High-pressure in-situ cured high-ionic-conductivity electrolyte material and preparation process thereof

Abstract

The invention discloses a high-pressure in-situ cured electrolyte material with high ionic conductivity, which is characterized by mainly comprising the following components: an organic polymer matrix; an inorganic filler; an ionic liquid; a cross-linking agent; and a catalyst. According to the high-pressure in-situ cured high-ionic-conductivity electrolyte material and the preparation process thereof, components such as the organic polymer matrix, the inorganic filler and the ionic liquid are reasonably selected, and a high-pressure in-situ curing process is combined, so that organic combination of high ionic conductivity and good mechanical performance is realized, meanwhile, the preparation process is simplified, and the preparation cost is reduced. The production cost is reduced, and the environmental adaptability of the material is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electrolyte materials, in particular to a high-pressure in-situ solidified high-ionic-conductivity electrolyte material and a preparation process thereof. BACKGROUND

[0002] Electrolyte materials, as the medium for ion transport, play a crucial role in many electrochemical fields. From traditional battery technology to modern supercapacitors, fuel cells, sensors, and solid-state electrochromic devices, the performance of electrolyte materials directly determines the energy density, power density, cycle stability, and safety of these devices.

[0003] Traditional electrolyte materials are mainly divided into two categories: liquid electrolytes and solid-state electrolytes. Although liquid electrolytes have high ionic conductivity, they have problems such as easy leakage, flammability, and poor stability at high temperatures, which greatly limits their use in some high-safety application scenarios, such as electric vehicles and portable electronic devices. In addition, the use of liquid electrolytes can also increase the number of side reactions inside the battery, thereby reducing the cycle life of the battery. Solid-state electrolytes overcome some of the shortcomings of liquid electrolytes to some extent. However, existing solid-state electrolyte materials also face many challenges. For example, although polymer-based solid-state electrolytes have good flexibility and processability, their ionic conductivity is usually low, making it difficult to meet the needs of high-power-density devices. Inorganic ceramic solid-state electrolytes have high ionic conductivity, but they are brittle, difficult to machine, and have poor interfacial compatibility with electrode materials, which can increase the electrochemical polarization at the interface and reduce the overall performance of the device. In addition, the preparation process of existing solid-state electrolyte materials often requires complex process conditions, such as high-temperature sintering and sol-gel methods, which not only increases production costs but also limits the feasibility of large-scale production. Ionic conductivity is one of the key indicators of the performance of electrolyte materials. High ionic conductivity means that ions can be transported more smoothly in the electrolyte material, thereby achieving faster charging and discharging rates and higher energy conversion efficiency. For batteries, high-ionic-conductivity electrolyte materials can significantly reduce the internal resistance of the battery, improving the output power and energy density of the battery. In the field of sensors, high-ionic-conductivity electrolytes can quickly respond to changes in ion concentration, thereby improving the sensitivity and detection accuracy of the sensor. However, the ionic conductivity of most existing electrolyte materials still cannot meet the needs of high-performance electrochemical devices, especially achieving high ionic conductivity at room temperature remains a pressing problem.

[0004] In view of the many shortcomings of existing electrolyte materials in terms of ionic conductivity, mechanical properties, and preparation process, the present application proposes a high-pressure in-situ solidified high-ionic-conductivity electrolyte material and a preparation process thereof. SUMMARY

[0005] The present application aims to provide a high-pressure in-situ cured high ionic conductivity electrolyte material and its preparation process to solve the problems raised in the background.

[0006] To achieve the above-mentioned purpose, the present application provides the following technical solutions:

[0007] A high-pressure in-situ cured high ionic conductivity electrolyte material, mainly composed of the following components:

[0008] An organic polymer matrix;

[0009] An inorganic filler;

[0010] An ionic liquid;

[0011] A crosslinking agent;

[0012] A catalyst.

[0013] Preferably, the organic polymer matrix includes but is not limited to one or more of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF) or polymethyl methacrylate (PMMA), and the organic polymer matrix accounts for 30%-70% in the total.

[0014] Preferably, the inorganic filler includes but is not limited to one or more of silicon dioxide (SiO2), aluminum oxide (Al2O3) or titanium white powder (TiO2), and the inorganic filler accounts for 10%-40% in the total.

[0015] Preferably, the ionic liquid includes but is not limited to one or more of 1-ethyl-3-methyl imidazole tetrafluoroborate (EMIMBF4), 1-butyl-3-methyl imidazole hexafluorophosphate (BMIMPF6) or 1-ethyl-3-methyl imidazole bis(trifluoromethylsulfonyl) imide (EMIMTFSI), and the ionic liquid accounts for 10%-30% in the total.

