CN111477948A - Preparation method of garnet type solid electrolyte and product - Google Patents

Preparation method of garnet type solid electrolyte and product Download PDF

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CN111477948A
CN111477948A CN202010337095.1A CN202010337095A CN111477948A CN 111477948 A CN111477948 A CN 111477948A CN 202010337095 A CN202010337095 A CN 202010337095A CN 111477948 A CN111477948 A CN 111477948A
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salt
solid electrolyte
lanthanum
mixed solution
zirconium
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薛丽红
张航
宋健
张五星
严有为
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Huazhong University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
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    • H01M2300/0068—Solid electrolytes inorganic
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Abstract

The invention discloses a preparation method of garnet type solid electrolyte and a product, belonging to the field of solid electrolyte, wherein the preparation method comprises L i7‑xMxLa3Zr2O12Weighing lithium salt, lanthanum salt, zirconium salt and M salt according to a stoichiometric ratio, dissolving the lithium salt, the lanthanum salt, the zirconium salt and the M salt in a solvent to obtain a mixed solution, placing the mixed solution in a reaction kettle for hydrothermal reaction to obtain a hydrothermal product, taking the dried hydrothermal product as a precursor, and carrying out heat treatment on the precursor to obtain L i7‑xMxLa3Zr2O12A solid electrolyte; wherein M is Ga or Al, and the value range of x is 0-0.4. The preparation method has the advantages of simple process, low cost, environmental protection and easy mass production.

Description

Preparation method of garnet type solid electrolyte and product
Technical Field
The invention belongs to the field of solid electrolytes, and particularly relates to a preparation method and a product of a garnet-type solid electrolyte.
Background
In the traditional lithium ion battery, an electrolyte mainly comprises lithium salt, ethers, esters and other organic solvents, the liquid electrolyte is easy to generate side reaction with electrode materials in the charging and discharging processes, so that the battery capacity is irreversibly attenuated, and the problems of gas expansion, liquid leakage, spontaneous combustion and the like are brought7La3Zr2O12As a typical solid electrolyte, there are many advantages, therefore, garnet L i7La3Zr2O12The solid electrolyte has good application prospect in the aspect of developing all-solid batteries.
At present, L i7La3Zr2O12The preparation method of the material mainly comprises a solid phase method, a sol-gel method, a coprecipitation method, a solution combustion method and the like, wherein the solid phase method has high synthesis temperature, long sintering time, energy waste and lithium volatilization, and the sol-gel method can obtain L i at a lower heat treatment temperature7La3Zr2O12The materials, however, a large amount of organic matters such as citric acid and the like are needed to be used as complexing agents or expensive organic metal salts are needed to be used as reaction raw materials, so that the cost is high, and environmental pollution and waste are easily caused; although the solution combustion method is rapid in preparation, a large amount of harmful gas is easily generated in the preparation process, the method is not environment-friendly, and the fuel is often incompletely decomposed and easily generates impurities. Therefore, the new preparation method of the garnet-type solid electrolyte which is cheap, simple, easy to operate and environment-friendly is found to have great application value.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a preparation method of a garnet type solid electrolyte and a product, thereby solving the technical problems of high cost, complex process and easy environmental pollution in the prior art.
To achieve the above objects, according to one aspect of the present invention, there is provided a method for preparing a garnet-type solid electrolyte, comprising the steps of:
(1) according to L i7-xMxLa3Zr2O12Weighing lithium salt, lanthanum salt, zirconium salt and M salt according to a stoichiometric ratio, and dissolving the lithium salt, the lanthanum salt, the zirconium salt and the M salt in a solvent to obtain a mixed solution;
(2) placing the mixed solution in a reaction kettle, carrying out hydrothermal reaction to obtain a hydrothermal product, taking the dried hydrothermal product as a precursor, and carrying out thermal treatment on the precursor to obtain L i7-xMxLa3Zr2O12A solid electrolyte;
wherein M is Ga or Al, and the value range of x is 0-0.4.
