Solid electrolyte and preparation method and application thereof

Abstract

The invention discloses a solid electrolyte as well as a preparation method and application thereof. The solid electrolyte comprises hydroxypyridinium; the preparation method of the hydroxypyridinium salt comprises the following steps: adding a certain proportion of a hydroxypyridine compound and corresponding metal hydride or metal hydroxide into a solvent in the presence of protic and aprotic solvents, stirring at a certain temperature, carrying out rotary evaporation, and removing the solvent, so as to obtain the hydroxypyridinium salt. Through a simple and feasible preparation method, the material is subjected to cold press molding for impedance testing, and the new material is found to have excellent electrochemical performance and can be applied as a solid electrolyte.

Description

TECHNICAL FIELD

[0001] The present application relates to a solid-state electrolyte and a preparation method and application thereof, and belongs to the technical field of electrolytic cells. BACKGROUND

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

[0003] The present application is based on a hydroxypyridine salt synthesized by a protic and aprotic solvothermal method.

[0004] According to one aspect of the present application, a solid-state electrolyte is provided, the solid-state electrolyte comprising a hydroxypyridine salt; the hydroxypyridine salt is selected from at least one of the structures shown in Formula I, Formula II or Formula III;

[0005]

[0006] In Formula I, Formula II, and Formula III, M is independently selected from one of Li, Na, and K.

[0007] Optionally, the thickness of the solid-state electrolyte is 0.5-1 mm.

[0008] Optionally, the thickness of the solid-state electrolyte is independently selected from any value of 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1 mm or a range value between any two of the above.

[0009] Optionally, the diameter of the solid-state electrolyte is 5-10 mm.

[0010] Optionally, the diameter of the solid-state electrolyte is independently selected from any value in the group consisting of 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, or a range between any two of the aforementioned values.

[0011] According to another aspect of the present application, there is provided a method for preparing the solid-state electrolyte as described above, the method comprising:

[0012] cold-pressing the hydroxypyridine salt to form the solid-state electrolyte.

[0013] Optionally, the method for preparing the hydroxypyridine salt comprises:

[0014] mixing a mixture I containing a hydroxypyridine compound, an alkali metal hydride, and water, stirring I, reacting I, and removing water to obtain the hydroxypyridine salt;

[0015] or, in a closed reactor, mixing a mixture II containing a hydroxypyridine compound, an alkali metal compound, and a solvent, stirring II until the end of reaction II, and removing the solvent to obtain the hydroxypyridine salt.

[0016] Optionally, the hydroxypyridine compound is selected from at least one of 2-hydroxypyridine, 3-hydroxypyridine, and 4-hydroxypyridine.

[0017] Optionally, the alkali metal hydride is selected from at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium bicarbonate, sodium bicarbonate, and potassium bicarbonate.

[0018] Optionally, the alkali metal compound is selected from at least one of lithium hydride, sodium hydride, potassium hydride, lithium amide, sodium amide, and potassium amide.

[0019] Optionally, the molar ratio of the hydroxypyridine compound to the alkali metal hydride is 1:0.7-1:1.3.

[0020] Optionally, the molar ratio of the hydroxypyridine compound to the alkali metal compound is 1:0.7-1:1.3.

[0021] Optionally, the molar concentration of the hydroxypyridine compound after being dissolved in water is 0.1-1.0 mol / L.

[0022] Optionally, the solvent is selected from at least one of tetrahydrofuran, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, and diethylene glycol dimethyl ether.

[0023] Optionally, the molar concentration of the hydroxypyridine compound after being dissolved in the solvent is 0.1-1.0 mol / L.

[0024] Optionally, the temperature of the stirring I is 20-60°C, and the stirring speed of the stirring I is 100-500 r / min.

[0025] Optionally, the reaction I is performed for 2-6 hours.

[0026] Optionally, the temperature of the stirring II is 20-120°C, and the stirring speed of the stirring II is 50-500 r / min.

