Bimetal organic compound ionic conductor and preparation method and application thereof

Abstract

The invention discloses a bi-metal organic compound ion conductor and a preparation method and application, the bi-metal organic compound ion conductor is prepared from sodium (lithium) aluminum hydride and phenol as raw materials, and the composite of two substrates as an ion conductor material can obviously improve the utilization rate of a single species as the ion conductor material. The ionic conduction performance can be realized at a relatively low temperature. The bimetal organic compound prepared by the invention is simple in preparation process and easily available in raw materials, and has potential application prospects in the field of ionic conductors.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of double metal organic compound ion conductor and preparation method and application, belong to material preparation technical field. BACKGROUND

[0002] Alkali metal ion batteries have high energy density, rechargeable, low self-discharge, no memory effect, wide operating temperature range and other advantages, and are widely used in electric vehicles, portable electronic products and large-scale grid energy storage facilities or equipment. In the past two decades, great success has been achieved, however, due to the formation of alkali metal dendrites and the use of flammable organic electrolyte during unintentional overcharging, collision, etc. Compared with electrolyte, solid electrolyte has many advantages. For example, solid electrolyte can inhibit the growth of alkali metal dendrites on the anode during charging, improving the safety of the battery. At the same time, using alkali metal as anode can improve the capacity and energy density (such as Li anode can provide 3860 mAh·g -1 or 2061 mAh·cm -3 ). Secondly, the combination of electrolyte and separator is replaced by solid electrolyte, which can significantly improve the energy density due to the weight reduction. Therefore, the development of solid electrolyte can simplify the battery manufacturing process, eliminate the problem of electrolyte leakage, and withstand impact and vibration. SUMMARY

[0003] The double metal organic compound ion conductor prepared by the present application spans the field of organic and inorganic hydrides. The present application uses double metal to replace the H atoms on the organic ring, develops a class of double metal organic compound ion conductors, which span the field of organic and inorganic hydrides. Through this strategy, due to the small volume of cations, it is easy to conduct in larger and multiple anions, improving the ionic conductivity. According to one aspect of the present application, a class of double metal organic compound ion conductors is provided, which has the structure shown in formula I:

[0004]

[0005] In formula I, M includes metal element I and metal element II;

[0006] The metal element I is Al;

[0007] The metal element II is selected from at least one of Li, Na;

[0008] n is an integer, and n is 1-5.

[0009] Optionally, the ionic conductivity of the double metal organic compound ion conductor is 6.6 x 10 -8 S / cm to 1.3 x 10 -6 S / cm.

[0010] Optionally, the ionic conductivity of the bimetallic organic compound ion conductor is independently selected from any value among 6.6 x 10 -8 S / cm, 7 x 10 -8 S / cm, 8 x 10 -8 S / cm, 1 x 10 -7 S / cm, 2 x 10 -7 S / cm, 3 x 10 -7 S / cm, 4 x 10 -7 S / cm, 5 x 10 - 7 S / cm, 9 x 10 -7 S / cm, 1 x 10 -6 S / cm, 1.1 x 10 -6 S / cm, 1.2 x 10 -6 S / cm, 1.3 x 10 -6 S / cm, or a range value between any two of the above.

[0011] According to another aspect of the present application, there is provided a preparation method of the bimetallic organic compound ion conductor as described above, the preparation method comprising:

[0012] stirring a mixture containing phenol, metal hydride, solvent in a closed reactor under a non-active atmosphere, and vacuum drying after the reaction is completed to obtain the bimetallic organic compound ion conductor.

[0013] Optionally, the metal hydride is selected from at least one of lithium aluminum hydride, sodium aluminum hydride.

[0014] Optionally, the solvent is selected from at least one of tetrahydrofuran, diethyl ether, dimethylformamide, chloroform, dichloromethane, dimethyl sulfoxide, carbon tetrachloride, acetone, dimethylformamide, diethylene glycol dimethyl ether.

[0015] Optionally, the molar ratio of the phenol to the metal hydride is 1:4-5.

[0016] Optionally, the molar concentration of the phenol after being dissolved in the solvent is 0.1-2.0 mol / L.

[0017] Optionally, the stirring speed is 400 r / min-600 r / min.

[0018] Optionally, the stirring speed is independently selected from any value among 400 r / min, 420 r / min, 450 r / min, 480 r / min, 500 r / min, 520 r / min, 550 r / min, 580 r / min, 600 r / min, or a range value between any two of the above.

[0019] Optionally, the temperature of the stirring is 25-120℃, and the time of the stirring is 0.5h-12h.

[0020] Optionally, the temperature of the stirring is independently selected from any value of 25℃, 30℃, 60℃, 80℃, 90℃, 100℃, 120℃ or a range between any two of the above values.

