CN112563564B - Soft chemical synthesis method for preparing sodium ion solid electrolyte - Google Patents
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Abstract
The invention discloses a soft chemical synthesis method for preparing a sodium ion solid electrolyte, which comprises the following steps: step 1: uniformly mixing the lithium ion solid electrolyte and a solid-phase sodium ion exchanger to obtain mixed powder; step 2: carrying out heat treatment on the mixed powder to synthesize a sodium ion solid electrolyte; the lithium ion solid electrolyte and the sodium ion exchanger are kept in a solid phase state in the heat treatment process; and step 3: dissolving redundant sodium ion exchangers and synthesized byproducts by using a solvent, and centrifuging to obtain a solid product containing sodium ion solid electrolyte; and 4, step 4: drying the obtained solid product, uniformly mixing the dried solid product with a sodium ion exchanger, and repeating the step 2-3 for a plurality of times to improve the content of sodium ion solid electrolyte in the solid product. The invention synthesizes the sodium ion solid electrolyte by solid phase exchange between the lithium ion solid electrolyte and the sodium ion exchanger under the condition of low-temperature heat treatment, has simple and convenient method and low cost, and is easy for industrial application.
Description
Technical Field
The invention relates to the field of new energy materials, in particular to a soft chemical synthesis method for preparing a sodium ion solid electrolyte.
Background
In nature, sodium ion batteries have the advantages of lower cost and more sustainable development due to the fact that sodium element is more abundant than lithium. Similar to lithium ion batteries using organic electrolytes, sodium ion batteries using organic liquids as electrolytes also have safety problems. The solid electrolyte has high thermal stability and wide electrochemical window, and the development of the all-solid-state sodium battery by replacing organic electrolyte with the sodium ion solid electrolyte not only can effectively solve the safety problem, but also can improve the energy density of the battery.
The types and amounts of sodium ion solid electrolytes are much smaller than those of lithium ion electrolytes, especially those with high ionic conductivity. Na (Na)3Zr2Si2PO12And Na-beta-A12O3Are two widely studied sodium ion solid electrolytes. Na (Na)3Zr2Si2PO12The room-temperature ionic conductivity of the material can reach 6.7 multiplied by 10-4S/cm。Na-beta-A12O3There are two different crystal structures: beta-A12O3(hexagonal system: P63/mmc) and beta-A12O3(diamond: R3m), the beta phase contains more sodium ions, and the ionic conductivity is higher than that of the beta phase, and can reach 2 x 10-3S/cm. By the reaction of Na3Zr2Si2PO12The element doping can obtain sodium ion solid electrolyte with higher ion conductivity, such as Na obtained by Sc doping3.4Sc0.4Zr1.6Si2PO12Room temperature ionic conductivity of 4X 10-3S/cm. However, the element doping is not easy to accurately control the element metering ratio of the product, and impurities are easy to generate, so that the repeatability is poor, and the large-scale production is not easy. Na-beta-A12O3Higher synthesis temperatures (1200 ℃ C. and 1600 ℃ C.) may also limit its large-scale application. Therefore, the development of a new method for preparing the sodium ion solid electrolyte is of great significance.
Currently, ion exchange methods have been used to prepare novel lithium ion solid electrolytes. CN201910563541.8 and CN201280041281.4, both of whom were filed by township et al and tai village, respectively, used a sodium ion conductor as a precursor to prepare a lithium ion solid electrolyte by an ion exchange method. Ionic liquids and molten salts are used as ion exchange media by tangwei et al and tsuji village et al, respectively. On one hand, however, molten salt is highly destructive due to high temperature, and thus the crystal structure of the product is easily collapsed in the ion exchange process, and a pure-phase exchange product cannot be obtained; on the other hand, when the ionic liquid is used as an exchange medium, the reaction conditions are relatively mild, and a high-purity exchange product can be obtained, but the cost is high.
Disclosure of Invention
The invention aims to provide a preparation method of a sodium ion solid electrolyte, which has the advantages of low cost, simplicity, convenience, easiness and mild reaction conditions.