[0027] Optionally, the pressure of the cold-pressing forming is 1.5-4 MPa.

[0028] According to still another aspect of the present application, there is provided an application of the solid-state electrolyte described above in an alkali metal ion battery.

[0029] As an optional embodiment, the present application is implemented by the following technical solutions:

[0030] Solvent-thermal method: in a glove box, equal-molar-ratio hydroxypyridine (2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine) and alkali metal hydride (lithium hydride, sodium hydride, potassium hydride) are weighed and placed in 30 ml (arbitrary volume) of tetrahydrofuran as a solvent, the reaction kettle is sealed, stirred at room temperature to 120°C, the stirring speed is 50-500 r / min, and the reaction is performed until the hydrogen release amount reaches the theoretical amount. The reaction kettle is moved into the glove box, the product is removed into a rotary evaporation flask, sealed with vacuum grease and taken out of the glove box, rotary evaporation is performed at room temperature to 70°C until the sample is dry. Finally, the sample is collected in the glove box and relevant performance tests are performed.

[0031] Aqueous solution acid-base method: equal-molar-ratio hydroxypyridine (2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine) and alkali metal hydroxide (lithium hydroxide, sodium hydroxide, potassium hydroxide) are weighed and placed in 30 ml (arbitrary volume) of deionized water as a solvent, stirred at room temperature in air, the stirring speed is 100-500 r / min, and the reaction is performed for 2-6 hours. After the reaction is completed, the product is removed into a rotary evaporation flask, rotary evaporation is performed at room temperature to 70°C until the sample is dry. Finally, the sample is collected in the glove box and relevant performance tests are performed.

[0032] The present application can produce the following beneficial effects:

[0033] The application adds a certain proportion of hydroxypyridine compound and corresponding metal hydride or metal hydroxide into a solvent under proton and aprotic solvent, stirs at a certain temperature, and then rotary evaporates to remove the solvent to obtain a hydroxypyridine metal salt. The preparation method has the advantages of simple operation, no reaction equilibrium point, low cost, complete reaction, controllable reaction process, and easy expansion. The hydroxypyridine salt material is cold-pressed into a shape for impedance test, and it is found that the new material has excellent electrochemical performance and can be applied as a solid-state electrolyte. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 The nuclear magnetic hydrogen spectrum of 2-hydroxypyridine lithium synthesized in Example 1 of the application.

[0035] Figure 2 The carbon spectrum of 2-hydroxypyridine lithium synthesized in Example 1 of the application.

[0036] Figure 3 The X-ray diffraction spectrum of 2-hydroxypyridine lithium synthesized in Example 1 of the application.

[0037] Figure 4 The nuclear magnetic hydrogen spectrum of 2-hydroxypyridine sodium synthesized in Example 2 of the application.

[0038] Figure 5 The carbon spectrum of 2-hydroxypyridine sodium synthesized in Example 2 of the application.

[0039] Figure 6 The X-ray diffraction spectrum of 2-hydroxypyridine sodium synthesized in Example 2 of the application.

[0040] Figure 7 The nuclear magnetic hydrogen spectrum of 2-hydroxypyridine potassium synthesized in Example 3 of the application.

[0041] Figure 8 The carbon spectrum of 2-hydroxypyridine potassium synthesized in Example 3 of the application.

[0042] Figure 9 The X-ray diffraction spectrum of 2-hydroxypyridine potassium synthesized in Example 3 of the application.

[0043] Figure 10 The nuclear magnetic hydrogen spectrum of 4-hydroxypyridine lithium synthesized in Example 7 of the application.

[0044] Figure 11 The carbon spectrum of 4-hydroxypyridine lithium synthesized in Example 7 of the application.

[0045] Figure 12 The X-ray diffraction spectrum of 4-hydroxypyridine lithium synthesized in Example 7 of the application.

