CN104362003A - Method for manufacturing gel polymer electrolyte - Google Patents

Abstract

The embodiment of the present invention discloses a method for manufacturing a gel polymer electrolyte, comprising: dissolving an electrolyte salt in a plasticizer solvent to obtain a liquid electrolyte solution; adding a polymer matrix material to the liquid electrolyte solution, adding an inorganic filler for composite modification, and adding an organic solvent and uniformly mixing to obtain a first mixed solution; adding an ionic liquid to the first mixed solution to obtain a second mixed solution; casting the second mixed solution in a mold and drying to obtain a gel polymer electrolyte. The method for manufacturing a blended ionic liquid composite gel polymer electrolyte provided by the present invention is simple to operate, has low production cost, high safety, and an easy-to-control preparation process, and can be widely used in the production of electrolytes.

Description

A method of making a gel polymer electrolyte

technical field

The invention relates to the technical field of electronic materials, in particular to a method for manufacturing a gel polymer electrolyte for capacitors. the

Background technique

Supercapacitors are mainly composed of polarized electrodes, collectors, electrolytes, separators, leads, and packaging materials. Among them, the electrolyte needs to have high conductivity and sufficient electrochemical stability to ensure that the supercapacitor can operate as much as possible. work under high voltage. Gel polymer electrolytes have the above excellent characteristics and are not leaky and have a wide temperature range. Therefore, there are more and more studies on the use of gel polymer electrolytes to improve capacitor performance. the

Polymer blending is an effective method to prepare new gel polymer electrolytes, which can improve the shortcomings of a single polymer matrix material such as low conductivity, poor mechanical properties, and narrow electrochemical window. the

Adding nano-inorganic fillers to the gel polymer electrolyte to form a composite gel polymer electrolyte can effectively improve the conductivity of the electrolyte. The high specific surface area of nano-inorganic fillers can inhibit the crystallization behavior of polymer molecular chains, thereby increasing the proportion of polymer amorphous regions, reducing the crystallinity and glass transition temperature of polymers, and improving the conductivity of electrolytes. the

Room temperature ionic liquids have the following characteristics: (1) almost no vapor pressure and non-volatile properties; (2) good electrical conductivity; (3) wide electrochemical window; (4) wide stable temperature range. Therefore, the ionic liquid is introduced into the gel polymer electrolyte to obtain the ionic liquid-gel polymer electrolyte, which can perfectly combine the advantages of the ionic liquid and the gel polymer electrolyte. the

At present, the existing methods for preparing polymer electrolytes are mostly blending, compounding, and introducing ionic liquids. However, polymer electrolytes prepared simply by blending, compounding, or introducing ionic liquids cannot meet the high conductivity, wide electrochemical window, wide operating temperature range, electrochemical stability and excellent electrolyte requirements. mechanical performance requirements. the

Contents of the invention

One of the objects of the present invention is to provide a method for manufacturing a gel polymer electrolyte, the gel polymer electrolyte manufactured according to the method has high electrical conductivity and a wider electrochemical window, and thermal stability, electrochemical stability and mechanical properties are relatively good. the

The technical solutions disclosed in the present invention include:

Provided is a method for manufacturing a gel polymer electrolyte, characterized in that it comprises: dissolving an electrolyte salt in a plasticizer solvent to obtain a liquid electrolyte solution; adding a polymer matrix material to the liquid electrolyte solution, adding an inorganic Composite modification of the filler, and uniform mixing after adding an organic solvent to obtain a first mixed solution; adding an ionic liquid to the first mixed solution to obtain a second mixed solution; flowing the second mixed solution in a mold After prolonged treatment and drying, a gel polymer electrolyte is obtained.

In one embodiment of the present invention, the electrolyte salt is lithium perchlorate, lithium hexafluorophosphate or tetraethylammonium hexafluorophosphate. the

In one embodiment of the present invention, the plasticizer solvent is one or more of propylene carbonate, diethyl carbonate, dimethyl carbonate and ethylene carbonate. the

In one embodiment of the present invention, in the liquid electrolyte solution, the concentration of the electrolyte salt is 0.6 mol/liter to 1.5 mol/liter. the

In one embodiment of the present invention, the polymer matrix material is polymethyl methacrylate and polyvinylidene fluoride-hexafluoropropylene, and the polymethyl methacrylate and the polyvinylidene fluoride-hexafluoropropylene The mass ratio of propylene is 1:10 to 1:4; and: the mass ratio of the polymer matrix material to the electrolyte salt is 1.8:1 to 2.6:1. the

In one embodiment of the present invention, the inorganic filler is nano silicon dioxide, nano aluminum oxide, nano magnesium oxide or nano titanium dioxide, and the mass ratio of the inorganic filler to the polymer matrix material is 1:9 to 1:10.5. the

