CN112374525A - Solid electrolyte material, solid electrolyte layer and preparation method thereof - Google Patents
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Abstract
The application relates to a solid electrolyte material, a solid electrolyte layer and a preparation method thereof, belonging to the technical field of new energy, and the preparation method of the solid electrolyte material comprises the following steps: 1) mixing deionized water and an organic solvent in proportion to prepare a mixed solvent; 2) respectively mixing the mixed solvent prepared in the step 1) with La3+Soluble salts of ions, containing Ba2+Mixing soluble salts of ions and ammonium fluoride to form three solutions, and mixing the three solutions under the assistance of ultrasonic waves to prepare the LaxBa1‑xF2+x(0<x < 1) is released and worked up to give dry LaxBa1‑xF2+x(0<x < 1) solid electrolyte material. The solid electrolyte material prepared by the method has uniform particle size, the ionic conductivity is superior to that of the solid electrolyte material prepared by a high-energy ball milling method, the process is simple, and long-time ball milling and high-temperature sintering are not needed.
Description
Technical Field
The application relates to the field of new energy materials, in particular to a solid electrolyte material, a solid electrolyte layer and a preparation method thereof.
Background
In the face of the increasing global energy demand and the shrinking fossil energy and the series of environmental problems caused by the use of the latter, the development of efficient, environmentally friendly and energy-dense energy storage systems is imperative. At present, lithium ion batteries play an important role in life, but because of potential safety hazards such as spontaneous combustion and explosion, the energy density is close to a bottleneck value, and the lithium resources are limited and the price is high, so that novel energy storage batteries with lower development cost, higher safety and higher energy density become research hotspots concerned by people.
Fluorine Ion Batteries (FIBs) are a new energy storage battery system, and although research of the Fluorine Ion Batteries (FIBs) is in the beginning stage, the Fluorine Ion Batteries (FIBs) attract more and more scientists to pay attention by virtue of the advantages of high energy density, wide electrochemical window, good migration kinetics of charge transport ions and the like. The difficulty in obtaining a high performance FIB is that F is allowed-The development of electrolyte which can be rapidly transmitted in the electrochemical reaction process and the development of electrode materials for realizing fluorine-based electrochemical reaction. The solid electrolyte can realize higher energy output and a wide electrochemical window, and has the advantages of high melting point, nonflammability and the like; on the other hand, the external package of the solid-state battery can be simplified, a unit with a larger area can be manufactured in a roll-to-roll mode, and a plurality of layers of electrodes can be laminated in the unit to form a series connection to manufacture a large-voltage unit; in addition, the solid electrolyte can avoid the liquid electrolyte leakage defect, and the battery can be made into a high-energy battery which is thinner (the thickness is only 0.1mm), higher in energy density and smaller in volume.
M.A.Reddy et al cerium lanthanum ore structure solid solution (La) by high energy ball milling1-xBaxF3-x0. ltoreq. x. ltoreq.0.55) as a solid electrolyte for FIB and by optimizing BaF2The doping concentration of (2.8X 10) at 160 ℃ is obtained-4Optimum F of S/cm-Electrical conductivity. Respectively preparing La by Dieudonne et al by solid phase synthesis1-xBaxF3-x，Sm1-xCaxF3-xA mischmetal of 6X 10 is obtained-5Room temperature conductivity of S/cm. L.Zhang and the like, and La with the thickness of only 4-5 mu m is prepared by using a spin coating process0.9Ba0.1F2.9Thin film electrolyte layer, F at 170 ℃-The conductivity can reach 1.6 multiplied by 10-4S/cm. Bhatia et al prepared La by wet chemical synthesis combined with solid phase sintering1-xBaxF3-x(x is more than or equal to 0 and less than or equal to 0.15) solid solution to obtain 1.26 multiplied by 10-4Conductivity S/cm (60 ℃).
International, especially japan, research and application of fluoride solid electrolytes are actively conducted. Among them, the toyota automotive co, which is the most studied, has already achieved certain results, and on this basis, a series of applications have been proposed in china, for example, patent document 1 with application No. 201711051104.5, patent document 2 with application No. 201911309509.3, and patent document 3 with application No. 201910279485.5, all of which relate to the preparation of FIB fluoride solid electrolytes. In the above patent applications, the solid electrolyte material is prepared by high-energy ball milling method, and raw material LaF is used3And BaF2Mixing according to a certain molar ratio, grinding and mixing for a long time at a high speed by a ball mill, and then carrying out heat treatment on the mixed powder at a high temperature to obtain La1-xBaxF3-xA solid electrolyte. Among them, in example 1 disclosed in patent document 1, LaF3And BaF2The mixed material needs to be subjected to ball milling and mixing for 12 hours, and then is subjected to heat treatment at 600 ℃ for 10 hours to obtain La0.9Ba0.1F2.9A solid electrolyte material.