[0046] Figure 13 NMR of 4-hydroxypyridine sodium synthesized in Example 8 of the present application.

[0047] Figure 14 Carbon spectrum of 4-hydroxypyridine sodium synthesized in Example 8 of the present application.

[0048] Figure 15 X-ray diffraction spectrum of 4-hydroxypyridine sodium synthesized in Example 8 of the present application.

[0049] Figure 16 NMR of 4-hydroxypyridine potassium synthesized in Example 9 of the present application.

[0050] Figure 17 Carbon spectrum of 4-hydroxypyridine potassium synthesized in Example 9 of the present application.

[0051] Figure 18 X-ray diffraction spectrum of 4-hydroxypyridine potassium synthesized in Example 9 of the present application. DETAILED DESCRIPTION

[0052] The present application will be described in detail below with reference to the examples, but the present application is not limited to these examples.

[0053] In the examples of the present application, the raw materials were purchased through commercial channels unless otherwise specified.

[0054] In the present application, nuclear magnetic hydrogen spectrum and carbon spectrum were characterized by using a Bruker 500 MHz instrument.

[0055] X-ray diffraction was performed by using a Panalytical X-ray diffractometer, Cu Kα (40 KV, 40 mA).

[0056] Example 1

[0057] Solvent thermal method: In a glove box, 2-hydroxypyridine and lithium hydride were weighed in an equimolar ratio and placed in 30 ml of tetrahydrofuran as a solvent. The reaction kettle was sealed and stirred at 60°C at a stirring speed of 500 rpm until the hydrogen release reached the theoretical amount. The reaction kettle was moved into the glove box, and the product was removed into a rotary evaporation flask, which was sealed with vacuum grease and taken out of the glove box. Rotary evaporation was performed at 50°C until the sample became dry, obtaining 2-hydroxypyridine lithium. Finally, the sample was collected in the glove box and tested for related conductivity performance.

[0058] Aqueous acid-base method: take equal molar ratio of 2-hydroxypyridine and lithium hydroxide in 50 milliliters of deionized water as solvent, stirring in air at room temperature, stirring speed is 150 revolutions per minute, reaction 2 hours. After the reaction, remove the product to the rotary evaporator bottle, rotary evaporation at 90℃ until the sample is dry, get 2-hydroxypyridine lithium. Finally, the sample is collected in the glove box, and the relevant conductivity performance test is done.

[0059] As shown in Figures 1 to 3 , it can be seen from Figure 1 that the signals of 2-hydroxypyridine lithium synthesized by the two methods are the same, and compared with the original 2-hydroxypyridine nuclear magnetic hydrogen spectrum, the shift occurs, which proves that new substances are generated; from Figure 2 , it can be seen that the signals of 2-hydroxypyridine lithium synthesized by the two methods are the same, and compared with the original 2-hydroxypyridine nuclear magnetic carbon spectrum, the shift occurs, which proves that new substances are generated; from Figure 3 , it can be seen that the spectra synthesized by the two methods are basically the same, which proves that 2-hydroxypyridine lithium has been successfully synthesized.

[0060] Example 2

[0061] Solvent thermal method: in the glove box, take equal molar ratio of 2-hydroxypyridine and sodium hydride in 30 milliliters of tetrahydrofuran as solvent, seal the reaction kettle, stirring at 25℃, stirring speed is 500 revolutions per minute, reaction until the hydrogen release amount reaches the theoretical amount. Move the reaction kettle into the glove box, and remove the product to the rotary evaporator bottle, seal with vacuum grease and take out of the glove box, rotary evaporation at 70℃ until the sample is dry, get 2-hydroxypyridine sodium. Finally, the sample is collected in the glove box, and the relevant conductivity performance test is done.