Further, the step (1) comprises:
according to L i7-xMxLa3Zr2O12Weighing lithium salt, lanthanum salt, zirconium salt and M salt according to a stoichiometric ratio, respectively dissolving the lithium salt, the lanthanum salt, the zirconium salt, the M salt and urea in a solvent, and mixing, wherein the molar ratio of the sum of the lithium salt, the lanthanum salt, the zirconium salt and the M salt to the urea is 2: 1-1: 5, so as to obtain a transparent mixed solution.
Further, the step (1) comprises:
according to L i7-xMxLa3Zr2O12Weighing lithium salt, lanthanum salt, zirconium salt and M salt according to a stoichiometric ratio, dissolving the lithium salt, the lanthanum salt, the zirconium salt and the M salt in a solvent respectively, mixing the lanthanum salt, the zirconium salt and the M salt, and then adding the lithium salt solution to obtain a suspended mixed solution.
Further, the content of lithium salt exceeds L i7-xMxLa3Zr2O12And weighing 5-20 wt% of the lithium salt according to the stoichiometric ratio.
Further, the solvent is deionized water, ethanol or a mixed solution of ethanol and deionized water.
Further, during the hydrothermal reaction, the volume filling rate of the mixed solution in the reaction kettle is 50-90%, the temperature of the hydrothermal reaction is 120-200 ℃, and the time is 6-48 hours.
Further, the specific implementation manner of drying is as follows:
and stirring and drying the hydrothermal product at 80-100 ℃.
Further, the specific implementation manner of the heat treatment is as follows:
and carrying out heat treatment on the precursor at 750-1000 ℃ for 1-6 h.
According to another aspect of the present invention, there is provided a garnet-type solid electrolyte prepared by the method, wherein the garnet-type solid electrolyte is a cubic phase having a chemical formula of L i7-xMxLa3Zr2O12Wherein M is Ga or Al, and the value range of x is 0-0.4.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) the present invention uses lithium salt, lanthanum salt, zirconium salt and M salt (M is Ga or Al) as raw materials, and the garnet type solid electrolyte is obtained by mixing, hydrothermal reaction, drying and heat treatment in turn.
(2) The mixed solution can be obtained by mixing the salt solution and the urea, and can also be obtained by different adding sequences of the salt solution. The mixed solution is various in acquisition form and simple in acquisition mode, the lithium salt in the raw material is excessive so as to be capable of fully reacting in the subsequent reaction, and deionized water, ethanol or ethanol and deionized water are used as solvents, so that the cost is low, the environment is friendly, and the purity of the subsequent product is high.
(3) The invention utilizes a reaction kettle to carry out hydrothermal reaction, the hydrothermal method takes aqueous solution or organic solution as reaction medium, a reaction system is heated to the temperature near critical temperature in a closed container such as a high-pressure reaction kettle and the like, and the system which does not react at normal temperature or has low reaction speed is promoted to react rapidly by utilizing the high-pressure physical environment generated by the reaction system, thereby preparing the required material. Particularly, the hydrothermal method has unique advantages in the controlled synthesis of powder with different shapes.
(4) According to the invention, when the reaction kettle is used for carrying out hydrothermal reaction, the volume filling rate is 50-90%, and the hydrothermal reaction is carried out for 6-48 hours at 120-200 ℃, so that a hydrothermal product is obtained, low-temperature synthesis is really realized, volatilization of substances is reduced, the accuracy of the stoichiometric ratio of the reaction product is ensured, and the synthesized powder has fine grains and good dispersibility by using the low-temperature high-pressure environment.
(5) The hydrothermal product is stirred and dried at the temperature of 80-100 ℃ to obtain a precursor, and then the precursor is subjected to heat treatment at the temperature of 750-1000 ℃ for 1-6 hours to obtain the cubic-phase garnet-type solid electrolyte.
(6) The product prepared by the invention can be applied to lithium ion batteries, and the chemical formula of the product is L i7-xMxLa3Zr2O12Wherein M is Ga or Al, the value range of x is 0-0.4, and if the value exceeds 0.4, a cubic phase cannot be obtained. The product has the following advantages: the fuel is non-combustible, so that safety problems such as combustion, leakage and the like can be effectively avoided; the battery has the double functions of conducting lithium ions and positive and negative diaphragms, and can simplify the structure of the battery; the battery has high working voltage, theoretically higher energy density than the traditional lithium ion battery, good chemical stability and electrochemical stability and wide working temperature range.