La prepared by the high-energy ball milling method1-xBaxF3-xThe inventors believe that the following drawbacks exist for solid state electrolyte materials: the long-time ball milling has high degree of dependence on equipment and long ball milling time, high-temperature sintering is needed after ball milling, and the preparation process is complex.
Disclosure of Invention
In order to solve the problem that the preparation of the solid electrolyte material is highly dependent on the ball milling process, the application provides the solid electrolyte material, the solid electrolyte layer and the preparation method thereof.
In a first aspect, the present application provides a method for preparing a solid electrolyte material, which adopts the following technical scheme:
a method of preparing a solid state electrolyte material comprising the steps of:
1) mixing deionized water and an organic solvent in proportion to prepare a mixed solvent;
2) respectively mixing the mixed solvent prepared in the step 1) with La3+Soluble salts of ions, Ba2+Mixing soluble salts of ions and ammonium fluoride to form three solutions, and mixing the three solutions under the assistance of ultrasonic waves to prepare the LaxBa1-xF2+x(0<x < 1) is released and post-treated to obtain LaxBa1-xF2+x(0<x < 1) solid electrolyte material.
By adopting the technical scheme, the powder La is preparedxBa1-xF2+x(0<x < 1) solid electrolyte material with uniform particle size and ion conductivity of 3.57 x 10 at room temperature of 25 deg.C-6S/cm, the ionic conductivity at 50 ℃ can reach 2.02 multiplied by 10-5S/cm, and the ionic conductivity at 75 ℃ can reach 3.61 multiplied by 10-5S/cm, and the ionic conductivity at 100 ℃ can reach 5.10 multiplied by 10-5S/cm, superior to La prepared by high-energy ball milling methodxBa1-xF2+x(0<x is less than 1), and the process is simple, and long-time ball milling and high-temperature sintering are not needed.
Preferably, the volume ratio of the deionized water to the organic solvent is (1:1) - (1:3), and preferably 1: 1.
The volume ratio of the deionized water to the organic solvent is controlled, so that the particle size of the solid electrolyte material is controlled, and the average size of the particle size is distributed in the range of 10-40 nm.
Preferably, x satisfies 0.3 ≦ x ≦ 0.7, preferably 0.3 to 0.4.
By adopting the technical scheme, the ionic conductivity of the prepared solid electrolyte material, particularly the ionic conductivity at low temperature, can be improved, the working temperature of the fluorine ion battery is reduced, the operability of the fluorine ion battery is improved, and the application field of the fluorine ion battery is expanded.
Preferably, among the three solutions, La3+The soluble salt solution of the ions is a saturated solution of soluble salt at room temperature of 25 ℃; ba2+The soluble salt solution of the ions is a saturated solution of soluble salt at room temperature of 25 ℃; the concentration of the ammonium fluoride solution is 5-6 mol/L, preferably 5 mol/L.
By adopting the technical scheme, the reaction efficiency and the yield of the released substances can be improved, and the average size of crystal grains of the solid electrolyte material powder can be controlled to be 10-40 nm.
Preferably, the La3+The soluble salt of the ion is nitrate or chloride, and the Ba2+Soluble salts of ions are nitrate or chloride, La3+The soluble salt of the ion is preferably La (NO)3)3，Ba2+The soluble salt of the ion is preferably Ba (NO)3)2。
Preferably, the working power of the ultrasonic wave is 50-100W, preferably 50W.
In a second aspect, the present application provides a solid electrolyte material prepared by the above method.
The electrochemical performance of the fluorine ion battery is improved by applying the solid electrolyte material to the FIB electrode material and the electrolyte material.
And in the third aspect, the solid electrolyte layer is obtained by cold pressing the solid electrolyte material into a blank and sintering at 200-1000 ℃ in an inert atmosphere, wherein the sintering time is 2-4 h.
By adopting the technical scheme, the solid electrolyte material is subjected to cold press molding and then sintered to obtain the submicron solid electrolyte layer with uniform particle size, and the ionic conductivity of the solid electrolyte layer is further improved compared with that of the solid electrolyte material.
