighed;
weighing LLZO and alkali metal halide eutectic salt according to the proportion of the quasi-solid electrolyte component for the thermal battery, mixing and grinding the LLZO and the alkali metal halide eutectic salt uniformly, putting the mixture into a stainless steel tank, heating the mixture to 400-500 ℃ under the protection of nitrogen or argon, maintaining the temperature, vacuumizing the mixture until the reading of a pressure gauge is less than-0.9 MPa, slowly introducing argon until the reading of the pressure gauge reaches 0.1-0.3MPa, and repeating the operations of vacuumizing and introducing argon for pressurizing for 3-5 times; and repeating the operations of vacuumizing and argon introducing for 3-5 times every 1h, cooling and recovering to normal pressure after 2-4 h, naturally cooling to room temperature, and performing ball milling and crushing on the blocky product to obtain the quasi-solid electrolyte for the thermal battery.
According to the invention, the solid electrolyte LLZO which is not decomposed and melted at high temperature is used as a matrix, the LLZO with a porous loose structure is synthesized by controlling a synthesis method, a small amount of alkali metal halide eutectic salt is doped into the LLZO, a rapid Li ion transmission channel is established, and the ionic conductivity of the electrolyte LLZO is improved.
Example 1
And calculating the dosage of each raw material according to the proportion of each component in the target product quasi-solid electrolyte. In this example, La was added under an environment with a dew point of less than-40 deg.C2O3Calcining at 900 deg.C for 12h to remove La (OH)3Impurity, weighing 98g of heat-treated La2O3，57g Li2CO3(excess 10%), 49g ZrO2，306g H2C2O4(occupied La)2O3、Li2CO3、ZrO2And H2C2O460 percent of the total mass of the four materials) and 30g of LiF-LiCl-LiBr system eutectic salt (accounting for 15 percent of the mass of the quasi-solid electrolyte), and Li is added2CO3、ZrO2、H2C2O4And putting the eutectic salt and a LiF-LiCl-LiBr system in a forced air drying oven, and drying for 2 hours at the drying temperature of 120 ℃. Mixing 98g of La2O3，57g Li2CO3，49g ZrO2And 306g H2C2O4And putting the mixture into an agate mortar, uniformly grinding the mixture, putting the mixture into a stainless steel tank, roasting the mixture for 2 hours at 1200 ℃, naturally cooling the mixture to room temperature, and ball-milling and crushing the blocky product to obtain the LLZO. Uniformly mixing the obtained LLZO and 30g of LiF-LiCl-LiBr system eutectic salt, then placing the mixture in an atmosphere protection furnace, rapidly heating to 500 ℃ under the protection of argon, stopping heating, maintaining the temperature at 500 ℃, vacuumizing to-1.0 MPa when the temperature just reaches 500 ℃, slowly introducing argon, pressurizing to 0.1MPa, repeating vacuumizing and pressurizing (introducing argon) for 3 times in this way, then repeating vacuumizing and pressurizing for 3 times every 1h, starting to cool and recovering to normal pressure after the temperature at 500 ℃ is maintained for 2h, and after the product is naturally cooled to room temperature, performing ball milling on the product and crushing to obtain the quasi-solid electrolyte for the thermal battery.
In this example, the evacuation and pressurization were repeated 2 times, and the number of repetitions was 3 times.
By CoS2The electrical properties of the single battery with the positive electrode, the lithium boron alloy as the negative electrode and the quasi-solid electrolyte prepared in the embodiment as the electrolyte are shown in fig. 1, and the quasi-solid electrolyte prepared in the embodiment 1 can be applied to a thermal battery, and the internal resistance of the single battery is about 70-80 m Ω.