Drawings
FIG. 1 is an X-ray diffraction pattern of sample # 1 in example 1 of the present invention;
FIG. 2 is an SEM photograph of sample No. 1 in example 1 of the present invention;
FIG. 3 is an SEM photograph of sample No. 2 in example 2 of the present invention;
FIG. 4 is an SEM photograph of sample # 3 in example 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a preparation method of garnet type solid electrolyte, which comprises the following steps:
(1) according to L i7-xMxLa3Zr2O12Weighing lithium salt, lanthanum salt, zirconium salt and M salt according to a stoichiometric ratio, and dissolving the lithium salt, the lanthanum salt, the zirconium salt and the M salt in a solvent to obtain a mixed solution;
(2) placing the mixed solution in a reaction kettle, carrying out hydrothermal reaction to obtain a hydrothermal product, taking the dried hydrothermal product as a precursor, and carrying out thermal treatment on the precursor to obtain L i7-xMxLa3Zr2O12A solid electrolyte;
wherein M is Ga or Al, and the value range of x is 0-0.4.
Further, the step (1) comprises:
according to L i7-xMxLa3Zr2O12Weighing lithium salt, lanthanum salt, zirconium salt and M salt according to a stoichiometric ratio, respectively dissolving the lithium salt, the lanthanum salt, the zirconium salt, the M salt and urea in a solvent, and mixing, wherein the molar ratio of the sum of the lithium salt, the lanthanum salt, the zirconium salt and the M salt to the urea is 2: 1-1: 5, so as to obtain a transparent mixed solution.
Further, the step (1) comprises:
according to L i7-xMxLa3Zr2O12Weighing lithium salt, lanthanum salt, zirconium salt and M salt according to a stoichiometric ratio, dissolving the lithium salt, the lanthanum salt, the zirconium salt and the M salt in a solvent respectively, mixing the lanthanum salt, the zirconium salt and the M salt, and then adding the lithium salt solution to obtain a suspended mixed solution.
The lithium salt is L iNO3Or L iOH, lanthanum salt L a (NO)3)3·6H2O, zirconium salt being ZrO (NO)3)2·xH2The salt of O, M is Ga (NO)3)3Or Al (NO)3)3。
Further, the content of lithium salt exceeds L i7-xMxLa3Zr2O12Weighing 5-20 wt% of lithium salt according to stoichiometric ratio％。
Further, the solvent is deionized water, ethanol or a mixed solution of ethanol and deionized water.
Further, during the hydrothermal reaction, the volume filling rate of the mixed solution in the reaction kettle is 50-90%, the temperature of the hydrothermal reaction is 120-200 ℃, and the time is 6-48 hours.
Further, the specific implementation manner of drying is as follows:
and stirring and drying the hydrothermal product at 80-100 ℃.
Further, the specific implementation manner of the heat treatment is as follows:
and carrying out heat treatment on the precursor at 750-1000 ℃ for 1-6 h.
Example 1
L iNO3、La(NO3)3·6H2O、ZrO(NO3)2·xH2O、Ga(NO3)3According to L i6.8Ga0.2La3Zr2O12Stoichiometric weighing of formula (la) wherein L iNO3The preparation method comprises the steps of weighing 5 wt% of urea according to a molar ratio of (L i salt + L a salt + Zr salt + Ga salt) to 1: 1, dissolving the reagents into a mixed solvent of deionized water and ethanol (the volume ratio of ethanol to water is 1: 1) respectively to obtain a transparent solution, mixing the transparent solution to obtain a transparent mixed solution, transferring the transparent mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal treatment at 120 ℃ for 48 hours, stirring and drying a hydrothermal product at 80 ℃ after the reaction is finished, obtaining a precursor, and carrying out thermal treatment on the precursor at 750 ℃ for 6 hours to obtain a sample No. 1.
