CN115602918A - Gel electrolyte membrane and preparation method and application thereof - Google Patents
Gel electrolyte membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a gel electrolyte membrane and a preparation method and application thereof, wherein the preparation method comprises the following steps: after modifying the natural polysaccharide polymer by using a silane coupling agent, dissolving the natural polysaccharide polymer in a first solvent, performing ultrasonic dispersion under an ice bath condition, and then stirring at a constant temperature to obtain a solution of the natural polysaccharide polymer; dissolving polyvinylidene fluoride-hexafluoropropylene in a second solvent, adding polyoxyethylene, and heating and stirring to obtain a mixed solution; mixing the dispersion liquid of the natural polysaccharide polymer with the mixed solution, and heating and stirring to obtain polymer electrolyte slurry; and solidifying and molding the polymer electrolyte slurry, and then immersing the polymer electrolyte slurry into electrolyte in an inert gas atmosphere for activation to obtain the gel electrolyte membrane. The gel electrolyte membrane prepared by the preparation method has a three-dimensional porous network for rapidly conducting lithium ions, and the structure can obviously improve the liquid absorption rate and the liquid holding rate of the electrolyte.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries. And more particularly, to a gel electrolyte membrane, a method of preparing the same, and applications thereof.
Background
Using solid electrolytesThe battery can replace the diaphragm in the traditional sense and avoid all or most of electrolyte, and is hopeful to solve the safety problem of the high-energy density battery. The inorganic electrolyte has high ionic conductivity (10) -4 ～10 -2 Scm -1 ) Thermal stability and mechanical strength are high, but processability and interface properties are poor; while the traditional polymer electrolyte has good flexibility and easy processing, but has low ionic conductivity and mechanical modulus. The gel electrolyte is formed by solidifying organic electrolyte with polymer to form gel electrolyte, improves the contact between the electrolyte and an electrode interface to a certain extent, and theoretically has good ionic conductivity (10) of liquid electrolyte -4 ～10 -3 Scm -1 ) And the high safety of solid electrolytes, and the like, become the research hotspot of the current high-performance and high-safety electrolytes.
Generally, an electrolyte solution containing an ion conductor is dispersed in a gel-state electrolyte, and a gel electrolyte membrane having a certain ion conductivity can be obtained, but the adsorption rate and the liquid holding rate of the conventional gel-state electrolyte to the electrolyte solution are very limited, and therefore, it is necessary to provide a gel electrolyte membrane having a unique structure to improve the liquid absorption rate and the liquid holding rate of the electrolyte solution.
Disclosure of Invention
In view of the above problems, the present invention has been made in order to provide a gel electrolyte membrane, a method of manufacturing the same, and applications thereof, which overcome the above problems or at least partially solve the above problems.
According to an aspect of the present invention, there is provided a method of preparing a gel electrolyte membrane, including: providing a diluent containing 1-10% of natural polysaccharide polymer by mass, then mixing and hydrolyzing a silane coupling agent, deionized water and methanol, then dropwise adding the mixture into the diluent, mixing and stirring, and washing and drying to obtain the silane coupling agent modified natural polysaccharide polymer; dissolving a silane coupling agent modified natural polysaccharide polymer in a first solvent, performing ultrasonic dispersion under an ice bath condition, and then stirring at a constant temperature to obtain a solution of the natural polysaccharide polymer; dissolving polyvinylidene fluoride-hexafluoropropylene in a second solvent, adding polyoxyethylene, and heating and stirring to obtain a mixed solution; mixing the solution of the natural polysaccharide polymer with the mixed solution, and heating and stirring to obtain polymer electrolyte slurry; and solidifying and molding the polymer electrolyte slurry, then immersing the polymer electrolyte slurry into the electrolyte in an inert gas atmosphere, and activating to obtain the gel electrolyte membrane.
Alternatively, in the preparation method of the gel electrolyte membrane according to the present invention, wherein the natural polysaccharide polymer is one or a combination of any of cellulose, chitosan, guar gum, β -cyclodextrin, and gum arabic.