[0016] Preferably, the crosslinking agent is a peroxide crosslinking agent, which can be selected from but is not limited to alkyl peroxide, diacyl peroxide, peroxide ester and peroxide ketal, and the crosslinking agent accounts for 1%-5% in the total.

[0017] Preferably, the catalyst is an organic amine catalyst, which can be selected from but is not limited to triethylene diamine, bisdimethylaminoethyl ether, N-alkyl morpholine, monoethanolamine and lysine derivatives, and the catalyst accounts for 1% in the total.

[0018] A high-pressure in-situ cured high ionic conductivity electrolyte material preparation process, comprising the following steps:

[0019] Step 1: Mixing raw materials: Mix the organic polymer matrix, inorganic filler, ionic liquid, crosslinking agent and catalyst in proportion and stir evenly to form a uniform mixture. Specifically:

[0020] Accurately weigh the organic polymer matrix, inorganic filler, ionic liquid, crosslinker, and catalyst in proportion and add them to a high-speed blender. During the blending process, gradually increase the stirring speed to 1000-2000 rpm and continue stirring for 30-60 minutes to ensure that all components are thoroughly mixed. During the blending process, heat the mixture to 40-60°C to reduce the viscosity of the polymer and further promote mixing uniformity.

[0021] The choice of stirring speed and time should be adjusted based on the specific properties of the raw materials and the performance of the equipment. A stirring speed that is too low may result in uneven mixing, while a speed that is too high may introduce excessive air, affecting the density of the material. Controlling the heating temperature is also crucial: too high a speed may cause premature reaction or decomposition of some components, while too low a speed may not effectively reduce viscosity. It is important to avoid excessive oxidation or moisture in the raw materials during the mixing process, especially for humidity-sensitive inorganic fillers and ionic liquids. Furthermore, the stirring equipment should be kept clean to prevent residual impurities from affecting material properties.

[0022] Step 2: Solution preparation: Dissolve the mixture in an appropriate amount of organic solvent to form a uniform solution. The organic solvent is selected from one of dichloromethane, tetrahydrofuran or acetonitrile, specifically:

[0023] Slowly add the mixed raw materials to an appropriate amount of organic solvent. The amount of organic solvent should be adjusted according to the solubility of the raw materials and the desired solution concentration. Generally, the amount of organic solvent used is 30%-50% of the total weight of the raw materials. Use ultrasonic dispersion equipment to treat the solution, set the ultrasonic power to 100-300W, and the treatment time is 10-30 minutes to ensure that the inorganic filler and other components are evenly dispersed in the solution. Subsequently, place the solution in a vacuum drying oven and evacuate to -0.1MPa for 30-60 minutes to remove bubbles and impurities in the solution;

[0024] The time and power of ultrasonic dispersion need to be adjusted according to the particle size and dispersion difficulty of the inorganic filler. For fillers with smaller particle size and easy agglomeration, longer time and higher power ultrasonic treatment may be required. The time and pressure of vacuum treatment should also be optimized according to the viscosity and bubble content of the solution to ensure the purity and uniformity of the solution. It should be noted that when adding organic solvents, they should be added slowly and stirred continuously to prevent local concentration from being too high and causing precipitation. During the ultrasonic dispersion process, attention should be paid to controlling the temperature to avoid local overheating caused by ultrasound that may lead to decomposition of the raw materials. During vacuum treatment, the sealing of the equipment should be ensured to prevent outside air from entering and affecting the quality of the solution.

[0025] Step 3: Casting: Pour the solution into a mold, place it in an autoclave, apply a pressure of 1-10 MPa, and a temperature of 50-100°C for 2-6 hours to solidify the solution under high pressure conditions. Specifically:

[0026] The treated solution is poured into a pre-prepared mold. The shape and size of the mold should be designed according to the final use of the desired electrolyte material. The mold filled with the solution is placed in an autoclave, and the autoclave door is slowly closed and sealed. The autoclave is pressurized by an external booster device. The pressure range is 1-10 MPa, and the heating rate is 2-5 ° C / min. The temperature is raised to 50-100 ° C and maintained at this temperature for 2-6 hours. The solution undergoes a cross-linking and curing reaction under high pressure and high temperature conditions to form an electrolyte material with a certain shape and performance.