[0021] Optionally, the time of the stirring is independently selected from any value of 0.5h, 1h, 2h, 4h, 6h, 8h, 10h, 12h or a range between any two of the above values.

[0022] Optionally, the non-reactive atmosphere is selected from at least one of argon, nitrogen, helium.

[0023] According to yet another aspect of the present application, there is provided a use of the above-mentioned double-metal organic compound ion conductor in a battery.

[0024] The beneficial effects that can be produced by the present application include:

[0025] The double-metal organic compound ion conductor prepared by the present application is prepared from sodium (lithium) aluminum hydride and phenol as raw materials. The combination of the two substrates as an ion conductor material can significantly improve the performance of a single species as an ion conductor material, and the ion conduction performance can be achieved at a lower temperature. The double-metal organic compound ion conductor prepared by the present application has a simple preparation process and readily available raw materials, and has potential application prospects in the field of ion conductors. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 Double-metal organic compound 1 prepared in Example 1 of the present application # XRD spectrum compared with phenol and lithium aluminum hydride.

[0027] Figure 2 Double-metal organic compound 1 prepared in Example 1 of the present application # XRD spectrum compared with phenol 1 H-NMR spectrum.

[0028] Figure 3 Double-metal organic compound 2 prepared in Example 2 of the present application # XRD spectrum compared with phenol and sodium aluminum hydride.

[0029] Figure 4 Double-metal organic compound 2 prepared in Example 2 of the present application # XRD spectrum compared with phenol 1 H-NMR spectrum. DETAILED DESCRIPTION

[0030] The application will be described in detail below with reference to examples, but the application is not limited to these examples.

[0031] The raw materials in the examples of the present application are all purchased through commercial channels unless otherwise specified.

[0032] In the examples of the present application, phenol (99%, Aldrich), tetrahydrofuran (AR, Kermel), lithium aluminum hydride (97%, Anjie Chemical), sodium aluminum hydride (~ 99%, Sigma-Aldrich).

[0033] British Hydride Temperature Programmed Desorption Mass Spectrometer (TPD-MS), PANalytical X-ray diffractometer (PANalytical X'Pert Pro), JEOL JNM-ECZL series nuclear magnetic resonance spectrometer, biologic VMP-300 for impedance testing.

[0034] Example 1

[0035]

[0036] In the glove box, under the protection of argon atmosphere, 0.9411 g of phenol powder and 0.0978 g of lithium aluminum hydride powder were accurately weighed, 30 mL of tetrahydrofuran solution was added into a high-pressure reaction kettle, sealed, stirred at room temperature, the stirring rate was 500 revolutions per minute, and the stirring was carried out for 3 h. After the stirring was completed, the reaction kettle was moved into the glove box, and all the solution was taken out into a 150 mL round-bottom flask, sealed, and then vacuum dried. After the solution was dried, it was moved into the glove box, evacuated overnight, and the powder was scraped and collected to obtain the bimetallic organic compound 1 # .

[0037] As shown in Figure 1 , it can be seen from Figure 1 that the bimetallic organic compound 1 # compared with phenol and lithium aluminum hydride, the XRD spectrum shows a new phase. As shown in Figure 2 , it can be seen from Figure 2 that the original -OH peak in phenol has disappeared, and other peak positions have been chemically shifted, indicating that the bimetallic organic compound 1 # has been successfully synthesized.

[0038] Example 2

[0039]

[0040] In a glove box, 0.9411 g of phenol powder and 0.1350 g of sodium aluminum hydride powder were accurately weighed, and 30 mL of tetrahydrofuran solution was added to a high-pressure reaction kettle, which was sealed and stirred at room temperature at a stirring rate of 500 revolutions per minute for 3 h. After stirring was completed, the reaction kettle was removed to the glove box, and the entire solution was taken out into a 150 mL round-bottom flask, which was sealed and vacuum dried. After the solution was dried, it was moved to the glove box warehouse and vacuumed overnight. The powder was scraped and collected to obtain the bimetallic organic compound 2 # .

[0041] As shown in Figure 3 , it can be seen from Figure 3 that the XRD spectrum of sodium aluminum phenolate shows a new phase compared with phenol and sodium aluminum hydride. As shown in Figure 4 , it can be seen from Figure 4 that the original -OH peak in phenol has disappeared, and the positions of other peaks have been chemically shifted, indicating that the bimetallic organic compound 2 # .