Optionally, in the preparation method of the gel electrolyte membrane according to the invention, the solute of the electrolyte is one or a combination of any several of lithium bis (oxalato) borate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonato) imide, lithium hexafluorophosphate, lithium perchlorate and lithium difluoro (oxalato) borate.
Alternatively, in the method for producing a gel electrolyte membrane according to the present invention, wherein the mass ratio of the natural polysaccharide polymer, polyethylene oxide, and polyvinylidene fluoride-hexafluoropropylene in the polymer electrolyte slurry is 0.01 to 0.1.
Alternatively, in the preparation method of the gel electrolyte membrane according to the present invention, wherein the first solvent is one or a combination of any of deionized water, ethanol, ethylene glycol, propylene glycol, isopropanol, acetone, N-methylpyrrolidone, and N, N-dimethylformamide.
Alternatively, in the preparation method of the gel electrolyte membrane according to the present invention, wherein the second solvent is one or a combination of any several of NMP, DMF, ethanol, acetonitrile, isopropanol, and acetone.
Alternatively, in the method for producing a gel electrolyte membrane according to the present invention, wherein the relative molecular mass of polyvinylidene fluoride-hexafluoropropylene is 3 × 10 5 ～6×10 5 。
Alternatively, in the method for producing a gel electrolyte membrane according to the present invention, wherein the relative molecular mass of polyethylene oxide is 6 × 10 5 ～1×10 6 。
Alternatively, in the method for manufacturing a gel electrolyte membrane according to the present invention, wherein the thickness of the gel electrolyte membrane is 40 μm to 60 μm.
Alternatively, in the method for preparing a gel electrolyte membrane according to the present invention, wherein the mixed hydrolysis is performed for 1 to 4 hours at 25 to 50 ℃ under magnetic stirring.
Alternatively, in the method for preparing a gel electrolyte membrane according to the present invention, wherein the mixing and stirring are performed at 20 ℃ to 50 ℃ at a rotation speed of 2000rpm to 4000rpm for 1 hour to 2 hours.
Alternatively, in the method for producing a gel electrolyte membrane according to the present invention, wherein the step of washing and drying includes: vacuum filtering with water filter membrane, washing twice with methanol and once with water to remove methanol and unreacted silane coupling agent, and drying in vacuum drying oven at 50-100 deg.C for 12-24 hr.
Alternatively, in the preparation method of the gel electrolyte membrane according to the invention, the ultrasonic dispersion under the ice bath condition is ultrasonic treatment for 1-3 h in an ice bath ultrasonic low-temperature tank with the ultrasonic power of 450W and the ultrasonic frequency of 50-60 kHz.
Alternatively, in the preparation method of the gel electrolyte membrane according to the present invention, wherein the constant temperature stirring is performed for 8 to 12 hours at 20 to 50 ℃ at a rotation speed of 300 to 500 rpm.
Alternatively, in the method for preparing a gel electrolyte membrane according to the present invention, the heating and stirring are performed at 50 ℃ to 80 ℃ at a rotation speed of 300rpm to 500rpm for 1 hour to 2 hours.
Alternatively, in the method for preparing a gel electrolyte membrane according to the present invention, wherein the activation time is 1 to 8 hours.
Alternatively, in the method for producing a gel electrolyte membrane according to the present invention, wherein the step of curing and molding includes: the polymer electrolyte slurry was cast into a mold, followed by vacuum drying.
Alternatively, in the method for preparing a gel electrolyte membrane according to the present invention, wherein the vacuum drying is performed for 12 to 24 hours at 60 to 100 ℃.
As still another aspect of the present invention, there is provided a gel electrolyte membrane manufactured by the above manufacturing method.
According to still another aspect of the present invention, there is provided a lithium ion battery comprising a cathode, an anode and the above gel electrolyte membrane, the gel electrolyte membrane being located between the cathode and the anode.