Example 2
L iNO3、La(NO3)3·6H2O、ZrO(NO3)2·xH2O according to L i7La3Zr2O12Stoichiometric weighing of formula (la) wherein L iNO3Adding 20 wt% of urea in a molar ratio of (L i salt + L a salt + Zr salt) to urea of 1: 5, dissolving the above reagents in deionized water to obtain transparent solutions, and mixing the above solutionsMixing the solutions to obtain a transparent mixed solution; transferring the transparent mixed solution into a hydrothermal reaction kettle with the volume filling rate of 90 percent, and carrying out hydrothermal treatment for 6 hours at 200 ℃. After the reaction is finished, stirring the hydrothermal product at 90 ℃ until the hydrothermal product is dried to obtain a precursor; the precursor was then heat treated at 1000 ℃ for 1h to give sample # 2.
Example 3
L iOH, L a (NO)3)3·6H2O、ZrO(NO3)2·xH2O、Al(NO3)3According to L i6.6Al0.4La3Zr2O12The stoichiometric ratio of formula (II) is measured, wherein L iOH is excessive by 10 wt%, the above reagents are respectively dissolved in absolute ethyl alcohol to obtain transparent solution, and L a (NO) is added3)3Solution, ZrO (NO)3)2Solution, Al (NO)3)3Mixing the solutions together to obtain a transparent solution, adding L iOH solution into the mixed solution of L a, Zr and Al to obtain a suspension, transferring the suspension into a hydrothermal reaction kettle, carrying out hydrothermal treatment at 190 ℃ for 40h to obtain a precursor, stirring the hydrothermal product at 100 ℃ to dry after the reaction is finished, and carrying out thermal treatment on the precursor at 900 ℃ for 2h to obtain a 3# sample.
Example 4
L iOH, L a (NO)3)3·6H2O、ZrO(NO3)2·xH2O、Al(NO3)3According to L i6.6Al0.4La3Zr2O12Weighing L iOH with the excess of 10 wt%, weighing urea with the molar ratio of L i salt + L a salt + Zr salt + Al salt to 2: 1, dissolving the reagents in absolute ethyl alcohol respectively to obtain transparent solutions, mixing the transparent solutions to obtain transparent mixed solutions, transferring the transparent mixed solutions into a hydrothermal reaction kettle with the volume filling rate of 80%, carrying out hydrothermal treatment at 150 ℃ for 43 hours, stirring the hydrothermal products at 100 ℃ to dry after the reaction is finished, obtaining precursors, carrying out thermal treatment at 900 ℃ for 2 hours to obtain 4# samples, and obtaining 4# samplesIs a pure garnet-type cubic phase structure.
Example 5
L iOH, L a (NO)3)3·6H2O、ZrO(NO3)2·xH2O、Al(NO3)3According to L i6.7Al0.3La3Zr2O12Weighing L iOH with the excess of 12 wt%, weighing urea according to the molar ratio of L i salt + L a salt + Zr salt + Al salt to 1: 3, respectively dissolving the reagents into absolute ethyl alcohol to obtain transparent solutions, mixing the transparent solutions to obtain transparent mixed solutions, transferring the transparent mixed solutions into a hydrothermal reaction kettle with the volume filling rate of 70%, carrying out hydrothermal treatment at 180 ℃ for 41 hours, after the reaction is finished, stirring and drying hydrothermal products at 95 ℃ to obtain precursors, and carrying out thermal treatment on the precursors at 800 ℃ for 3 hours to obtain 5# samples, wherein the 5# samples are pure garnet-type cubic phase structures.
FIG. 1 is the X-ray diffraction pattern of sample # 1 in example 1, and it can be seen that the sample # 1 after heat treatment has a pure garnet-type cubic phase structure.
FIG. 2 is an SEM photograph of sample No. 1 of example 1, and it can be seen that the sample No. 1 has a uniform particle size distribution, a small particle size, and an average particle size of about 0.2 μm.
FIG. 3 is an SEM photograph of sample No. 2 of example 2, from which it can be seen that the sample No. 2 is composed of irregular particles having an average size of about 1.0. mu.m.
FIG. 4 is an SEM photograph of sample # 3 of example 3. As can be seen from the figure, the microstructure of the sample No. 2 is a porous network structure, and the radial dimension of the particles is about 0.5 μm.