[0042] Test Example 1

[0043] 35-70 mg of the bimetallic organic compound 1 # was taken and placed in two stainless steel plug cell devices with the same diameter (15 mm), and the powder was uniformly distributed by oscillation. The powder was formed into a "sandwich" structure by applying static pressure, and the cell shell was sealed by applying pressure. The thickness of the round sheet formed by pressing was 1.00 mm. The above assembled battery was connected to an electrochemical workstation, and after the open circuit voltage was stable, the measurement was started. The temperature was set to 30°C, 50°C, 70°C, 90°C, 110°C, 130°C, and 150°C, respectively. Each temperature was measured after constant temperature for 1 hour to make the battery stable. Table 1 is the conductivity of the bimetallic organic compound 1 # . As shown in Table 1, the ionic conductivity of the bimetallic organic compound 1 # reached 4.03 x 10 -7 S / cm at 150°C.

[0044] Table 1: Conductivity of the bimetallic organic compound 1 # at different temperatures

[0045] Temperature (℃) Conductivity (S / cm) 70 4.65 x 10 -7 ]] 90 5.12 x 10 -7 ]]> 110 4.45 x 10 -7 ]]> 130 3.84x10 -7 ]] 150 4.03 x 10 -7 ]]

[0046] Test Example 2

[0047] 35-70 mg of the bimetallic organic compound 2 #The powder was placed in a mold with a diameter of 15 mm, and was uniformly distributed by oscillation. The powder was formed by applying static pressure, and was pressed into a disc with a thickness of 1.00 mm. The disc was then placed between two stainless steel sheets with the same diameter, forming a "sandwich" structure. The "sandwich" structure was wrapped with a commercial battery shell, and was sealed by applying pressure. The assembled battery was connected to an electrochemical workstation. After the open circuit voltage was stabilized, the measurement was started. The temperature was set to 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, and 120°C, respectively. Each temperature was measured after 1 hour of constant temperature, so that the battery was in a stable state. Table 2 is the conductivity of the bimetallic organic compound 2 # at different temperatures. As shown in Table 2, the ionic conductivity of the bimetallic organic compound 2 # reached 1.31 x 10 -6 S / cm at 120°C.

[0048] Table 2: Conductivity of the bimetallic organic compound 2 # at different temperatures

[0049] Temperature (℃) Conductivity (S / cm) 70 6.62x10 -7 ]]> 80 2.06 x 10 -7 ]] 90 3.91 x 10 -7 ]]> 100 5.99x10 -7 ]]> 110 9.04 x 10 -7 ]] 120 1.31 x 10 -6 ]]>

[0050] The above is only a few embodiments of the present application, and does not limit the present application in any form. Although the preferred embodiments are disclosed above, the present application is not limited thereto. Any person skilled in the art can make some changes or modifications to the above disclosed technical content without departing from the scope of the present application, and such changes or modifications are equivalent to equivalent embodiments, and are within the scope of the technical solution.

Claims

1. A class of double metal organic compound ion conductors characterized in that, The double metal organic compound ion conductor has a structure shown in formula I: In formula I, M includes metal element I and metal element II; The metal element I is Al; The metal element II is at least one selected from Li and Na; n is an integer, and n is 1-5.

2. The dimetallo-organic ionic conductor according to claim 1, wherein, The ionic conductivity of the double metal organic compound ion conductor is 6.6 x 10 -8 S / cm ~ 1.3 x 10 -6 S / cm.

3. The method for producing a double metal organic compound ion conductor according to any one of claims 1 to 2, characterized by, The preparation method comprises: Under a non-active atmosphere, a mixture containing phenol, metal hydride and solvent is stirred in a closed reactor until the reaction is completed, and then vacuum drying is performed to obtain the double metal organic compound ion conductor.

4. The production method according to claim 3, characterized by, The metal hydride is at least one selected from lithium aluminum hydride and sodium aluminum hydride.

5. The preparation method according to claim 3, characterized in that The solvent is at least one selected from tetrahydrofuran, diethyl ether, dimethylformamide, chloroform, dichloromethane, dimethyl sulfoxide, carbon tetrachloride, acetone, dimethylformamide, and diethylene glycol dimethyl ether.

6. The preparation method according to claim 3, characterized in that The molar ratio of the metal hydride to the phenol is 1:4-5.

7. The preparation method according to claim 3, characterized in that The molar concentration of the phenol after being dissolved in the solvent is 0.1-2.0 mol / L.

8. The preparation method according to claim 3, characterized in that The stirring speed is 400 r / min-600 r / min. Preferably, the stirring temperature is 25-120°C, and the stirring time is 0.5 h-12 h.

9. The preparation method according to claim 3, characterized in that The non-active atmosphere is at least one selected from argon, nitrogen and helium.

10. Use of the double metal organic compound ion conductor according to any one of claims 1-2 in a battery.

Images