[0027] The applied pressure and temperature are key factors affecting the performance of the material. Higher pressure helps to improve the density and mechanical strength of the material, but too high pressure may cause damage to the equipment or decomposition of the raw materials. The choice of temperature needs to be adjusted according to the reaction characteristics of the organic polymer matrix and the cross-linking agent. Too low a temperature may lead to incomplete cross-linking reaction, and too high a temperature may trigger side reactions. The length of the curing time will also affect the performance of the material. Too short a time may lead to insufficient cross-linking inside the material, and too long a time may cause aging of the material. When pouring the solution into the mold, the mixing of bubbles should be avoided as much as possible, and vacuum casting can be used for operation. During the heating and pressurization process of the autoclave, the operating procedures should be strictly followed to ensure the safe operation of the equipment. During the curing process, the operating status of the equipment should be checked regularly to ensure the stability of temperature and pressure.

[0028] Step 4: Post-processing: Remove the solidified electrolyte material from the mold, clean the residual solvent on the surface with deionized water, and dry it to obtain the final electrolyte material. Specifically:

[0029] After curing is completed, the autoclave is slowly depressurized to normal pressure at a cooling rate of 2-3°C / minute to avoid stress concentration inside the material due to rapid changes in temperature and pressure. After the temperature drops to room temperature, open the autoclave and carefully remove the mold. Demold the electrolyte material in the mold and repeatedly clean the surface of the material with deionized water to remove residual organic solvents and unreacted raw materials. The cleaned material is placed in a drying oven and dried at 40-60°C for 12-24 hours to completely remove moisture and residual solvents to obtain the final electrolyte material;

[0030] Controlling the cooling rate is crucial to preventing the buildup of internal stress in the material. Excessively rapid cooling rates can cause cracks or delamination within the material. The drying temperature and time should be adjusted based on the material's water absorption and thickness to ensure complete removal of moisture and solvents. Overdrying should also be avoided, which can degrade the material's performance. During the demolding process, care should be taken to avoid damaging the material. For cleaning, use deionized water; avoid using water containing impurities that could contaminate the surface. Regularly check the material's dryness during the drying process to avoid overdrying or incomplete drying.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] 1. This high-pressure in-situ cured high-ionic conductivity electrolyte material and its preparation process. By rationally selecting components such as an organic polymer matrix, inorganic filler, and ionic liquid, and combining it with a high-pressure in-situ curing process, this material achieves an organic combination of high ionic conductivity and good mechanical properties. At the same time, it simplifies the preparation process, reduces production costs, and improves the environmental adaptability of the material.

[0033] 2. This high-pressure, in-situ cured, high-ionic conductivity electrolyte material exhibits excellent ionic conductivity at room temperature and maintains stable performance over a wide temperature range, meeting the application requirements of a variety of electrochemical devices. Furthermore, the preparation process is simple and easy to implement, allowing for large-scale production, possessing broad application prospects and significant practical significance.

[0034] 3. This high-pressure in-situ solidified high ionic conductivity electrolyte material significantly improves the ionic conductivity of the electrolyte material by introducing ionic liquid and inorganic filler, making it reach 10-3-10-2S / cm at room temperature.

[0035] 4. This high-pressure in-situ cured high ionic conductivity electrolyte material, the high-pressure in-situ curing process gives the material high mechanical strength and toughness, can withstand certain external forces, and maintain stable performance in a wide temperature range, suitable for a variety of working environments. DETAILED DESCRIPTION

[0036] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0037] The present invention provides a high-ionic conductivity electrolyte material with high-pressure in-situ curing and a preparation process technology solution thereof:

[0038] A high-pressure in-situ solidified high ionic conductivity electrolyte material, characterized by being mainly composed of the following components:

[0039] organic polymer matrix;

[0040] Inorganic fillers;

[0041] Ionic liquids;

[0042] cross-linking agent;

[0043] catalyst.

[0044] The organic polymer matrix includes but is not limited to one or more of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF) or polymethyl methacrylate (PMMA), and the organic polymer matrix accounts for 30%-70% of the total.

[0045] The inorganic filler includes but is not limited to one or more of silicon dioxide (SiO2), aluminum oxide (Al2O3) or titanium dioxide (TiO2), and the inorganic filler accounts for 10%-40% of the total.

[0046] The ionic liquid includes but is not limited to one or more of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF4), 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6) or 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIMTFSI), and the ionic liquid accounts for 10%-30% of the total.