According to the scheme of the invention, a silane coupling agent modified natural polysaccharide polymer material is subjected to ultrasonic treatment and constant-temperature stirring to be dispersed in a solvent for later use, polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) is used as a polymer electrolyte matrix to be dissolved in an organic solvent, polyethylene oxide (PEO) with a certain mass fraction is added to obtain a mixed solution, then a natural polysaccharide polymer dispersion solution is added into the mixed solution according to a certain solid content proportion, and heating and stirring are carried out to obtain uniform polymer electrolyte slurry. And casting the uniform slurry into a mold, and performing vacuum drying to obtain the polymer film. And (3) punching the polymer film into a round sheet, putting the round sheet into an Ar-atmosphere glove box, and immersing the round sheet into electrolyte for activation to obtain the gel polymer electrolyte film. The natural polysaccharide polymer has rich hydroxyl groups, can form intermolecular hydrogen bonds with polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) and polyethylene oxide (PEO), is bonded to construct a three-dimensional porous network with rapid lithium ion conduction, increases the liquid absorption rate and liquid holding rate of the gel electrolyte to the electrolyte, and improves the ionic conductivity. And secondly, the natural polysaccharide polymer has excellent mechanical property and thermal stability, and the mechanical property and high temperature resistance of the gel electrolyte membrane are improved, so that the gel electrolyte membrane can normally work in a wider temperature environment.
The preparation method provided by the invention can be used for preparing the gel electrolyte membrane with a three-dimensional porous network structure capable of rapidly conducting ions. The gel electrolyte with the structure not only can obviously improve the liquid absorption rate and the liquid retention rate of the electrolyte, but also has good flexibility, and particularly, the gel electrolyte membrane provided by the invention is used for treating lithium hexafluorophosphate (LiPF) 6 ) The liquid absorption rate of the electrolyte is improved to 432%, and the liquid retention rate in 8h after liquid absorption is still as high as 415%.
The gel electrolyte membrane provided by the invention has excellent ionic conductivity and obvious inhibition effect on lithium dendrites, so that the assembled lithium ion battery has longer service life and good cycle stability.
The preparation method of the gel electrolyte membrane provided by the invention has the advantages of low cost and simple process, and is suitable for large-scale industrial production.
The above description is only an overview of the technical solutions of the present invention, and the present invention can be implemented in accordance with the content of the description so as to make the technical means of the present invention more clearly understood, and the above and other objects, features, and advantages of the present invention will be more clearly understood.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 shows a schematic flow diagram of a method 100 for making a gel electrolyte membrane according to one embodiment of the invention;
FIG. 2 shows a scanning electron micrograph of a gel electrolyte membrane prepared according to an embodiment of the present invention;
fig. 3 shows EIS diagrams of gel electrolyte membranes prepared according to example 1 of the present invention and comparative examples 1 to 4;
FIG. 4 shows a lithium symmetric cell cycle test pattern of a gel electrolyte membrane prepared according to example 1 of the present invention;
fig. 5 is a graph showing voltage versus capacity of lithium batteries assembled with gel electrolyte membranes prepared according to example 1 and comparative examples 1 to 3, respectively, of the present invention;
fig. 6 is a graph showing a cycle performance test of a lithium battery assembled by a gel electrolyte membrane, LFP lithium iron phosphate and a lithium sheet prepared according to example 1 of the present invention;
fig. 7 shows a cycle performance test chart of a lithium battery assembled by a gel electrolyte membrane, graphite and a lithium sheet prepared according to example 1 of the present invention.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
Fig. 1 shows a schematic flow diagram of a method 100 for producing a gel electrolyte membrane according to an embodiment of the invention.
As shown in fig. 1, the object of the method is to prepare a gel electrolyte membrane having a three-dimensional porous network structure that conducts ions rapidly. The gel electrolyte with the structure can obviously improve the liquid absorption rate and the liquid retention rate of the electrolyte and has good flexibility. The lithium ion battery assembled by the lithium ion battery has higher ionic conductivity and cycling stability.