Example 2
And calculating the dosage of each raw material according to the proportion of each component in the target product quasi-solid electrolyte. In this example, La was added under an environment with a dew point of less than-40 deg.C2O3Calcining at 900 deg.C for 12h to remove La (OH)3Impurity, weighing 98g of heat-treated La2O3，57g Li2CO3(excess 10%), 49g ZrO2，408g H2C2O4(occupied La)2O3、Li2CO3、ZrO2And H2C2O467% of the total mass of the four materials) and 9g of LiCl-KCl system eutectic salt (accounting for 5% of the mass of the quasi-solid electrolyte), and Li is added2CO3、ZrO2、H2C2O4Co-melting salt with LiCl-KCl system, placing in a blast drying oven, and dryingDrying for 2h at 120 ℃. Mixing 98g of La2O3，57g Li2CO3，49g ZrO2And 408g H2C2O4And putting the mixture into an agate mortar, uniformly grinding the mixture, putting the mixture into a stainless steel tank, roasting the mixture for 2 hours at 1200 ℃, naturally cooling the mixture to room temperature, and ball-milling and crushing the blocky product to obtain the LLZO. Uniformly mixing the obtained LLZO and 9g of LiCl-KCl eutectic salt, then placing the mixture in an atmosphere protection furnace, rapidly heating to 400 ℃ under the protection of argon, maintaining the temperature at 400 ℃, vacuumizing to-1.0 MPa when the temperature just reaches 400 ℃, slowly introducing argon to pressurize to 0.3MPa, repeating the vacuumizing and pressurizing for 3 times (namely repeating the vacuumizing and the pressurizing for 3 times), then repeating the vacuumizing and the pressurizing for 3 times every 1h, starting to cool and recovering to normal pressure after the temperature at 400 ℃ is maintained for 4h, and after the product is naturally cooled to room temperature, ball-milling and crushing the product to obtain the quasi-solid electrolyte for the thermal battery.
In this example, the evacuation and pressurization were repeated 4 times, and the number of repetitions was 3 times each.
By CoS2The electrical properties of the single cell in which the positive electrode is a lithium boron alloy negative electrode and the quasi-solid electrolyte prepared in this embodiment is an electrolyte are shown in fig. 2, and the quasi-solid electrolyte prepared in embodiment 2 can be applied to a thermal battery, and the internal resistance of the single cell is about 110 to 120m Ω.
Example 3
And calculating the dosage of each raw material according to the proportion of each component in the target product quasi-solid electrolyte. In this example, La was added under an environment with a dew point of less than-40 deg.C2O3Calcining at 900 deg.C for 12h to remove La (OH)3Impurity, weighing 98g of heat-treated La2O3，62g Li2CO3(excess of 20%), 49g ZrO2，314g H2C2O4(occupied La)2O3、Li2CO3、ZrO2And H2C2O460 percent of the total mass of the four materials) and 9g of LiF-LiCl-LiBr system eutectic salt (accounting for 5 percent of the mass of the quasi-solid electrolyte), and Li is added2CO3、ZrO2、H2C2O4And LiF-And (3) putting the LiCl-LiBr system eutectic salt into a forced air drying oven, and drying for 2h at the drying temperature of 120 ℃. Mixing 98g of La2O3，62g Li2CO3，49g ZrO2And 314g H2C2O4And putting the mixture into an agate mortar, uniformly grinding the mixture, putting the mixture into a stainless steel tank, roasting the mixture for 2 hours at 1200 ℃, naturally cooling the mixture to room temperature, and ball-milling and crushing the blocky product to obtain the LLZO. Uniformly mixing the obtained LLZO and 9g of LiF-LiCl-LiBr system eutectic salt, then placing the mixture in an atmosphere protection furnace, rapidly heating to 500 ℃ under the protection of argon, stopping heating (the heating rate is 50 ℃/min), maintaining 500 ℃, vacuumizing to-1.0 MPa when the temperature just reaches 500 ℃, slowly introducing argon, pressurizing to 0.3MPa, repeating the steps for 3 times, then repeating the vacuumizing and pressurizing operations for 3 times every 1h, starting to cool and recovering to normal pressure after the 500 ℃ is maintained for 2h, and after the product is naturally cooled to room temperature, performing ball milling on the product and crushing to obtain the quasi-solid electrolyte for the thermal battery.
In this example, the evacuation and pressurization were repeated 2 times, and the number of repetitions was 3 times.