[0062] Aqueous acid-base method: take equal molar ratio of 2-hydroxypyridine and sodium hydroxide in 50 milliliters of deionized water as solvent, stirring in air at room temperature, stirring speed is 150 revolutions per minute, reaction 2 hours. After the reaction, remove the product to the rotary evaporator bottle, rotary evaporation at 80℃ until the sample is dry. Finally, the sample is collected in the glove box, get 2-hydroxypyridine sodium, and the relevant conductivity performance test is done.

[0063] As shown in Figures 4 to 6 , it can be seen from Figure 4 that the signals of 2-hydroxypyridine sodium synthesized by the two methods are the same, and compared with the original 2-hydroxypyridine nuclear magnetic hydrogen spectrum, the shift occurs, and the hydroxyl peak disappears, which proves that the metal substitution is successful; from Figure 5 , it can be seen that the signals of 2-hydroxypyridine sodium synthesized by the two methods are the same, and compared with the original 2-hydroxypyridine nuclear magnetic carbon spectrum, the shift occurs, which proves that new substances are generated; from Figure 6 , it can be seen that the spectra synthesized by the two methods are basically the same, which proves that 2-hydroxypyridine sodium has been successfully synthesized.

[0064] Example 3

[0065] Solvent-thermal method: In the glove box, equal molar ratio of 2-hydroxypyridine and potassium hydride were weighed and put into 30 ml of tetrahydrofuran as solvent, the reactor was sealed, stirred at 25°C, the stirring speed was 500 rpm, and the reaction was carried out until the hydrogen release reached the theoretical amount. The reactor was moved into the glove box, and the product was removed into a rotary evaporation flask, sealed with vacuum grease and taken out of the glove box, rotary evaporation was carried out at 60°C until the sample was dry, and 2-hydroxypyridine potassium was obtained. Finally, the sample was collected in the glove box and the relevant conductivity performance test was carried out.

[0066] Aqueous solution acid-base method: Equal molar ratio of 2-hydroxypyridine and potassium hydroxide were weighed and put into 50 ml of deionized water as solvent, stirred at room temperature in air, the stirring speed was 150 rpm, and the reaction was carried out for 2 hours. After the reaction was completed, the product was removed into a rotary evaporation flask, rotary evaporation was carried out at 80°C until the sample was dry, and 2-hydroxypyridine potassium was obtained. Finally, the sample was collected in the glove box and the relevant conductivity performance test was carried out.

[0067] As shown in Figures 7 to 9 , it can be seen from Figure 7 that the signals of 2-hydroxypyridine potassium synthesized by the two methods are the same, and compared with the original 2-hydroxypyridine nuclear magnetic hydrogen spectrum, the hydroxyl peak disappears, which proves that the metal substitution is successful; from Figure 8 , it can be seen that the signals of 2-hydroxypyridine potassium synthesized by the two methods are the same, and compared with the original 2-hydroxypyridine nuclear magnetic carbon spectrum, which proves that new substances are generated; from Figure 9 , it can be seen that the spectra synthesized by the two methods are basically the same, which proves that 2-hydroxypyridine potassium has been successfully synthesized.

[0068] Example 4

[0069] Solvent-thermal method: In the glove box, equal molar ratio of 3-hydroxypyridine and lithium hydride were weighed and put into 30 ml of tetrahydrofuran as solvent, the reactor was sealed, stirred at 70°C, the stirring speed was 500 rpm, and the reaction was carried out until the hydrogen release reached the theoretical amount. The reactor was moved into the glove box, and the product was removed into a rotary evaporation flask, sealed with vacuum grease and taken out of the glove box, rotary evaporation was carried out at 60°C until the sample was dry, and 3-hydroxypyridine lithium was obtained. Finally, the sample was collected in the glove box, and the relevant conductivity performance test was carried out.