Preferably, the sintering temperature is 400-800 ℃, preferably 800 ℃, and the sintering time is 2 h.
By adopting the technical scheme, the density of the sintered solid electrolyte layer of the solid electrolyte layer obtained after sintering can reach 95%, the particle size is uniform, the size distribution is 100-600 nm, the average particle size is 300nm, and the ionic conductivity at room temperature of 25 ℃ can reach 7.93 multiplied by 10-5S/cm, and 100 ℃ ion conductivity can reach 1.19 multiplied by 10-3S/cm, the working temperature of FIB prepared by the solid electrolyte layer can be reduced.
In a third aspect, the present application provides a solid electrolyte layer prepared by the above method.
By applying a solid electrolyte layer to the FIB, the battery performance of the FIB can be improved.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the preparation method of the solid electrolyte material is simple in process and short in process flow, and can be used for preparing La with the average particle size of 10-40 nmxBa1-xF2+x(0<x is less than 1), the powder particle size of the solid electrolyte material is uniform, and the solid electrolyte material has higher fluorine ion conductivity and high chemical/electrochemical stability, can be applied to FIB and realizes good electrochemical performance;
2. according to the preparation method of the solid electrolyte layer, the solid electrolyte material is sintered after being pressed into a compact, the solid electrolyte layer with submicron and uniform particle size can be prepared, and the fluorine ion conductivity of the solid electrolyte layer can be further improved compared with that of the solid electrolyte material. After sintering, the density of the solid electrolyte layer can reach 95%, the particle size is uniform, the particle size distribution is 100-600 nm, the average particle size is 300nm, and the ionic conductivity at room temperature of 25 ℃ can reach 7.93 multiplied by 10-5S/cm, 100 ℃ ion conductivity can reach 1.19 multiplied by 10-3S/cm, capable of reducing FIB operation prepared from solid electrolyte layerAnd (3) temperature.
Drawings
FIG. 1 shows La prepared in example 1 of the present application0.4Ba0.6F2.4An XRD diffraction pattern of the solid state electrolyte material;
FIG. 2 shows La prepared in example 1 of the present application0.4Ba0.6F2.4TEM photographs of the solid electrolyte material;
FIG. 3 shows La prepared in example 1 of the present application0.4Ba0.6F2.4A photograph of the ion blocking electrode made of the solid electrolyte material of (1);
FIG. 4 is an electrochemical impedance spectrum of a solid electrolyte material of example 1 of the present application at room temperature of 25 ℃ and 100 ℃;
FIG. 5 is an electrochemical impedance spectrum of the solid electrolyte layer obtained after sintering the solid electrolyte material of example 1 of the present application at room temperature of 25 ℃ and 100 ℃;
fig. 6 is an SEM photograph of the solid electrolyte layer obtained after sintering of the solid electrolyte material of example 1 of the present application;
FIG. 7 shows La prepared in examples 2 to 4 of the present application and comparative examples 1 and 2xBa1-xF2+xAn XRD diffraction pattern of the solid state electrolyte material;
FIG. 8 shows La prepared in comparative examples 3 and 4 of the present application0.7Ba0.3F2.7XRD diffractogram of solid state electrolyte material.
Detailed Description
The present application will be described in further detail with reference to the following drawings and examples.
The embodiment of the application discloses a solid electrolyte material, a solid electrolyte layer and a preparation method thereof. Hereinafter, the solid electrolyte material, the solid electrolyte layer, and the method for producing the same according to the present application will be described in detail.
A. Solid electrolyte material
The solid electrolyte material of the present application is a fluoride solid electrolyte material for FIB, which has LaxBa1- xF2+x(0<x < 1) solid phase structure. According to the application, since there are specific groupsThe phase structure and the microstructure, so that the fluoride solid electrolyte material with high ion conductivity can be prepared. Further, as shown in examples described later, the solid electrolyte material of the present application can have an ionic conductivity of 3.57 × 10 at room temperature of 25 ℃ even in the state of powder molding-6S/cm, the ionic conductivity at 50 ℃ can reach 2.02 multiplied by 10-5S/cm, and the ionic conductivity at 75 ℃ can reach 3.61 multiplied by 10-5S/cm, and the ionic conductivity at 100 ℃ can reach 5.10 multiplied by 10-5S/cm is superior to the solid electrolyte material prepared by the high-energy ball milling method in patent document 1, and the process is simple and does not need long-time ball milling and high-temperature sintering.