In one embodiment of the present invention, the organic solvent is tetrahydrofuran, acetonitrile, N,N-dimethylformamide or 1-methyl-2-pyrrolidone, and the volume of the organic solvent and the polymer matrix material The mass ratio is 5:1 to 10:1. the

In one embodiment of the present invention, the ionic liquid is 1,2-dimethyl-3-N-butylimidazole, 1-methyl-3-ethylimidazole tetrafluoroboric acid or 1-methyl-3- Butylimidazole hexafluorophosphate, and the mass ratio of the ionic liquid to the polymer matrix material is 1.5:1 to 2.2:1. the

The method for manufacturing the blended ionic liquid composite gel polymer electrolyte provided in the embodiments of the present invention is simple in operation, low in production cost, high in safety and easy to control in the preparation process, and can be widely used in the production of electrolytes. the

Description of drawings

FIG. 1 is a schematic flowchart of a method for manufacturing a gel polymer electrolyte according to an embodiment of the present invention. the

Detailed ways

The specific steps of the method for manufacturing a gel polymer electrolyte according to an embodiment of the present invention will be described in detail below with reference to the accompanying drawings. the

FIG. 1 is a schematic flowchart of a method for manufacturing a gel polymer electrolyte according to an embodiment of the present invention. Each step of the method will be described in detail below in conjunction with specific embodiments. the

Step 10: Preparation of Liquid Electrolyte Solution. the

As shown in FIG. 1 , in step 10, the electrolyte salt may be dissolved in a plasticizer solvent to obtain a liquid electrolyte solution. the

In one embodiment, the electrolyte salt here may be lithium perchlorate (LiClO ₄ ), lithium hexafluorophosphate (LiPF ₆ ), or tetraethylammonium hexafluorophosphate ((C ₂ H ₅ ) ₄ NPF ₆ ), and the like.

In one embodiment, the plasticizer solvent here can be one or more of propylene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC) and ethylene carbonate (EC), And the volume fraction of each component in the plasticizer solvent can be the same. the

In one embodiment, in the liquid electrolyte solution obtained in step 10, the concentration of the electrolyte salt may be 0.6 mol/L (mol/L) to 1.5 mol/L (mol/L). the

Step 12: Prepare the first mixed solution. the

After the liquid electrolyte solution is obtained, in step 12, the polymer matrix material can be added to the electrolyte solution, and the inorganic filler can be added for composite modification, and the organic solvent can be added and mixed uniformly, so as to obtain the first mixed solution. the

In one embodiment, the polymer matrix material here can be polymethyl methacrylate (PMMA) and polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), and in this polymer matrix material, PMMA and PVDF- The mass ratio of HFP can be 1:10～1:4. Moreover, in an embodiment, the mass ratio of the total polymer matrix material (ie, PMMA and PVDF-HFP) to the aforementioned electrolyte salt may be 1.8:1˜2.6:1. the

In one embodiment, the inorganic filler here can be nano silicon dioxide (SiO ₂ ), nano aluminum oxide (Al ₂ O ₃ ), nano magnesia (MgO) or nano titanium dioxide (TiO ₂ ), etc., and the The mass ratio of the inorganic filler to the aforementioned polymer matrix material may be 1:9˜1:10.5.

In one embodiment, the organic solvent here can be tetrahydrofuran (THF), acetonitrile, N,N-dimethylformamide (DMF) or 1-methyl-2-pyrrolidone (NMP) or the like, and the organic solvent and The volume-to-mass ratio of the aforementioned polymer matrix material may be 5:1˜10:1. the

In one embodiment of the present invention, in step 12, the aforementioned components may be mixed and stirred on a magnetic stirrer for 12 to 15 hours, so that the components are fully mixed, thereby obtaining the aforementioned first mixed solution. the

Step 14: Prepare a second mixed solution. the

After the first mixture solution is prepared in step 12, in step 14, an ionic liquid may be added to the first mixture solution to obtain a second mixture solution. the

In one embodiment, the ionic liquid here can be 1,2-dimethyl-3-N-butylimidazole (DMBITFSI), 1-methyl-3-ethylimidazole tetrafluoroboric acid (EMIBF ₄ ) or 1- Methyl-3-butylimidazolium hexafluorophosphate (BMIPF ₆ ), etc., and the mass ratio of the ionic liquid to the aforementioned polymer matrix material may be 1.5:1˜2.2:1.