In order to achieve the above object, the present invention provides a soft chemical synthesis method for preparing a sodium ion solid electrolyte, comprising:
step 1: uniformly mixing the lithium ion solid electrolyte and a solid-phase sodium ion exchanger to obtain mixed powder;
step 2: carrying out heat treatment on the mixed powder to enable lithium ions in the lithium ion solid electrolyte and sodium ions in the sodium ion exchanger to generate ion exchange so as to synthesize a sodium ion solid electrolyte; the lithium ion solid electrolyte and the sodium ion exchanger are kept in a solid phase state during the heat treatment;
and step 3: dissolving redundant sodium ion exchangers and synthesized byproducts by using a solvent, and centrifuging to obtain a solid product containing sodium ion solid electrolyte;
and 4, step 4: drying the obtained solid product, uniformly mixing the dried solid product with a sodium ion exchanger, and repeating the step 2-3 for a plurality of times to improve the content of sodium ion solid electrolyte in the solid product.
Preferably, the lithium ion solid electrolyte comprises: garnet-type solid electrolyte Li7La3Zr2O12NASICON-type solid electrolyte Li1+yAlyTi2-y(PO4)3、Li1+zAlzGe2-z(PO4)3And LiTimZr2-m(PO4)3Perovskite type solid electrolyte Li3xLa2/3-xTi3O3Or sulfide solid electrolyte Li10GeP2S12、Li3.25Ge0.25P0.75S4、Li3PS4、Li3Zn0.5GeS4、Li3.4Si0.4P0.6S4And Li7P3S11Wherein x is more than or equal to 0 and less than or equal to 2/3, y is more than or equal to 0 and less than or equal to 2, z is more than or equal to 0 and less than or equal to 2, and m is more than or equal to 0 and less than or equal to 2.
Preferably, the sodium ion exchanger comprises: anhydrous sodium acetate, sodium nitrate or sodium bistrifluoromethylsulfonimide.
Preferably, the solvent is deionized water, absolute ethyl alcohol or absolute ethyl ether.
Preferably, the heat treatment is performed at 20-400 ℃ in step 2, and the time for each heat treatment is 20-1440 min.
Preferably, the heat treatment is carried out at 200-270 ℃ for 120min each time.
Preferably, the molar ratio of the lithium ion solid electrolyte to the sodium ion exchanger is (1:1) - (1: 100).
Preferably, the molar ratio of the lithium ion solid electrolyte to the sodium ion exchanger is (1:1) - (1: 40).
Preferably, in step 1, the lithium ion solid electrolyte and the sodium ion exchanger are mixed by milling.
Preferably, in step 4, the drying temperature is 60-80 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention can rapidly prepare the novel sodium ion solid electrolyte in a short time by taking the existing lithium ion solid electrolyte as a precursor through a simple ion exchange method, enriches the variety and the quantity of the novel sodium ion solid electrolyte and provides more solid electrolyte choices for the development of all-solid-state sodium batteries.
(2) The invention can avoid destructive influence on products caused by high-temperature molten salt.
(3) The invention prepares the solid electrolyte by the ion exchange method, can avoid the design of a novel solid electrolyte which is complex and difficult, and can also reduce the difficulty of preparing the novel sodium ion solid electrolyte by a high-temperature solid phase method or a liquid phase method.
Drawings
Fig. 1 is an ac impedance spectrum of a sodium ion solid electrolyte prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings and examples.
Example 1
Weighing n-butyl titanate (C) according to stoichiometric ratio4H9O)4Ti、Al(NO3)3·9H2O、85wt％H3PO4(in water) and a 5 mol% excess of CH3COOLi. Will (C)4H9O)4Ti is added into deionized water for full hydrolysis, and organic matters generated by hydrolysis are removed by ethanol centrifugation. Then, adding the white precipitate obtained by hydrolysis into 2M oxalic acid aqueous solution, adding the rest raw materials after the precipitate is completely dissolved, heating and stirring at 80 ℃ to obtain a clear transparent solution, continuing heating and stirring, evaporating to remove water, and drying in an oven at 80 ℃ overnight to obtain the white precipitate. Heat treating the precipitate at 400 deg.C for 2h, ball milling at 450r/min for 12h, and calcining at 750 deg.C for 12h to obtain Li1.3Al0.3Ti1.7(PO4)3White powder.