The method 100 starts with step 102, and in step 102, a diluent containing 1% to 10% by mass of a natural polysaccharide polymer is provided, and then a silane coupling agent, deionized water and methanol are mixed and hydrolyzed, and then the mixture is added dropwise into the diluent, mixed and stirred, washed and dried to obtain the silane coupling agent modified natural polysaccharide polymer. Wherein the natural polysaccharide polymer is one or more of cellulose, chitosan, guar gum, beta-cyclodextrin and gum arabic.
When the deionized water and the methanol are mixed and hydrolyzed, the hydrolysis is carried out for 1 to 4 hours under the condition of magnetic stirring at the temperature of between 25 and 50 ℃.
The mixing and stirring are carried out for 1 to 2 hours at a temperature of between 20 and 50 ℃ and a rotation speed of between 2000 and 4000 rpm.
The cleaning and drying process specifically comprises the following steps: vacuum filtering with water filter membrane, washing twice with methanol and once with water to remove methanol and unreacted silane coupling agent, and drying in vacuum drying oven at 50-100 deg.C for 12-24 hr.
Then, in step 104, the silane coupling agent-modified natural polysaccharide polymer is dissolved in a first solvent, and subjected to ultrasonic dispersion in an ice bath, followed by constant-temperature stirring to obtain a solution of the natural polysaccharide polymer. Wherein, the first solvent is one or the combination of any more of deionized water, ethanol, ethylene glycol, propylene glycol, isopropanol, acetone, N-methyl pyrrolidone and N, N-dimethylformamide.
In some embodiments, the ultrasonic dispersion under the ice bath condition is ultrasonic treatment for 1-3 h in an ice bath ultrasonic low-temperature tank with the ultrasonic power of 450W and the ultrasonic frequency of 50-60 kHz.
The constant-temperature stirring is carried out for 8 to 12 hours at the temperature of between 20 and 50 ℃ and at the rotating speed of between 300 and 500 rpm.
Subsequently, in step 106, polyvinylidene fluoride-hexafluoropropylene is dissolved in a second solvent, polyethylene oxide is added, and heating and stirring are performed to obtain a mixed solution. Wherein, the second solvent is one or the combination of any more of NMP, DMF, ethanol, acetonitrile, isopropanol and acetone. The relative molecular mass of polyvinylidene fluoride-hexafluoropropylene is 3 × 10 5 ～6×10 5 . The relative molecular mass of the polyethylene oxide was 6X 10 5 ～1×10 6 . The heating and stirring are carried out for 1 to 2 hours under the conditions of 50 to 80 ℃ and the rotating speed of 300 to 500 rpm.
Then, in step 108, the solution of the natural polysaccharide polymer is mixed with the mixed solution, and the mixture is heated and stirred to obtain polymer electrolyte slurry. Wherein, in the obtained polymer electrolyte slurry, the mass ratio of the natural polysaccharide polymer, the polyethylene oxide and the polyvinylidene fluoride-hexafluoropropylene is 0.01-0.1.
Finally, in step 110, the polymer electrolyte slurry is cured and molded, and then immersed in an electrolyte solution in an inert gas atmosphere for activation, resulting in a gel electrolyte membrane as shown in fig. 2. Referring to fig. 2, the gel electrolyte membrane prepared by the preparation method provided by the present example has a rich three-dimensional network porous structure, and the thickness of the gel electrolyte membrane can be maintained at 40 μm to 60 μm (the scale bar in the figure is 5 μm).
In step 110, the process of curing and forming specifically includes: the polymer electrolyte slurry was cast into a mold, followed by vacuum drying. Wherein the vacuum drying is carried out for 12 to 24 hours at the temperature of between 60 and 100 ℃.
Preferably, the atmosphere of the inert gas may be realized as an Ar-atmosphere glove box. The solute of the electrolyte is selected from one or the combination of any several of lithium bis (oxalato) borate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium hexafluorophosphate, lithium perchlorate and lithium difluoro (oxalato) borate.