[0070] Aqueous acid-base method: equal molar ratio of 3-hydroxypyridine and lithium hydroxide was weighed in 50 mL of deionized water as solvent, stirred at room temperature in air, the stirring speed was 150 rpm, and the reaction was carried out for 3 hours. After the reaction was completed, the product was removed to a rotary evaporation flask, rotary evaporation was carried out at 90°C until the sample was dry, and lithium 3-hydroxypyridine was obtained. Finally, the sample was collected in a glove box, the substance was characterized, and the relevant conductivity performance test was carried out. Characterization proved that 3-hydroxypyridine lithium was successfully synthesized by two preparation methods.

[0071] Example 5

[0072] Solvent-thermal method: equal molar ratio of 3-hydroxypyridine and sodium hydride was weighed in 30 mL of tetrahydrofuran as solvent in a glove box, the reaction kettle was sealed, stirred at 80°C, the stirring speed was 500 rpm, and the reaction was carried out until the hydrogen release amount reached the theoretical amount. The reaction kettle was moved into the glove box, the product was removed to a rotary evaporation flask, sealed with vacuum grease and taken out of the glove box, rotary evaporation was carried out at 80°C until the sample was dry, and 3-hydroxypyridine sodium was obtained. Finally, the sample was collected in a glove box, the substance was characterized, and the relevant conductivity performance test was carried out.

[0073] Aqueous acid-base method: equal molar ratio of 3-hydroxypyridine and sodium hydroxide was weighed in 50 mL of deionized water as solvent, stirred at room temperature in air, the stirring speed was 200 rpm, and the reaction was carried out for 2 hours. After the reaction was completed, the product was removed to a rotary evaporation flask, rotary evaporation was carried out at 80°C until the sample was dry, and 3-hydroxypyridine sodium was obtained. Finally, the sample was collected in a glove box, the substance was characterized, and the relevant conductivity performance test was carried out. Characterization proved that 3-hydroxypyridine sodium was successfully synthesized by two preparation methods.

[0074] Example 6

[0075] Solvent-thermal method: equal molar ratio of 3-hydroxypyridine and potassium hydride was weighed in 30 mL of tetrahydrofuran as solvent in a glove box, the reaction kettle was sealed, stirred at 70°C, the stirring speed was 500 rpm, and the reaction was carried out until the hydrogen release amount reached the theoretical amount. The reaction kettle was moved into the glove box, the product was removed to a rotary evaporation flask, sealed with vacuum grease and taken out of the glove box, rotary evaporation was carried out at 80°C until the sample was dry, and 3-hydroxypyridine potassium was obtained. Finally, the sample was collected in a glove box, the substance was characterized, and the relevant conductivity performance test was carried out.

[0076] Aqueous Acid-Base Method: Weigh 3-hydroxypyridine and potassium hydroxide in equal molar ratios in 50 ml of deionized water as the solvent. Stir in air at room temperature at 200 rpm for 2 hours. After the reaction, transfer the product to a rotary evaporator and evaporate at 80°C until the sample is dry to obtain potassium 3-hydroxypyridine. The sample is collected in a glove box, characterized, and tested for electrical conductivity. Characterization confirmed that both preparation methods successfully synthesized potassium 3-hydroxypyridine.

[0077] Example 7

[0078] Solvothermal method: In a glove box, weigh 4-hydroxypyridine and lithium hydride in equal molar ratios and place them in 30 ml of tetrahydrofuran as the solvent. Seal the reactor and stir at 30°C at 500 rpm until the hydrogen release reaches the theoretical amount. Transfer the reactor back into the glove box and transfer the product to a rotary evaporator. Seal the flask with vacuum grease and remove it from the glove box. Rotary evaporate the flask at 80°C until the sample is dry to obtain lithium 4-hydroxypyridine. Collect the sample in the glove box and perform relevant conductivity performance tests.

[0079] Aqueous Acid-Base Method: Weigh 4-hydroxypyridine and lithium hydroxide in equal molar ratios in 50 ml of deionized water. Stir in air at room temperature at 250 rpm for 2 hours. After the reaction, transfer the product to a rotary evaporator and evaporate at 70°C until dry to obtain lithium 4-hydroxypyridine. Collect the sample in a glove box and perform conductivity testing.