Weighing Li with a molar ratio of 1:401.3Al0.3Ti1.7(PO4)3The powder and anhydrous sodium acetate were placed in a mortar and mixed uniformly, and then the mixed powder was poured into an alumina crucible and heat-treated at 240 ℃ for 2 hours. Then centrifuging with deionized water for 5 times to remove excessive sodium acetate and lithium acetate produced by exchange, centrifuging with ethanol to remove water, and concentrating at 60-80 deg.CThe material was dried. The above steps are repeated several times until the ion exchange reaction reaches equilibrium.
After 1 exchange, the content of sodium ions in the product is up to 90.84 percent, which indicates that Li1.3Al0.3Ti1.7(PO4)3And Li of anhydrous sodium acetate+/Na+The exchange reaction is very fast because of Li1.3Al0.3Ti1.7(PO4)3The lithium ion mobility is high, the melting point of the ionic compound anhydrous sodium acetate is low, the crystal lattice energy is small, and the negative and positive ions are easy to dissociate. As shown in Table 1, the ICP analysis showed that after two exchanges the sodium ion content of the product was 95.44%, the exchange was essentially complete, and the product was noted as Na1.3Al0.3Ti1.7(PO4)3。
TABLE 1
FIG. 1 shows a sodium ion solid electrolyte Na prepared by an ion exchange method1.3Al0.3Ti1.7(PO4)3An AC impedance spectrum at room temperature, the ionic conductivity of which is 2.01X 10-4S/cm。
Example 2
In a drying room, Li with a molar ratio of 1:40 is weighed7La3Zr2O12The powder and anhydrous sodium acetate were placed in a mortar and mixed uniformly, and then the mixed powder was poured into an alumina crucible and heat-treated at 240 ℃ for 2 hours. Then, the sodium acetate is removed by ether centrifugation for 4 times, the lithium acetate generated by ion exchange reaction is removed by absolute ethyl alcohol centrifugation for 4 times, and finally the product is dried in a drying room at 60-80 ℃. The above steps are repeated several times until the ion exchange reaction reaches equilibrium.
Example 3
Weighing Li with a molar ratio of 1:400.5La0.5TiO3Placing the powder and anhydrous sodium acetate in a mortar, mixing, and adding the mixed powder into a containerIn an aluminum crucible, heat treatment was carried out at 240 ℃ for 2 hours. Then, the residual sodium acetate and the lithium acetate generated by exchange are removed by 5 times of centrifugation by deionized water, finally, the water is removed by ethanol centrifugation, and the product is dried at 60-80 ℃. The above steps are repeated several times until the ion exchange reaction reaches equilibrium.
The principle of the invention is that the crystal structure of the lithium ion solid electrolyte consists of an anion framework and lithium ions, the lithium ions in the framework have high mobility, and under the driving force of temperature and concentration, Li can be rapidly generated with sodium ions of a sodium ion exchanger through ion diffusion+/Na+And (3) performing exchange reaction, wherein lithium ions are removed from a crystal skeleton of the solid electrolyte, and sodium ions are diffused into the crystal skeleton, so that the sodium ion type solid electrolyte is generated. The ionic radii of sodium ions and lithium ions are respectively
And
the radius difference is small, and the ion exchange reaction does not cause the crystal structure of the solid electrolyte to be damaged at a proper temperature.
The heat treatment temperature of the present invention is lower than the melting point of the sodium ion exchanger. In addition, the ion exchange reaction speed, the exchange degree and the phase purity of the product can be controlled by controlling the heat treatment temperature; the reaction speed is accelerated when the temperature is increased. The ion exchange degree can be controlled by controlling the heat treatment time and times.
The molar ratio of the lithium ion solid electrolyte to the sodium ion exchanger is preferably 1: 40. The drying temperature is 20-200 deg.C, preferably 60-80 deg.C.