In some embodiments, the time of activation is 1h to 8h.
In summary, in the preparation method 100 provided by the present invention, a silane coupling agent modified natural polysaccharide polymer material is subjected to ultrasonic treatment and stirred at a constant temperature to be dispersed in a solvent for use, polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) is used as a polymer electrolyte matrix to be dissolved in an organic solvent, a certain mass fraction of polyethylene oxide (PEO) is added to obtain a mixed solution, then the natural polysaccharide polymer dispersion is added to the mixed solution according to a certain solid content ratio, and heating and stirring are performed to obtain a uniform polymer electrolyte slurry. And casting the uniform slurry into a mold, and performing vacuum drying to obtain a polymer film. And (3) punching the polymer film into a round sheet, putting the round sheet into an Ar-atmosphere glove box, and immersing the round sheet into electrolyte for activation to obtain the gel polymer electrolyte film. The natural polysaccharide polymer has rich hydroxyl groups, can form intermolecular hydrogen bonds with polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) and polyethylene oxide (PEO), is bonded to construct a three-dimensional porous network with rapid lithium ion conduction, increases the liquid absorption rate and liquid holding rate of the gel electrolyte to the electrolyte, and improves the ionic conductivity. And secondly, the natural polysaccharide polymer has excellent mechanical property and thermal stability, and improves the mechanical property and high temperature resistance of the gel electrolyte membrane, so that the gel electrolyte membrane can normally work in a wider temperature environment.
The gel electrolyte membrane and the method of preparing the same according to the present invention will be illustrated below by specific examples, which are only for the purpose of better understanding the present invention by those skilled in the art, but are not intended to limit the present invention in any way.
Example 1
(1) Dispersing Cellulose Nano Fiber (CNFs) dry powder in water, continuously adding water to dilute until the solid content is 1% -5%, and stirring in a high-speed grinding machine at the speed of 2000-4000 rpm for 1-2 h at the temperature of 20-30 ℃; putting a silane coupling agent into a beaker, adding deionized water and methanol, magnetically stirring at 25 ℃ and hydrolyzing the silane coupling agent for 1-2 h; dropwise adding the hydrolyzed silane coupling agent into diluted CNFs water diluent, stirring and reacting for 1-2 h at the speed of 2000-3000 rpm at the temperature of 20-30 ℃, carrying out vacuum filtration on the reacted mixed solution through a 0.45-micron water-based filter membrane, washing twice with methanol and once with water to remove the methanol and the unreacted silane coupling agent, centrifuging for three times by using a high-speed centrifuge (the rotating speed is 10000-20000 rpm, the centrifuging time is 3-5 min), removing the residual solvent, putting the obtained product into a vacuum drying box at the temperature of 100 ℃, and drying for 12h to obtain the silane coupling agent modified CNFs dry powder.
(2) Dissolving 1.0060g of silane coupling agent modified CNFs dry powder in 100mL of deionized water, stirring for 12h in a constant-temperature stirrer with the rotation speed of 500rpm and the temperature of 25 ℃, and preparing 10mg/mL cellulose nanofiber dispersion;
(3) Dissolving 1.0130g of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) with the molecular weight of 455000 in 14.0000mL of acetone, and stirring for 1h in a constant-temperature stirrer with the rotation speed of 500rpm and the temperature of 60 ℃ to obtain a uniform polymer matrix solution;
(4) Dissolving 0.0507g of polyethylene oxide (PEO) with the molecular weight of 600000 in the polymer matrix solution of the step (3), and stirring for 2 hours in a constant-temperature stirrer with the rotating speed of 500rpm and the temperature of 60 ℃ to obtain a mixed solution;
(5) Mixing and stirring the 10mg/mL cellulose nanofiber dispersion prepared in the step (2) with the mixed solution obtained in the step (4) to form a stable polymer slurry, wherein the solid phase content (PVDF-HFP: PEO: CNFs = 100;
(6) Pouring the polymer slurry prepared in the step (5) into a mould, carrying out vacuum drying at 60 ℃ for 24h, and curing to obtain a polymer film with the thickness of 51 microns;
(7) The obtained polymer film was punched into a sheet, put into an Ar-atmosphere glove box, and immersed in1MLiPF 6 (EC: DMC: EMC =1: 1) and 1 VoL%) was activated in the electrolyte for 2h to obtain a gel electrolyte membrane, which is noted as PVDF-HFP @ PEO @ CNFs.