In addition, in LaxBa1-xF2+x(0<x < 1) in the solid electrolyte material, x is 0.3 or more, may be 0.4 or more, and may be 0.5 or more. On the other hand, x is 0.7 or less. Preferably 0.3 to 0.7, and more preferably 0.3 to 0.4.
Preferably, the particle size of the solid electrolyte material powder of the embodiment of the present application is controlled to be 10 to 40 nm.
B. Method for preparing solid electrolyte material
The solid electrolyte material is prepared by the following preparation method: 1) mixing deionized water and an organic solvent in proportion to prepare a mixed solvent; 2) respectively mixing the mixed solvent prepared in the step 1) with La3+Soluble salts of ions, containing Ba2+Mixing soluble salts of ions and ammonium fluoride to form three solutions, and mixing the three solutions under the assistance of ultrasonic waves to prepare the LaxBa1-xF2+x(0<x < 1) is released and post-treated to obtain LaxBa1-xF2+x(0<x < 1) solid electrolyte material.
The post-treatment comprises the steps of centrifugal washing, drying and grinding to obtain the powder solid electrolyte material.
The mixed solvent is formed by mixing deionized water and an organic solvent, wherein the organic solvent can be ethanol or acetone. The volume of the deionized water and the ethanol or acetone is 1: 1-1: 3, can be 1:2, can be 1:3, and is preferably 1: 1.
Optionally, La of the present application3+Soluble salts of ions, containing Ba2+The soluble salt of the ion is nitrate or chloride, and the nitrate or chloride is soluble in water and does not react with the organic solvent solution to form other impurity precipitates or reactants.
In addition, the La is contained3+Soluble salt solution of ion, containing Ba2+The soluble salt solution of the ion is preferably a saturated solution at room temperature of 25 ℃, La (NO)3)3The concentration of the saturated solution is 0.4mol/L, Ba (NO)3)2The concentration of the saturated solution is 0.02 mol/L. The ammonium fluoride solution is preferably 5 to 6mol/L, and may be 5mol/L, 5.5mol/L, or 6 mol/L. The amount of ammonium fluoride added is at least 4 times the stoichiometric ratio.
The working power of the ultrasonic wave in the embodiment of the application is 50-100W, can be 50W, can be 75W, also can be 100W.
C. Solid electrolyte layer
The solid electrolyte layer is obtained by sintering the powder solid electrolyte material after being pressed into a compact at the temperature of 200-1000 ℃ and then preserving heat for 2-4 h. The sintering time may be 2 hours or more, 2.5 hours or more, and 4 hours or less. The optional green compact pressure is (0.7-1.2) x 105N, preferably 1X 105N, the sintering temperature can be 200 ℃, 400 ℃, 600 ℃, 800 ℃ and 1000 ℃, preferably 800 ℃.
The solid electrolyte layer prepared herein is a layer containing at least a solid electrolyte material. The solid electrolyte layer may contain only the solid electrolyte material, or may further contain a binder material.
Examples
Example 1
Preparing mixed solvent from deionized water and anhydrous ethanol at a volume ratio of 1:1, and preparing Ba (NO) with concentration of 0.02mol/L with the mixed solvent3)2Saturated solution, 0.4mol/L La (NO)3)3Saturated solution, 5mol/L NH4And F, solution. 300ml of Ba (NO)3)2The saturated solution was stirred with the aid of ultrasound (power 50W) and10ml of La (NO) was slowly added3)3The saturated solution was stirred for 5min, and then 22ml of NH were slowly added dropwise4F, stirring is continued for 30 min. La produced0.4Ba0.6F2.4Centrifuging and washing the white release for multiple times until the supernatant is dropped into FeSO4No precipitate was formed after the solution. Washing the La0.4Ba0.6F2.4Putting the released material into an oven, drying for 1h at 100 ℃, and then taking out the material, and grinding the material by using a mortar until the powder material is free of agglomerated particles.
FIG. 1 is La prepared in example 10.4Ba0.6F2.4XRD diffraction pattern of solid electrolyte material, La is shown in FIG. 10.4Ba0.6F2.4A solid electrolyte material having a good lattice structure and LaF3Bastnaesite structure and BaF2The main characteristic peak of fluorite structure.