[0047] The crosslinking agent is a peroxide crosslinking agent, which may be selected from but not limited to alkyl peroxides, diacyl peroxides, peroxyesters and peroxyketals, and the crosslinking agent accounts for 1%-5% of the total.

[0048] The catalyst is an organic amine catalyst, which may be selected from but not limited to triethylenediamine, bisdimethylaminoethyl ether, N-alkylmorpholine, monoethanolamine and lysine derivatives, and the catalyst accounts for 1% of the total.

[0049] A process for preparing a high-ionic conductivity electrolyte material by high-pressure in-situ curing comprises the following steps:

[0050] Step 1: Mixing raw materials: Mix the organic polymer matrix, inorganic filler, ionic liquid, crosslinking agent and catalyst in proportion and stir evenly to form a uniform mixture. Specifically:

[0051] Accurately weigh the organic polymer matrix, inorganic filler, ionic liquid, crosslinker, and catalyst in proportion and add them to a high-speed blender. During the blending process, gradually increase the stirring speed to 1000-2000 rpm and continue stirring for 30-60 minutes to ensure that all components are thoroughly mixed. During the blending process, heat the mixture to 40-60°C to reduce the viscosity of the polymer and further promote mixing uniformity.

[0052] The choice of stirring speed and time should be adjusted based on the specific properties of the raw materials and the performance of the equipment. A stirring speed that is too low may result in uneven mixing, while a speed that is too high may introduce excessive air, affecting the density of the material. Controlling the heating temperature is also crucial: too high a speed may cause premature reaction or decomposition of some components, while too low a speed may not effectively reduce viscosity. It is important to avoid excessive oxidation or moisture in the raw materials during the mixing process, especially for humidity-sensitive inorganic fillers and ionic liquids. Furthermore, the stirring equipment should be kept clean to prevent residual impurities from affecting material properties.

[0053] Step 2: Solution preparation: Dissolve the mixture in an appropriate amount of organic solvent to form a uniform solution. The organic solvent is selected from one of dichloromethane, tetrahydrofuran or acetonitrile, specifically:

[0054] Slowly add the mixed raw materials to an appropriate amount of organic solvent. The amount of organic solvent should be adjusted according to the solubility of the raw materials and the desired solution concentration. Generally, the amount of organic solvent used is 30%-50% of the total weight of the raw materials. Use ultrasonic dispersion equipment to treat the solution, set the ultrasonic power to 100-300W, and the treatment time is 10-30 minutes to ensure that the inorganic filler and other components are evenly dispersed in the solution. Subsequently, place the solution in a vacuum drying oven and evacuate to -0.1MPa for 30-60 minutes to remove bubbles and impurities in the solution;

[0055] The time and power of ultrasonic dispersion need to be adjusted according to the particle size and dispersion difficulty of the inorganic filler. For fillers with smaller particle size and easy agglomeration, longer time and higher power ultrasonic treatment may be required. The time and pressure of vacuum treatment should also be optimized according to the viscosity and bubble content of the solution to ensure the purity and uniformity of the solution. It should be noted that when adding organic solvents, they should be added slowly and stirred continuously to prevent local concentration from being too high and causing precipitation. During the ultrasonic dispersion process, attention should be paid to controlling the temperature to avoid local overheating caused by ultrasound that may lead to decomposition of the raw materials. During vacuum treatment, the sealing of the equipment should be ensured to prevent outside air from entering and affecting the quality of the solution.

[0056] Step 3: Casting: Pour the solution into a mold, place it in an autoclave, apply a pressure of 1-10 MPa, and a temperature of 50-100°C for 2-6 hours to solidify the solution under high pressure conditions. Specifically:

[0057] The treated solution is poured into a pre-prepared mold. The shape and size of the mold should be designed according to the final use of the desired electrolyte material. The mold filled with the solution is placed in an autoclave, and the autoclave door is slowly closed and sealed. The autoclave is pressurized by an external booster device. The pressure range is 1-10 MPa, and the heating rate is 2-5 ° C / min. The temperature is raised to 50-100 ° C and maintained at this temperature for 2-6 hours. The solution undergoes a cross-linking and curing reaction under high pressure and high temperature conditions to form an electrolyte material with a certain shape and performance.