Example 2
(1) Dispersing Chitosan (CS) dry powder in water, continuously adding water to dilute until the solid content is 1-5%, and stirring in a high-speed grinding machine at the speed of 2000-4000 rpm for 1-2 h at the temperature of 20-30 ℃; putting a silane coupling agent into a beaker, adding deionized water and methanol, magnetically stirring at 25 ℃ and hydrolyzing the silane coupling agent for 1-2 h; dropwise adding the hydrolyzed silane coupling agent into diluted CS water diluent, stirring and reacting for 1-2 h at the temperature of 20-30 ℃ at the speed of 2000-3000 rpm, carrying out vacuum filtration on the mixed solution after reaction through a 0.45-micron water-based filter membrane, washing twice with methanol, washing once with water, removing the methanol and unreacted silane coupling agent, centrifuging for three times by using a high-speed centrifuge (the rotating speed is 10000-20000 rpm, the centrifuging time is 3-5 min), removing residual solvent, putting into a vacuum drying oven at the temperature of 100 ℃, and drying for 12h to obtain the silane coupling agent modified CS dry powder.
(2) Dissolving 1.0080g of silane coupling agent modified CS dry powder in 100.8000mL of deionized water, stirring for 12 hours in a constant-temperature stirrer with the rotation speed of 500rpm and the temperature of 25 ℃, and preparing 10mg/mL chitosan dispersion;
(3) Dissolving 1.0160g of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) with the molecular weight of 455000 in 14.1000mL of acetone, and stirring for 1h in a constant-temperature stirrer with the rotation speed of 500rpm and the temperature of 60 ℃ to obtain a uniform polymer matrix solution;
(4) Dissolving 0.0508g of polyethylene oxide (PEO) with molecular weight of 600000 in the polymer matrix solution of step (3), and stirring for 2h in a constant-temperature stirrer with the rotation speed of 500rpm and the temperature of 60 ℃ to obtain a mixed solution;
(5) Mixing and stirring the 10mg/mL chitosan dispersion prepared in the step (2) with the mixed solution obtained in the step (4) to form a stable polymer slurry, ensuring the solid phase content (PVDF-HFP: PEO: CS = 100;
(6) Pouring the polymer slurry prepared in the step (5) into a mould, carrying out vacuum drying at 60 ℃ for 24h, and curing to obtain a polymer film with the thickness of 60 micrometers;
(7) The obtained polymer film was punched into a sheet, put into an Ar-atmosphere glove box, and immersed in 1MLiPF 6 (EC: DMC: EMC = 1).
Example 3
(1) Dispersing Guar Gum (GG) dry powder in water, continuously adding water to dilute until the solid content is 1-5%, and stirring in a high-speed grinder at the speed of 2000-4000 rpm for 1-2 h at the temperature of 20-30 ℃; putting a silane coupling agent into a beaker, adding deionized water and methanol, magnetically stirring at 25 ℃ and hydrolyzing the silane coupling agent for 1-2 h; dropwise adding the hydrolyzed silane coupling agent into diluted GG water diluent, stirring and reacting for 1-2 h at the temperature of 20-30 ℃ at the speed of 2000-3000 rpm, carrying out vacuum filtration on the reacted mixed solution through a 0.45-micron water-based filter membrane, washing twice with methanol, washing once with water, removing the methanol and unreacted silane coupling agent, centrifuging for three times by using a high-speed centrifuge (the rotating speed is 10000-20000 rpm, the centrifuging time is 3-5 min), removing residual solvent, putting into a vacuum drying oven at the temperature of 100 ℃, and drying for 12h to obtain the silane coupling agent modified GG dry powder.