[0080] like Figures 10 to 12 As shown, from Figure 10 It can be seen that the signals of lithium 4-hydroxypyridine synthesized by the two methods are the same, and are shifted compared with the H NMR spectrum of the original 4-hydroxypyridine, and the hydroxyl peak disappears, proving that the metal substitution is successful; Figure 11 It can be seen that the signals of lithium 4-hydroxypyridine synthesized by the two methods are the same, and there is a shift compared with the NMR carbon spectrum of the original 4-hydroxypyridine, proving that a new substance is generated; Figure 12 It can be seen that the spectra synthesized by the two methods are basically the same, proving that 4-hydroxypyridine lithium has been successfully synthesized.

[0081] Example 8

[0082] Solvent-thermal method: In the glove box, 4-hydroxypyridine and sodium hydride with equal molar ratio were weighed and put into 30 ml of tetrahydrofuran as solvent. The reactor was sealed and stirred at 80°C with a stirring speed of 500 rpm until the amount of hydrogen released reached the theoretical amount. The reactor was moved into the glove box, and the product was removed into a rotary evaporation flask, sealed with vacuum grease and taken out of the glove box. Rotary evaporation was carried out at 75°C until the sample was dry to obtain sodium 4-hydroxypyridine. Finally, the sample was collected in the glove box and tested for related conductivity performance.

[0083] Aqueous acid-base method: 4-hydroxypyridine and sodium hydroxide with equal molar ratio were weighed and put into 50 ml of deionized water as solvent. The mixture was stirred at room temperature in air with a stirring speed of 150 rpm for 2 hours. After the reaction was completed, the product was removed into a rotary evaporation flask and rotary evaporation was carried out at 65°C until the sample was dry to obtain sodium 4-hydroxypyridine. Finally, the sample was collected in the glove box and tested for related conductivity performance.

[0084] As shown in FIG. 1, it can be seen from FIG. 2 that the signals of sodium 4-hydroxypyridine synthesized by the two methods are the same, and compared with the nuclear magnetic hydrogen spectrum of the original 4-hydroxypyridine, the hydroxyl peak disappears, proving that the metal substitution is successful; as shown in FIG. 3, it can be seen from FIG. 4 that the signals of sodium 4-hydroxypyridine synthesized by the two methods are the same, and compared with the nuclear magnetic carbon spectrum of the original 4-hydroxypyridine, proving that a new substance is generated; as shown in FIG. 5, it can be seen from FIG. 6 that the spectra synthesized by the two methods are basically the same, proving that sodium 4-hydroxypyridine has been successfully synthesized. Figures 13 to 15 Figure 13 As shown in FIG. 1, it can be seen from FIG. 2 that the signals of sodium 4-hydroxypyridine synthesized by the two methods are the same, and compared with the nuclear magnetic hydrogen spectrum of the original 4-hydroxypyridine, the hydroxyl peak disappears, proving that the metal substitution is successful; as shown in FIG. 3, it can be seen from FIG. 4 that the signals of sodium 4-hydroxypyridine synthesized by the two methods are the same, and compared with the nuclear magnetic carbon spectrum of the original 4-hydroxypyridine, proving that a new substance is generated; as shown in FIG. 5, it can be seen from FIG. 6 that the spectra synthesized by the two methods are basically the same, proving that sodium 4-hydroxypyridine has been successfully synthesized. Figure 14 Figure 15 As shown in FIG. 1, it can be seen from FIG. 2 that the signals of sodium 4-hydroxypyridine synthesized by the two methods are the same, and compared with the nuclear magnetic hydrogen spectrum of the original 4-hydroxypyridine, the hydroxyl peak disappears, proving that the metal substitution is successful; as shown in FIG. 3, it can be seen from FIG. 4 that the signals of sodium 4-hydroxypyridine synthesized by the two methods are the same, and compared with the nuclear magnetic carbon spectrum of the original 4-hydroxypyridine, proving that a new substance is generated; as shown in FIG. 5, it can be seen from FIG. 6 that the spectra synthesized by the two methods are basically the same, proving that sodium 4-hydroxypyridine has been successfully synthesized.