FIG. 2 is La prepared in example 10.4Ba0.6F2.4Transmission electron microscopy of the solid electrolyte material, from FIG. 2, the La produced can be obtained0.4Ba0.6F2.4The solid electrolyte material is powder with uniform particle size distribution, and the particle size distribution of the particles is within the range of 10-20 nm.
And (3) performance characterization of the solid electrolyte material:
1) 0.35 g of dried La was taken0.4Ba0.6F2.4Placing the powder into a tungsten steel die with a diameter of 10mm and a pressure of 105N (pressure of 1.2GPa), and the powder is pressed into a circular sheet with the thickness of 1.12 mm.
2) Thickness measurement of solid electrolyte: the thickness of the circular sheet was measured with a digital vernier caliper (accurate to 0.02mm), and 7 points were arbitrarily set to calculate the average value.
3) Ionic conductivity: plating palladium electrodes on two sides of the electrolyte wafer by adopting a magnetron sputtering method (the back bottom vacuum is 5 multiplied by 10)-4Pa, argon flow of 25sccm, DC sputtering power of 100W, sputtering time of 1h, and platinum wire (purity 99.99%) adhered on both sides of conductive silver adhesive (model UN-6889) as lead wire to manufacture ion blocking electrode, and FIG. 3 shows the manufactured ion blocking electrodeAnd (4) a pole. Measuring impedance by electrochemical ac impedance spectroscopy, using the formula: sigma-L/SRbCalculating the ionic conductivity, wherein L is the thickness of the circular thin plate, S is the area of the ion-blocking electrode, and RbImpedance measured by electrochemical impedance spectroscopy.
FIG. 4 is La prepared in example 10.4Ba0.6F2.4Electrochemical impedance spectra of the solid electrolyte material measured at room temperature of 25 ℃ and 100 ℃. Measured La0.4Ba0.6F2.4The ion conductivity of the solid electrolyte material is shown in table 1.
Placing the round slice prepared in the step 1) in a tube furnace under the protection of argon (the flow rate is 500ml/min) to sinter at 800 ℃, the heating rate is 10 ℃/min, sintering is carried out for 2h, furnace cooling is carried out, and La is prepared0.4Ba0.6F2.4A solid electrolyte layer.
FIG. 5 is La0.4Ba0.6F2.4Electrochemical impedance spectra of the solid electrolyte layer at room temperature of 25 ℃ and 100 ℃. Preparation of the obtained La0.4Ba0.6F2.4The ion conductivity of the solid electrolyte layer is shown in table 1.
TABLE 1La0.4Ba0.6F2.4Ionic conductivity of solid electrolyte material and sintered solid electrolyte layer
The solid electrolyte material prepared in the embodiment 1 of the application can obtain better ionic conductivity of 5.1 multiplied by 10 at 100 DEG C-5S/cm, much higher than that in example 2 disclosed in patent document 1, La obtained by mixing by ball milling and then sintering0.9Ba0.1F2.9The ionic conductivity of the solid electrolyte material of (2). In patent document 1, the ionic conductivity at 110 ℃ is 6.14X 10- 6S/cm, which is nearly 10 times lower than the ionic conductivity at 100 ℃ in example 1 of the present application, and La in patent document 1 at 200 ℃0.9Ba0.1F2.9Solid electrolyte material ion electricityThe conductivity reaches 7.55X 10-5S/cm, equivalent to the ionic conductivity at 100 ℃ of example 1 of the present application.
After sintering, the room temperature of the obtained solid electrolyte layer at 25 ℃ can reach 7.93 multiplied by 10-5S/cm, and an ionic conductivity at 200 ℃ of 7.55X 10 in patent document 1-5The S/cm is equivalent, namely the solid electrolyte layer prepared in the embodiment 1 of the application can reduce the operation temperature of the fluorine ion battery from 200 ℃ to 25 ℃ at room temperature, and can be applied to the fluorine ion battery at room temperature, so that the application range and operability of the fluorine ion battery are greatly improved.
FIG. 6 shows La obtained by the preparation of example 10.4Ba0.6F2.4SEM photograph of the solid electrolyte layer of (1). From fig. 6, it can be seen that the solid electrolyte layer has a compact structure, and through density test analysis, the density of the solid electrolyte layer reaches 95%, and the solid electrolyte layer has uniform particle size, the particle size distribution of the particles is within the range of 100-600 nm, and the average particle size is 300 nm.