In one embodiment, after the aforementioned ionic liquid is added to the first mixed solution, the second mixed solution can be obtained by stirring on a magnetic stirrer at room temperature for 1-2 hours and then standing for 5 minutes to remove air bubbles. the

Step 16: Casting and drying the second mixed solution to obtain a gel polymer electrolyte. the

After the second mixture solution is obtained in step 14, in step 16, the second mixture solution may be placed in a mold for casting, then placed in a drying oven, and dried at a temperature of 60 to 120 degrees Celsius for 40 to 50 hours. the

In this way, the required gel polymer electrolyte can be obtained through the aforementioned steps. the

Several specific examples of the present invention will be described in detail below. the

Example 1:

Weigh 0.6g LiClO ₄ and dissolve in 9.43ml PC and DEC mixed solution (the volume ratio of PC and DEC is 1:1), fully dissolve and prepare 0.6mol/L liquid electrolyte; another weigh 0.098g PMMA and Add 0.982g PVDF-HFP mixed polymer matrix, 0.108g Al ₂ O ₃ to the above liquid electrolyte, add 10ml NMP to mix, stir magnetically at room temperature for 12h to obtain solution A; take 1.62g EMIBF ₄ and add to solution A, room temperature Stir at low temperature for 1 hour, let it stand for 5 minutes to remove air bubbles, and obtain solution B; pour solution B into a polytetrafluoroethylene mold for casting, move it to an 80°C drying oven, dry it for 40 hours, and peel it off to obtain a blended ionic liquid compound Gel polymer electrolyte membrane.

The resulting blended ionic liquid composite gel polymer electrolyte membrane and stainless steel electrodes were used to form a blocking cell and tested on an electrochemical workstation. The conductivity was 3.5mS/cm, and the electrochemical working window was 4.2V. the

Example 2:

Weigh 0.8g LiClO ₄ and dissolve it in 9.43ml PC and DEC mixed solution (wherein the volume ratio of PC and DEC is 1:1), fully dissolve and prepare 0.8mol/L liquid electrolyte; another weigh 0.13g PMMA and Add 1.31g PVDF-HFP mixed polymer matrix, 0.137g Al ₂ O ₃ to the above liquid electrolyte, add 10ml NMP to mix, and stir magnetically at room temperature for 12h to obtain solution A; take 2.2g EMIBF ₄ and add to solution A, room temperature Stir at low temperature for 1 hour, let it stand for 5 minutes to remove air bubbles, and obtain solution B; pour solution B into a polytetrafluoroethylene mold for casting, move it to an 80°C drying oven, dry it for 40 hours, and peel it off to obtain a blended ionic liquid compound Gel polymer electrolyte membrane.

The resulting blended ionic liquid composite gel polymer electrolyte membrane and stainless steel electrodes were used to form a blocking cell and tested on an electrochemical workstation. The conductivity was 5.22mS/cm, and the electrochemical working window was 4.1V. the

Example 3:

Weigh 1g LiClO ₄ and dissolve it in 9.43ml PC and DEC mixed solution (wherein the volume ratio of PC and DEC is 1:1), fully dissolve and prepare a 1mol/L liquid electrolyte; another weigh 0.182g PMMA and 1.818g PVDF-HFP mixed polymer matrix, 0.2g Al ₂ O ₃ was added to the above liquid electrolyte, and 10ml NMP was added to mix, and magnetically stirred at room temperature for 12h to obtain solution A; 3g EMIBF ₄ was added to solution A, and stirred at room temperature for 1h , let it stand for 5 minutes to remove air bubbles, and obtain solution B; pour solution B into a polytetrafluoroethylene mold for casting, move it to an 80°C drying oven, dry it for 40 hours, and peel it off to obtain a blended ionic liquid composite gel polymer electrolyte membrane.

The resulting blended ionic liquid composite gel polymer electrolyte membrane and stainless steel electrodes were used to form a blocking cell and tested on an electrochemical workstation. The conductivity was 7.36mS/cm, and the electrochemical working window was 4.5V. the

Example 4:

Weigh 1.2g LiClO ₄ and dissolve it in 9.43ml PC and DEC mixed solution (wherein the volume ratio of PC and DEC is 1:1), fully dissolve and prepare 1.2mol/L liquid electrolyte; another weigh 0.4g PMMA and Add 2g PVDF-HFP mixed polymer matrix, 0.24g Al ₂ O ₃ to the above liquid electrolyte, add 10ml NMP to mix, and stir magnetically at room temperature for 12h to obtain solution A; take 3.6g EMIBF ₄ and add it to solution A, Stir for 1 hour, let it stand for 5 minutes to remove air bubbles, and obtain solution B; pour solution B into a polytetrafluoroethylene mold for casting, move it to an 80°C drying oven, dry it for 40 hours, and peel it off to obtain a blended ionic liquid composite gel. gel polymer electrolyte membrane.