Example 4
And calculating the dosage of each raw material according to the proportion of each component in the target product quasi-solid electrolyte. In this example, La was added under an environment with a dew point of less than-40 deg.C2O3Calcining at 900 deg.C for 12h to remove La (OH)3Impurity, weighing 98g of heat-treated La2O3，62g Li2CO3(excess of 20%), 49g ZrO2，418g H2C2O4(occupied La)2O3、Li2CO3、ZrO2And H2C2O467 percent of the total mass of the four materials) and 30g of LiCl-LiBr-KBr system eutectic salt (accounting for 15 percent of the mass of the quasi-solid electrolyte), and Li is added2CO3、ZrO2、H2C2O4And putting the eutectic salt and a LiCl-LiBr-KBr system in a forced air drying oven, and drying for 2h at the drying temperature of 120 ℃. Mixing 98g of La2O3，62g Li2CO3，49g ZrO2And 418g H2C2O4And putting the mixture into an agate mortar, uniformly grinding the mixture, putting the mixture into a stainless steel tank, roasting the mixture for 2 hours at 1200 ℃, naturally cooling the mixture to room temperature, and ball-milling and crushing the blocky product to obtain the LLZO. Uniformly mixing the obtained LLZO and 30g LiCl-LiBr-KBr system eutectic salt, then placing the mixture in an atmosphere protection furnace, rapidly heating to 400 ℃ under the protection of argon, stopping heating, maintaining the temperature at 400 ℃, vacuumizing to-1.0 MPa when the temperature just reaches 400 ℃, slowly introducing argon, pressurizing to 0.1MPa, repeating the steps for 3 times, then repeating the operations of vacuumizing and pressurizing for 3 times every 1h, starting to cool and recovering to normal pressure after the temperature at 400 ℃ is maintained for 4h, and after the product is naturally cooled to room temperature, ball-milling and crushing the product to obtain the quasi-solid electrolyte for the thermal battery.
In this example, the evacuation and pressurization were repeated 4 times, and the number of repetitions was 3 times each.
In conclusion, the quasi-solid electrolyte for the missile-borne thermal battery suitable for the harsh mechanical environment is synthesized for the first time, and the electrolyte material has the main advantages that the conventionally used liquid electrolyte (eutectic salt) is replaced by the LLZO solid electrolyte which does not flow at high temperature;
secondly, a small amount of molten salt electrolyte is added into the LLZO, so that a rapid ion transmission channel is established, the ionic conductivity of the electrolyte material is improved, and the requirement of high-power output of a thermal battery is met;
thirdly, in the preparation process, the working characteristics of the thermal battery are considered, the added eutectic salt is better soaked in the LLZO, the sintering time of the LLZO is shortened, the preparation process of the LLZO is simplified, the large-scale industrial production of the LLZO is possible, and the LLZO has military significance and economic value.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to limit the present invention, and those skilled in the art can make variations and modifications of the present invention without departing from the spirit and scope of the present invention by using the methods and technical contents disclosed above.