(2) Dissolving 1.0020g of silane coupling agent modified GG dry powder in 100.2000mL of deionized water, and stirring for 12h in a constant-temperature stirrer with the rotation speed of 500rpm and the temperature of 25 ℃ to prepare 10mg/mL guar gum dispersion;
(3) Dissolving 1.0080g of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) with the molecular weight of 455000 in 13.8000mL of acetone, and stirring for 1h in a constant-temperature stirrer with the rotation speed of 500rpm and the temperature of 60 ℃ to obtain a uniform polymer matrix solution;
(4) Dissolving 0.1080g of polyethylene oxide (PEO) with the molecular weight of 600000 in the polymer matrix solution of the step (3), and stirring for 2 hours in a constant-temperature stirrer with the rotation speed of 500rpm and the temperature of 60 ℃ to obtain a mixed solution;
(5) Mixing and stirring the 10mg/mL guar gum dispersion prepared in the step (2) with the mixed solution obtained in the step (4) to form a stable polymer slurry, and ensuring the solid phase content (PVDF-HFP: PEO: GG =100 1;
(6) Pouring the polymer slurry prepared in the step (5) into a mould, carrying out vacuum drying for 24h at 60 ℃, and curing to obtain a 56-micron-sized polymer film;
(7) The obtained polymer film was punched into a sheet, put into an Ar-atmosphere glove box, and immersed in 1MLiPF 6 (EC: DMC: EMC = 1).
Example 4
(1) Dispersing beta-cyclodextrin (beta-CD) dry powder in water, continuously adding water to dilute until the solid content is 1-5%, and stirring in a high-speed grinding machine at the speed of 2000-4000 rpm for 1-2 h at the temperature of 20-30 ℃; putting a silane coupling agent into a beaker, adding deionized water and methanol, magnetically stirring at 25 ℃ and hydrolyzing the silane coupling agent for 1-2 h; dropwise adding the hydrolyzed silane coupling agent into the diluted beta-CD water diluent, stirring and reacting for 1-2 h at the temperature of 20-30 ℃ at the speed of 2000-3000 rpm, carrying out vacuum filtration on the reacted mixed solution through a 0.45-micron water-based filter membrane, washing twice with methanol, washing once with water, removing the methanol and unreacted silane coupling agent, centrifuging for three times by using a high-speed centrifuge (the rotating speed is 10000-20000 rpm, the centrifuging time is 3-5 min), removing the residual solvent, putting the obtained product into a 100-DEG C vacuum drying box, and drying for 12h to obtain the silane coupling agent modified beta-CD dry powder.
(2) Dissolving 1.0150g of silane coupling agent modified beta-CD dry powder in 101.5000mL of deionized water, stirring for 12 hours in a constant-temperature stirrer with the rotation speed of 500rpm and the temperature of 25 ℃, and preparing 10mg/mL beta-cyclodextrin dispersion liquid;
(3) Dissolving 0.9980g of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) with the molecular weight of 455000 in 13.5000mL of acetone, and stirring for 1h in a constant-temperature stirrer with the rotation speed of 500rpm and the temperature of 60 ℃ to obtain a uniform polymer matrix solution;
(4) Dissolving 0.0499g of polyethylene oxide (PEO) with the molecular weight of 600000 in the polymer matrix solution of step (3), and stirring for 2h in a constant-temperature stirrer with the rotation speed of 500rpm and the temperature of 60 ℃ to obtain a mixed solution;
(5) Mixing and stirring the 10mg/mL beta-cyclodextrin dispersion prepared in the step (2) with the mixed solution obtained in the step (4) to form a stable polymer slurry, wherein the solid phase content (PVDF-HFP: PEO: beta-CD = 100;
(6) Pouring the polymer slurry prepared in the step (5) into a mould, carrying out vacuum drying at 60 ℃ for 24h, and curing to obtain a polymer film with the thickness of 43 microns;
(7) The obtained polymer film was punched into a sheet, put into an Ar-atmosphere glove box, and immersed in 1MLiPF 6 (EC: DMC: EMC = 1.