The resulting blended ionic liquid composite gel polymer electrolyte membrane and stainless steel electrodes were used to form a blocking cell and tested on an electrochemical workstation. The conductivity was 4.3mS/cm, and the electrochemical working window was 4.05V. the

Example 5:

Weigh 1.5g LiClO ₄ and dissolve it in 9.43ml PC and DEC mixed solution (wherein the volume ratio of PC and DEC is 1:1), fully dissolve and prepare 1.5mol/L liquid electrolyte; another weigh 0.5g PMMA and Add 2.5g PVDF-HFP mixed polymer matrix, 0.3g Al ₂ O ₃ to the above liquid electrolyte, add 10ml NMP to mix, stir magnetically at room temperature for 12h to obtain solution A; take 4.5g EMIBF ₄ and add to solution A, room temperature Stir at low temperature for 1 hour, let it stand for 5 minutes to remove air bubbles, and obtain solution B; pour solution B into a polytetrafluoroethylene mold for casting, move it to an 80°C drying oven, dry it for 40 hours, and peel it off to obtain a blended ionic liquid compound Gel polymer electrolyte membrane.

The resulting blended ionic liquid composite gel polymer electrolyte membrane and stainless steel electrodes were used to form a blocking cell and tested on an electrochemical workstation. The conductivity was 3.4mS/cm, and the electrochemical working window was 4.1V. the

In the embodiment of the present invention, aiming at the fact that traditional gel polymer electrolytes cannot have the advantages of thermal stability, high electrical conductivity and wide electrochemical window at the same time, it is proposed to modify the gel polymer electrolyte by blending and compounding , and the introduction of room temperature ionic liquids to prepare blended ionic liquid composite gel polymer electrolytes. The electrolyte prepared by the method of the embodiment of the present invention has high conductivity, good thermal stability, wide electrochemical window, good mechanical properties and good compatibility with electrode materials, etc., which can meet the requirements of supercapacitors and lithium-ion batteries. and other usage requirements. the

The method for manufacturing the blended ionic liquid composite gel polymer electrolyte provided in the embodiments of the present invention is simple in operation, low in production cost, high in safety and easy to control in the preparation process, and can be widely used in the production of electrolytes. the

The present invention has been described above through specific examples, but the present invention is not limited to these specific examples. Those skilled in the art should understand that various modifications, equivalent replacements, changes, etc. can also be made to the present invention. As long as these changes do not deviate from the spirit of the present invention, they should all be within the protection scope of the present invention. In addition, "one embodiment" described in many places above represents different embodiments, and of course all or part of them may be combined in one embodiment. the

Claims (8)

1. manufacture a method for gel polymer electrolyte, it is characterized in that, comprising:

Electrolytic salt is dissolved in plasticizer solvent, obtains liquid electrolyte solution;

Matrix material is added in described liquid electrolyte solution, adds inorganic filler and carry out composite modified, and Homogeneous phase mixing after adding organic solvent, obtain the first mixed solution;

In described first mixed solution, add ionic liquid, obtain the second mixed solution;

Described second mixed solution is carried out in a mold curtain coating process and drying, obtain gel polymer electrolyte.

2. the method for claim 1, is characterized in that: described electrolytic salt is lithium perchlorate, lithium hexafluoro phosphate or hexafluorophosphoric acid tetraethyl amine.

3. as described in claim 1 or 2 method, is characterized in that: described plasticizer solvent is one or more in propene carbonate, diethyl carbonate, dimethyl carbonate and ethylene carbonate.

4. method as claimed any one in claims 1 to 3, it is characterized in that: in described liquid electrolyte solution, the concentration of described electrolytic salt is 0.6 mol/L to 1.5 mol/L.

5. the method according to any one of Claims 1-4, it is characterized in that: described matrix material is polymethyl methacrylate and Kynoar-hexafluoropropylene, and the mass ratio of described polymethyl methacrylate and described Kynoar-hexafluoropropylene is 1:10 to 1:4; And: the mass ratio of described matrix material and described electrolytic salt is 1.8:1 to 2.6:1.

6. the method for claim 1, it is characterized in that: described inorganic filler is nano silicon, nano-aluminium oxide, nano magnesia or nano titanium oxide, and the mass ratio of described inorganic filler and described matrix material is 1:9 to 1:10.5.

7. the method according to any one of claim 1 to 6, it is characterized in that: described organic solvent is oxolane, acetonitrile, N, dinethylformamide or 1-Methyl-2-Pyrrolidone, and described organic solvent is 5:1 to 10:1 with the volume mass ratio of described matrix material.

8. the method for claim 1, it is characterized in that: described ionic liquid is 1,2-dimethyl-3-N-butyl imidazole, 1-methyl-3-ethyl imidazol(e) tetrafluoro boric acid or 1-methyl-3-butyl imidazole hexafluorophosphoric acid, and the mass ratio of described ionic liquid and matrix material is 1.5:1 to 2.2:1.