[0085] Example 9

[0086] Solvent-thermal method: In the glove box, 4-hydroxypyridine and potassium hydride with equal molar ratio were weighed and put into 30 ml of tetrahydrofuran as solvent. The reactor was sealed and stirred at 60°C with a stirring speed of 500 rpm until the amount of hydrogen released reached the theoretical amount. The reactor was moved into the glove box, and the product was removed into a rotary evaporation flask, sealed with vacuum grease and taken out of the glove box. Rotary evaporation was carried out at 80°C until the sample was dry to obtain potassium 4-hydroxypyridine. Finally, the sample was collected in the glove box and tested for related conductivity performance.

[0087] Aqueous acid-base method: 4-hydroxypyridine and potassium hydroxide with equal molar ratio were weighed and put into 50 ml of deionized water as solvent. The mixture was stirred at room temperature in air with a stirring speed of 150 rpm for 2 hours. After the reaction was completed, the product was removed into a rotary evaporation flask and rotary evaporation was carried out at 80°C until the sample was dry to obtain potassium 4-hydroxypyridine. Finally, the sample was collected in the glove box and tested for related conductivity performance.

[0088] As shown in FIG. 1, it can be seen from FIG. 2 that the signals of sodium 4-hydroxypyridine synthesized by the two methods are the same, and compared with the nuclear magnetic hydrogen spectrum of the original 4-hydroxypyridine, the hydroxyl peak disappears, proving that the metal substitution is successful; as shown in FIG. 3, it can be seen from FIG. 4 that the signals of sodium 4-hydroxypyridine synthesized by the two methods are the same, and compared with the nuclear magnetic carbon spectrum of the original 4-hydroxypyridine, proving that a new substance is generated; as shown in FIG. 5, it can be seen from FIG. 6 that the spectra synthesized by the two methods are basically the same, proving that sodium 4-hydroxypyridine has been successfully synthesized. Figures 16 to 18 ​​As shown, from Figure 16 It can be seen that the signals of potassium 4-hydroxypyridine synthesized by the two methods are the same, and are shifted compared with the H NMR spectrum of the original 4-hydroxypyridine, and the hydroxyl peak disappears, proving that the metal substitution is successful; Figure 17 It can be seen that the signals of potassium 4-hydroxypyridine synthesized by the two methods are the same, and there is a shift compared with the NMR carbon spectrum of the original 4-hydroxypyridine, proving that a new substance is generated; Figure 18 It can be seen that the spectra synthesized by the two methods are basically the same, proving that potassium 4-hydroxypyridine has been successfully synthesized.

[0089] Application Example 1

[0090] Conductivity test: Sodium 2-hydroxypyridine was cold-pressed into a circular electrolyte sheet with a thickness of 0.56 mm and a diameter of 8 mm. Inert electrodes (stainless steel) were used on both sides to perform impedance testing on a French Bio-Logic multi-channel electrochemical workstation VMP-300 instrument, with a perturbation voltage of 10 mV.

[0091] Application Example 2

[0092] Conductivity test: Potassium 2-hydroxypyridine was cold-pressed into a circular electrolyte sheet with a thickness of 0.62 mm and a diameter of 8 mm. Inert electrodes (stainless steel) were used on both sides to perform impedance testing on a French Bio-Logic multi-channel electrochemical workstation VMP-300 instrument, with a perturbation voltage of 10 mV.