Claims (4)
1. The preparation method of the quasi-solid electrolyte for the thermal battery comprises the steps of preparing a quasi-solid electrolyte for the thermal battery, wherein the quasi-solid electrolyte for the thermal battery is composed of LLZO and alkali metal halide eutectic salt which are in a porous loose structure, the mass percentage of the LLZO is 85-95%, and the mass percentage of the alkali metal halide eutectic salt is 5-15%;
the LLZO preparation method comprises the following steps:
1) at the dew point of less than-40 ℃, adding La2O3Roasting at 800-1000 deg.c for 12-15 hr to eliminate La (OH)3Impurities of Li2CO3、ZrO2And H2C2O4Drying in a forced air drying oven;
2) according to the component content of LLZO, calculating and respectively weighing the required Li2CO3、La2O3And ZrO2Weighing appropriate amount of H2C2O4Mixing and grinding the four materials uniformly, roasting for 2-8 h at 1000-1200 ℃, then naturally cooling, and performing ball milling and uniform crushing to obtain LLZO; h2C2O4Accounting for 60-67% of the total mass of the four materials;
in said step 1), Li2CO3、ZrO2And H2C2O4Drying the mixture for 2 to 4 hours in a blast drying oven at the drying temperature of between 120 and 150 ℃;
in said step 2), Li2CO3The excess is 10-20%;
it is characterized by comprising:
step one, La is added under the environment with the dew point less than minus 40 DEG C2O3Roasting at 800-1000 deg.c for 12 hr to eliminate La (OH)3Impurities of Li2CO3、ZrO2、H2C2O4Co-molten salt with alkali metal halide is placed in a forced air drying oven for drying;
step two, calculating and respectively weighing the required Li according to the component content of the LLZO2CO3、La2O3And ZrO2Weighing appropriate amount of H2C2O4Mixing and grinding the four materials uniformly, roasting for 2-8 h at 1000-1200 ℃, then naturally cooling, and performing ball milling and uniform crushing to obtain LLZO; h2C2O4Accounting for 60-67% of the total mass of the four materials;
weighing the LLZO and alkali metal halide eutectic salt, wherein the mass percentage of the LLZO is 85-95%, and the mass percentage of the alkali metal halide eutectic salt is 5-15%; mixing and grinding LLZO and alkali metal halide eutectic salt uniformly, heating to 400-500 ℃ under the protection of argon, maintaining the temperature unchanged, vacuumizing until the reading of a pressure gauge is less than-0.9 MPa, slowly introducing argon until the reading of the pressure gauge reaches 0.1-0.3MPa, and repeating the operations of vacuumizing and introducing argon for pressurizing for 3-5 times; and repeating the operations of vacuumizing and argon introducing for 3-5 times every 1h, cooling and recovering to normal pressure after 2-4 h, naturally cooling to room temperature, and performing ball milling and crushing on the blocky product to obtain the quasi-solid electrolyte for the thermal battery.
2. The method for preparing a quasi-solid electrolyte for a thermal battery according to claim 1, wherein, in the first step, the alkali halide eutectic salt is a LiF-LiCl-LiBr system, a LiCl-LiBr-KBr system, or a LiCl-KCl system.
3. The method of claim 1, wherein in the second step, Li is added2CO3、ZrO2、H2C2O4And putting the eutectic salt and alkali metal halide into a forced air drying oven to dry for 2 to 4 hours at the drying temperature of between 120 and 150 ℃.
4. The method of claim 1, wherein in step two, Li is added to the quasi-solid electrolyte for a thermal battery2CO3The excess is 10-20%.
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| CN113461050B (en) * | 2021-07-20 | 2024-01-23 | 中国科学院上海硅酸盐研究所 | Porous LLZO ceramic powder inhibitor for thermal battery electrolyte and preparation method thereof |
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| CN102244257B (en) * | 2011-06-15 | 2014-02-05 | 清华大学深圳研究生院 | High-temperature manganic acid lithium cathode material and preparation method thereof |
| KR101405588B1 (en) * | 2011-11-15 | 2014-06-20 | 현대자동차주식회사 | Construction Method of Solid Electrolytes of the Porous Membrance Film and Dye-Sensitized Solar Cell Using thereof |
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| CN103594725B (en) * | 2012-08-17 | 2016-02-17 | 万向电动汽车有限公司 | A kind of lithium ion battery solid electrolyte material Li 7la 3zr 2o 12preparation method |
| CN104332651B (en) * | 2014-11-06 | 2018-03-20 | 山东大学 | A kind of molten-salt growth method prepares carbuncle type Li7La3Zr2O12The method of electrolyte powder |
| CN105428705A (en) * | 2015-10-30 | 2016-03-23 | 中南大学 | Low-temperature rapid sintering-based method for preparing Li<7>La<3>Zr<2>O<12> solid electrolyte |
| CN108417889B (en) * | 2018-02-02 | 2020-08-28 | 中国科学院宁波材料技术与工程研究所 | Preparation method of lithium lanthanum zirconium oxide based oxide powder |
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