[0058] The applied pressure and temperature are key factors affecting the performance of the material. Higher pressure helps to improve the density and mechanical strength of the material, but too high pressure may cause damage to the equipment or decomposition of the raw materials. The choice of temperature needs to be adjusted according to the reaction characteristics of the organic polymer matrix and the cross-linking agent. Too low a temperature may lead to incomplete cross-linking reaction, and too high a temperature may trigger side reactions. The length of the curing time will also affect the performance of the material. Too short a time may lead to insufficient cross-linking inside the material, and too long a time may cause aging of the material. When pouring the solution into the mold, the mixing of bubbles should be avoided as much as possible, and vacuum casting can be used for operation. During the heating and pressurization process of the autoclave, the operating procedures should be strictly followed to ensure the safe operation of the equipment. During the curing process, the operating status of the equipment should be checked regularly to ensure the stability of temperature and pressure.

[0059] Step 4: Post-processing: Remove the solidified electrolyte material from the mold, clean the residual solvent on the surface with deionized water, and dry it to obtain the final electrolyte material. Specifically:

[0060] After curing is completed, the autoclave is slowly depressurized to normal pressure at a cooling rate of 2-3°C / minute to avoid stress concentration inside the material due to rapid changes in temperature and pressure. After the temperature drops to room temperature, open the autoclave and carefully remove the mold. Demold the electrolyte material in the mold and repeatedly clean the surface of the material with deionized water to remove residual organic solvents and unreacted raw materials. The cleaned material is placed in a drying oven and dried at 40-60°C for 12-24 hours to completely remove moisture and residual solvents to obtain the final electrolyte material;

[0061] Controlling the cooling rate is crucial to preventing the buildup of internal stress in the material. Excessively rapid cooling rates can cause cracks or delamination within the material. The drying temperature and time should be adjusted based on the material's water absorption and thickness to ensure complete removal of moisture and solvents. Overdrying should also be avoided, which can degrade the material's performance. During the demolding process, care should be taken to avoid damaging the material. For cleaning, use deionized water; avoid using water containing impurities that could contaminate the surface. Regularly check the material's dryness during the drying process to avoid overdrying or incomplete drying.

[0062] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A high-ionic conductivity electrolyte material cured in situ under high pressure, characterized in that: It is mainly composed of the following ingredients: organic polymer matrix; Inorganic fillers; Ionic liquids; cross-linking agent; catalyst.

2. The high-pressure in-situ cured high ionic conductivity electrolyte material according to claim 1, characterized in that: The organic polymer matrix includes but is not limited to one or more of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF) or polymethyl methacrylate (PMMA), and the organic polymer matrix accounts for 30%-70% of the total.

3. The high-pressure in-situ solidified high ionic conductivity electrolyte material and its preparation process according to claim 1, characterized in that: The inorganic filler includes but is not limited to one or more of silicon dioxide (SiO2), aluminum oxide (Al2O3) or titanium dioxide (TiO2), and the inorganic filler accounts for 10%-40% of the total.

4. The high-pressure in-situ cured high ionic conductivity electrolyte material according to claim 1, characterized in that: The ionic liquid includes but is not limited to one or more of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF4), 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6) or 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIMTFSI), and the ionic liquid accounts for 10%-30% of the total.

5. The high-pressure in-situ cured high ionic conductivity electrolyte material according to claim 1, characterized in that: The crosslinking agent is a peroxide crosslinking agent. The crosslinking agent may be selected from but is not limited to alkyl peroxides, diacyl peroxides, peroxyesters and peroxyketals, and the crosslinking agent accounts for 1%-5% of the total.

6. The high-pressure in-situ cured high ionic conductivity electrolyte material according to claim 1, characterized in that: The catalyst is an organic amine catalyst, which may be selected from but not limited to triethylenediamine, bisdimethylaminoethyl ether, N-alkylmorpholine, monoethanolamine and lysine derivatives, and the catalyst accounts for 1% of the total.

7. A process for preparing a high-ionic conductivity electrolyte material by high-pressure in-situ curing, characterized in that: The following steps are involved: Step 1: Mixing raw materials: Mix the organic polymer matrix, inorganic filler, ionic liquid, crosslinking agent and catalyst in proportion, stir evenly to form a uniform mixture; Step 2: Solution preparation: dissolving the mixture in an appropriate amount of an organic solvent to form a uniform solution. The organic solvent is selected from dichloromethane, tetrahydrofuran, or acetonitrile; Step 3: Casting and molding: Pour the solution into a mold, place it in an autoclave, apply a pressure of 1-10 MPa, and a temperature of 50-100°C for 2-6 hours to solidify the solution under high pressure conditions; Step 4: Post-processing: The solidified electrolyte material is removed from the mold, the residual solvent on the surface is cleaned with deionized water, and the final electrolyte material is obtained after drying.