[0093] Application Example 3

[0094] Conductivity test: Potassium 3-hydroxypyridine was cold-pressed into a circular electrolyte sheet with a thickness of 0.7 mm and a diameter of 8 mm. Inert electrodes (stainless steel) were used on both sides to perform impedance testing on a French Bio-Logic multi-channel electrochemical workstation VMP-300 instrument, with a perturbation voltage of 5 mV.

[0095] Application Example 4

[0096] Conductivity test: Potassium 4-hydroxypyridine was cold-pressed into a circular electrolyte sheet with a thickness of 0.65 mm and a diameter of 10 mm. Inert electrodes (stainless steel) were used on both sides to perform impedance testing on a French Bio-Logic multi-channel electrochemical workstation VMP-300 instrument, with a perturbation voltage of 10 mV.

[0097] Table 1 Conductivity of various hydroxypyridinium salts at different temperatures

[0098]

[0099]

[0100] As can be seen from Table 1, different hydroxypyridine salts all exhibit certain conductivity at different temperature ranges, and meet the requirements of solid-state batteries at different temperatures.

[0101] 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 contents without departing from the scope of the present application, and such changes or modifications are equivalent to equivalent embodiments, and all belong to the scope of the technical solutions.

Claims

1. A solid state electrolyte, characterized by, The solid-state electrolyte comprises a hydroxypyridine salt; the hydroxypyridine salt is selected from at least one of the structures shown in Formula I, Formula II or Formula III; In Formula I, Formula II, Formula III, M is independently selected from one of Li, Na, K.

2. The solid-state electrolyte of claim 1, wherein, The thickness of the solid-state electrolyte is 0.5-1 mm; Preferably, the diameter of the solid-state electrolyte is 5-10 mm.

3. The method of producing a solid-state electrolyte according to any one of claims 1 to 2, characterized by, The preparation method comprises: The hydroxypyridine salt is cold-pressed to form the solid-state electrolyte.

4. The production method according to claim 3, characterized by, The preparation method of the hydroxypyridine salt comprises: A mixture I containing a hydroxypyridine compound, an alkali metal hydride and water is stirred, reacted, and water is removed to obtain the hydroxypyridine salt; Alternatively, in a closed reactor, a mixture II containing a hydroxypyridine compound, an alkali metal compound and a solvent is stirred until the reaction II is completed, and the solvent is removed to obtain the hydroxypyridine salt.

5. The preparation method according to claim 4, characterized in that The hydroxypyridine compound is selected from at least one of 2-hydroxypyridine, 3-hydroxypyridine and 4-hydroxypyridine; Preferably, the alkali metal hydride is selected from at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium bicarbonate, sodium bicarbonate and potassium bicarbonate; Preferably, the alkali metal compound is selected from at least one of lithium hydride, sodium hydride, potassium hydride, lithium amide, sodium amide, potassium amide, lithium imide, sodium imide and potassium imide.

6. The preparation method according to claim 4, characterized in that The molar ratio of the hydroxypyridine compound to the alkali metal hydride is 1:0.7-1:1.3; Preferably, the molar ratio of the hydroxypyridine compound to the alkali metal compound is 1:0.7-1:1.

3.

7. The preparation method according to claim 4, characterized in that The molar concentration of the hydroxypyridine compound dissolved in water is 0.1-1.0 mol / L; Preferably, the solvent is selected from at least one of tetrahydrofuran, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide and diethylene glycol dimethyl ether; Preferably, the molar concentration of the hydroxypyridine compound dissolved in the solvent is 0.1-1.0 mol / L.

8. The preparation method according to claim 4, characterized in that The stirring I is carried out at a temperature of 20-60°C and a stirring speed of 100-500 r / min; Preferably, the reaction I is carried out for 2-6 h; Preferably, the stirring II is carried out at a temperature of 20-120°C and a stirring speed of 50-500 r / min.

9. The production method according to claim 3, wherein The cold-pressing is carried out at a pressure of 1.5-4 MPa.

10. The solid-state electrolyte according to any one of claims 1-2 for use in an alkali metal ion battery.

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