The steps of mixing the obtained solid product with a new sodium ion exchanger and heat-treating can be repeated several times until Li in the lithium ion solid electrolyte+Is completely covered by Na+By substitution of Na in solid electrolytes+Does not increase with the number of exchanges. The ion exchange process does not involve the use of a solution or the generation of a molten salt, and is referred to herein as solid phase exchange.
The product prepared by the ion exchange method is of a metastable state structure and cannot be synthesized by the traditional high-temperature solid phase method.
In conclusion, the method can synthesize the sodium ion solid electrolyte through solid phase exchange between the lithium ion solid electrolyte and the sodium ion exchanger under the condition of low-temperature heat treatment, has the advantages of simplicity, convenience, low cost and easiness in industrial application, can enrich the types and the number of sodium ion conductors, and promotes the development of the sodium ion solid battery.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (10)
1. A soft chemical synthesis method for preparing a sodium ion solid electrolyte is characterized by comprising the following steps:
step 1: uniformly mixing the lithium ion solid electrolyte and a solid-phase sodium ion exchanger to obtain mixed powder;
step 2: carrying out heat treatment on the mixed powder to enable lithium ions in the lithium ion solid electrolyte and sodium ions in the sodium ion exchanger to generate ion exchange so as to synthesize a sodium ion solid electrolyte; the lithium ion solid electrolyte and the sodium ion exchanger are kept in a solid phase state during the heat treatment;
and step 3: dissolving redundant sodium ion exchangers and synthesized byproducts by using a solvent, and centrifuging to obtain a solid product containing sodium ion solid electrolyte;
and 4, step 4: drying the obtained solid product, uniformly mixing the dried solid product with a sodium ion exchanger, and repeating the step 2-3 for a plurality of times to improve the content of sodium ion solid electrolyte in the solid product.
2. The soft chemical synthesis method for preparing a sodium ion solid electrolyte according to claim 1,the lithium ion solid electrolyte comprises: garnet-type solid electrolyte Li7La3Zr2O12NASICON-type solid electrolyte Li1+yAlyTi2-y(PO4)3、Li1+zAlzGe2-z(PO4)3And LiTimZr2-m(PO4)3Perovskite type solid electrolyte Li3xLa2/3-xTi3O3Or sulfide solid electrolyte Li10GeP2S12、Li3.25Ge0.25P0.75S4、Li3PS4、Li3Zn0.5GeS4、Li3.4Si0.4P0.6S4And Li7P3S11Wherein x is more than or equal to 0 and less than or equal to 2/3, y is more than or equal to 0 and less than or equal to 2, z is more than or equal to 0 and less than or equal to 2, and m is more than or equal to 0 and less than or equal to 2.
3. The soft chemical synthesis method for preparing a sodium ion solid electrolyte according to claim 1, wherein the sodium ion exchanger comprises: anhydrous sodium acetate, sodium nitrate or sodium bistrifluoromethylsulfonimide.
4. The soft chemical synthesis method for preparing sodium ion solid electrolyte according to claim 1, wherein the solvent is deionized water, absolute ethyl alcohol or absolute ethyl ether.
5. The soft chemical synthesis method for preparing sodium ion solid electrolyte according to claim 1, wherein the heat treatment is performed at 20-400 ℃ in step 2, and each heat treatment time is 20-1440 min.
6. The soft chemical synthesis method for preparing sodium ion solid electrolyte as claimed in claim 5, wherein the heat treatment is carried out at 200-270 ℃ for 120min each time.
7. The soft chemical synthesis method for preparing a sodium ion solid electrolyte according to claim 1, wherein the molar ratio of the lithium ion solid electrolyte to the sodium ion exchanger is (1:1) - (1: 100).
8. The soft chemical synthesis method for preparing sodium ion solid electrolyte according to claim 7, wherein the molar ratio of the lithium ion solid electrolyte to the sodium ion exchanger is (1:1) - (1: 40).
9. The soft chemical synthesis method for preparing sodium ion solid electrolyte according to claim 1, wherein in step 1, the lithium ion solid electrolyte and the sodium ion exchanger are mixed by grinding.
10. The soft chemical synthesis method for preparing sodium ion solid electrolyte according to claim 1, wherein the drying temperature in step 4 is 60-80 ℃.
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