Example 2
The difference from example 1 is that 0.02mol/L of Ba (NO) is used3)2The volume of the saturated solution was 350ml, and 0.4mol/L of La (NO) was used3)3La was prepared in the same manner as in example 1 except that the volume of the saturated solution was 7.5ml0.3Ba0.7F2.3The solid electrolyte material of (1).
Example 3
The difference from example 1 is that 0.02mol/L of Ba (NO) is used3)2The volume of the saturated solution was 250ml, and 0.4mol/L of La (NO) was used3)3La was prepared in the same manner as in example 1 except that the volume of the saturated solution was 12.5ml0.5Ba0.5F2.5The solid electrolyte material of (1).
Example 4
The difference from example 1 is that 0.02mol/L of Ba (NO) is used3)2The volume of the saturated solution was 150ml, and 0.4mol/L of La (NO) was used3)3Volume of saturated solution was 17.5ml, whichLa was obtained in the same manner as in example 10.7Ba0.3F2.7The solid electrolyte material of (1).
Comparative example 1
The difference from example 1 is that La (NO)3)3BaF was prepared in the same manner as in example 1 except that the amount of the saturated solution added was 02The solid electrolyte material of (1).
Comparative example 2
The difference from example 1 is that Ba (NO)3)2LaF was prepared in the same manner as in example 1 except that the amount of the saturated solution added was 03The solid electrolyte material of (1).
FIG. 7 shows La prepared in examples 2 to 4 of the present application and comparative examples 1 and 2xBa1-xF2+xXRD diffractogram of solid state electrolyte material. It can be seen from FIG. 7 that the main characteristic peak of the crystal phase is represented by BaF as x is gradually increased from 0 to 12Fluorite structure gradually towards LaF3The characteristic peaks of the lanthanum bastnaside structure are shifted. Table 2 shows the results of XRD on La obtained by calculation according to the Sherle formula in examples 1 to 4 and comparative examples 1 and 2xBa1-xF2+xAverage grain size of the solid state electrolyte material.
TABLE 2 LaxBa1-xF2+xAverage grain size of solid electrolyte material
| LaxBa1-xF2+x | x＝0 | x＝0.3 | x＝0.4 | x＝0.5 | x＝0.7 | x＝1 |
| Average grain size (nm) | 37.5 | 25.5 | 19.8 | 18.6 | 16.4 | 17.8 |
Examples 2 to 4 and comparative examples 1 and 2 the method for measuring the ion conductivity of the solid electrolyte material was the same as in example 1, and the La was measuredxBa1-xF2+xThe ionic conductivity of the solid electrolyte material at 100 ℃ is shown in Table 3, and the measured La after 2h of sintering at 800 ℃ isxBa1-xF2+xThe ion conductivity of the solid electrolyte layer at 100 ℃ is shown in table 4.
TABLE 3 LaxBa1-xF2+xIonic conductivity of solid electrolyte material at 100 DEG C
| LaxBa1-xF2+x | x＝0 | x＝0.3 | x＝0.4 | x＝0.5 | x＝0.7 | x＝1 |
| Ionic conductivity (. times.10) at 100 ℃-6S/cm) | 3.82 | 59.4 | 51 | 18.3 | 21.8 | 6.01 |
TABLE 4 LaxBa1-xF2+xIon conductivity of solid electrolyte layer at 100 DEG C
| LaxBa1-xF2+x | x＝0 | x＝0.3 | x＝0.4 | x＝0.5 | x＝0.7 | x＝1 |
| Ionic conductivity (. times.10) at 100 ℃-5S/cm) | 8.69 | 62.5 | 119 | 34.8 | 34.1 | 12.3 |
As can be seen from tables 3 and 4, when x is 0.3, the ionic conductivity of the solid electrolyte material is the highest at 100 ℃; and when x is 0.4, the ionic conductivity of the sintered solid electrolyte layer is highest at 100 ℃.
Examples 5 to 8
Examples 5 to 8 differ from example 1 in that La was obtained in the same manner as in example 1 except that the sintering temperatures were changed to 200 ℃, 400 ℃, 600 ℃ and 1000 ℃ respectively0.4Ba0.6F2.4The ionic conductivity of the solid electrolyte layer at 100 ℃ is shown in table 5.
TABLE 5 La at different sintering temperatures0.4Ba0.6F2.4Ion conductivity of solid electrolyte layer at 100 DEG C
| La0.4Ba0.6F2.4 | 200 |
400 |
600℃ | 800 |
1000℃ |
| Ionic conductivity (. times.10) at 100 ℃-4S/cm) | 2.07 | 4.26 | 9.48 | 11.9 | 8.63 |
As can be seen from Table 5, La0.4Ba0.6F2.4The ionic conductivity increased during the sintering temperature increase, reaching a maximum at 800 ℃.