It is easily understood by those skilled in the art that the kind, quality and reaction temperature, time, doping, etc. of the raw materials used in the present invention are not limited to the specific values in the above examples. The above description is only exemplary of the present invention and should not be taken as limiting, and any modifications, equivalents, improvements, etc. that are made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A preparation method of a garnet-type solid electrolyte is characterized by comprising the following steps:
(1) according to L i7-xMxLa3Zr2O12Weighing lithium salt, lanthanum salt, zirconium salt and M salt according to a stoichiometric ratio, and dissolving the lithium salt, the lanthanum salt, the zirconium salt and the M salt in a solvent to obtain a mixed solution;
(2) placing the mixed solution in a reaction kettle, carrying out hydrothermal reaction to obtain a hydrothermal product, taking the dried hydrothermal product as a precursor, and carrying out thermal treatment on the precursor to obtain L i7-xMxLa3Zr2O12A solid electrolyte;
wherein M is Ga or Al, and the value range of x is 0-0.4.
2. The method of claim 1, wherein the step (1) comprises:
according to L i7-xMxLa3Zr2O12Weighing lithium salt, lanthanum salt, zirconium salt and M salt according to a stoichiometric ratio, respectively dissolving the lithium salt, the lanthanum salt, the zirconium salt, the M salt and urea in a solvent, and mixing, wherein the molar ratio of the sum of the lithium salt, the lanthanum salt, the zirconium salt and the M salt to the urea is 2: 1-1: 5, so as to obtain a transparent mixed solution.
3. The method of claim 1, wherein the step (1) comprises:
according to L i7-xMxLa3Zr2O12Weighing lithium salt, lanthanum salt, zirconium salt and M salt according to a stoichiometric ratio, dissolving the lithium salt, the lanthanum salt, the zirconium salt and the M salt in a solvent respectively, mixing the lanthanum salt, the zirconium salt and the M salt, and then adding the lithium salt solution to obtain a suspended mixed solution.
4. The method for preparing a garnet-type solid electrolyte as claimed in any of claims 1 to 3, whereinThe content of the lithium salt exceeds L i7-xMxLa3Zr2O12And weighing 5-20 wt% of the lithium salt according to the stoichiometric ratio.
5. The method of any one of claims 1 to 3, wherein the solvent is deionized water, ethanol, or a mixed solution of ethanol and deionized water.
6. The method for producing a garnet-type solid electrolyte as claimed in any one of claims 1 to 3, wherein the volume filling rate of the mixed solution in the reaction vessel at the hydrothermal reaction is 50 to 90%.
7. The method for producing a garnet-type solid electrolyte as claimed in any one of claims 1 to 3, wherein the hydrothermal reaction is carried out at a temperature of 120 to 200 ℃ for 6 to 48 hours.
8. The method of any of claims 1 to 3, wherein the drying is carried out by:
and stirring and drying the hydrothermal product at 80-100 ℃.
9. The method of any of claims 1 to 3, wherein the heat treatment is carried out by:
and carrying out heat treatment on the precursor at 750-1000 ℃ for 1-6 h.
10. The garnet-type solid electrolyte prepared by the method of any one of claims 1 to 9, wherein the garnet-type solid electrolyte is a cubic phase having a chemical formula of L i7- xMxLa3Zr2O12Wherein M is Ga or Al, and the value range of x is 0-0.4.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112047736A (en) * 2020-08-19 2020-12-08 上海纳米技术及应用国家工程研究中心有限公司 Preparation and ceramic sintering method of high-conductivity solid electrolyte lithium lanthanum zirconium oxide powder
CN112467116A (en) * 2020-11-30 2021-03-09 湖南中科星城石墨有限公司 Graphite coating material, preparation method thereof and battery cathode
CN113336547A (en) * 2021-04-22 2021-09-03 海南大学 Oxide type solid electrolyte film and preparation method thereof
CN113336547B (en) * 2021-04-22 2022-05-31 海南大学 Oxide type solid electrolyte film and preparation method thereof
CN114605152A (en) * 2022-04-27 2022-06-10 佛山(华南)新材料研究院 Cubic-phase lithium lanthanum zirconium oxide and preparation method thereof
CN114605152B (en) * 2022-04-27 2022-11-29 佛山(华南)新材料研究院 Cubic-phase lithium lanthanum zirconium oxide and preparation method thereof

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Application publication date: 20200731