Comparative example 3
The difference from example 4 is that the mixed solvent used was only deionized water, and no ethanol was added.
Comparative example 4
The difference from the example 4 is that the volume ratio of the deionized water to the ethanol used in the mixed solvent is 1: 4.
FIG. 8 shows La obtained in comparative examples 3 and 40.7Ba0.3F2.7XRD diffractogram of solid state electrolyte material. According to the calculation of the Sheer formula, the La can be obtained when the volume ratio of the deionized water to the ethanol is changed from 1:0 to 1:40.7Ba0.3F2.7The grain size of the solid electrolyte material powder is reduced from 22.8nm to 11.6 nm. The La of comparative example 3 and comparative example 4 was tested0.7Ba0.3F2.7The ionic conductivity of the solid electrolyte material at 100 ℃ is 5.01 multiplied by 10 respectively-6S/cm，9.16×10-6S/cm。
Comparative example 5
The difference from example 1 is that NH4The concentration of the F solution was 3 mol/L. The white release obtained by the preparation is obviously reduced compared with that of the example 1, and the La obtained by the preparation0.4Ba0.6F2.4The solid electrolyte material has an ionic conductivity of 2.23X 10 at 100 DEG C-5S/cm。
Comparative example 6
The difference from example 1 is that NH4The concentration of the F solution was 7 mol/L. The white precipitate is separated out faster than that of example 1, and the prepared La0.4Ba0.6F2.4The solid electrolyte material has an ionic conductivity of 4.08X 10 at 100 DEG C-5S/cm。
The above embodiments are preferred embodiments of the present application, and the protection scope of the present application is not limited by the above embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (10)
1. A method for producing a solid electrolyte material, characterized by: the method comprises the following steps:
1) mixing deionized water and an organic solvent in proportion to prepare a mixed solvent;
2) respectively mixing the mixed solvent prepared in the step 1) with La3+Soluble salts of ions, Ba2+Mixing soluble salts of ions and ammonium fluoride to form three solutions, and mixing the three solutions under the assistance of ultrasonic waves to prepare the LaxBa1-xF2+x(0<x < 1) is released and post-treated to obtain LaxBa1-xF2+x(0<x < 1) solid electrolyte material.
2. The method for producing a solid electrolyte material according to claim 1, characterized in that: the volume ratio of the deionized water to the organic solvent is (1:1) - (1:3), and preferably 1: 1.
3. The method for producing a solid electrolyte material according to claim 1, characterized in that: x is more than or equal to 0.3 and less than or equal to 0.7, preferably 0.3-0.4.
4. The method for producing a solid electrolyte material according to claim 1, characterized in that: among the three solutions, La3+The soluble salt solution of the ions is saturated with soluble salt at room temperature of 25 DEG CA solution; ba2+The soluble salt solution of the ions is a saturated solution of soluble salt at room temperature of 25 ℃; the concentration of the ammonium fluoride solution is 5-6 mol/L, preferably 5 mol/L.
5. The method for producing a solid electrolyte material according to claim 1, characterized in that: the La3+The soluble salt of the ion is nitrate or chloride, and the Ba2+Soluble salts of ions are nitrate or chloride, La3+The soluble salt of the ion is preferably La (NO)3)3，Ba2+The soluble salt of the ion is preferably Ba (NO)3)2。
6. The method for producing a solid electrolyte material according to claim 1, characterized in that: the working power of the ultrasonic wave is 50-100W, and preferably 50W.
7. A solid electrolyte material prepared by the method for preparing a solid electrolyte material according to any one of claims 1 to 6.
8. A method for producing a solid electrolyte layer, characterized by: the method comprises the following steps:
1) cold pressing the solid state electrolyte material of claim 7 into a billet,
2) and sintering the blank at 200-1000 ℃ in an inert atmosphere to obtain the solid electrolyte layer, wherein the sintering time is 2-4 h.
9. The method for producing a solid electrolyte layer according to claim 8, characterized in that: the sintering temperature is 400-800 ℃, preferably 800 ℃, and the sintering time is 2 h.
10. A solid electrolyte layer produced by the method for producing a solid electrolyte layer according to claim 9.
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