Example 5
(1) Dispersing Arabic gum (AS) dry powder in water, continuously adding water to dilute until the solid content is 1-5%, and stirring in a high-speed grinding machine at the speed of 2000-4000 rpm for 1-2 h at the temperature of 20-30 ℃; putting a silane coupling agent into a beaker, adding deionized water and methanol, magnetically stirring at 25 ℃ and hydrolyzing the silane coupling agent for 1-2 h; dropwise adding the hydrolyzed silane coupling agent into the diluted AS water diluent, stirring and reacting for 1-2 h at the temperature of 20-30 ℃ at the speed of 2000-3000 rpm, carrying out vacuum filtration on the mixed solution after reaction through a 0.45-micron water-based filter membrane, washing twice with methanol, washing once with water, removing the methanol and the unreacted silane coupling agent, centrifuging for three times by using a high-speed centrifuge (the rotating speed is 10000-20000 rpm, the centrifuging time is 3-5 min), removing the residual solvent, putting the obtained product into a vacuum drying box at the temperature of 100 ℃, and drying for 12h to obtain the silane coupling agent modified AS dry powder.
(2) Dissolving 1.0030g of silane coupling agent modified AS dry powder in 100.3000mL of deionized water, stirring for 12h in a constant-temperature stirrer with the rotation speed of 500rpm and the temperature of 25 ℃, and preparing 10mg/mL of gum arabic dispersion;
(3) Dissolving 1.080g of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) with the molecular weight of 455000 in 13.8000mL of acetone, and stirring for 1h in a constant-temperature stirrer with the rotation speed of 500rpm and the temperature of 60 ℃ to obtain a uniform polymer matrix solution;
(4) Dissolving 0.0540g of polyethylene oxide (PEO) with the molecular weight of 600000 in the polymer matrix solution of step (3), and stirring for 2 hours in a constant-temperature stirrer with the rotation speed of 500rpm and the temperature of 60 ℃ to obtain a mixed solution;
(5) Mixing and stirring the 10mg/mL gum arabic dispersion prepared in step (2) with the mixed solution obtained in step (4) to form a stable polymer slurry, ensuring solid phase content (PVDF-HFP: PEO: AS = 5;
(6) Pouring the polymer slurry prepared in the step (5) into a mold, carrying out vacuum drying at 60 ℃ for 24h, and curing to obtain a polymer film with the thickness of 42 microns;
(7) The obtained polymer film was punched into a sheet, put into an Ar-atmosphere glove box, and immersed in 1MLiPF 6 (EC: DMC: EMC = 1).
Comparative example 1
(1) Dissolving 1.0050g of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) with the molecular weight of 455000 in 13.2000mL of acetone, and stirring for 1h in a constant-temperature stirrer with the rotation speed of 500rpm and the temperature of 60 ℃ to obtain a uniform polymer matrix solution;
(2) Pouring the polymer slurry prepared in the step (1) into a mould, carrying out vacuum drying at 60 ℃ for 24h, and curing to obtain a polymer film with the thickness of 15 microns;
(3) The obtained polymer film was punched into a sheet, put into an Ar-atmosphere glove box, and immersed in 1MLiPF 6 (EC: DMC: EMC = 1) in the electrolyte for 2h, a gel electrolyte membrane was obtained, noted PVDF-HFP.
Comparative example 2
(1) Dissolving 1.0100g of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) with the molecular weight of 455000 in 13.5000mL of acetone, and stirring for 1h in a constant-temperature stirrer with the rotation speed of 500rpm and the temperature of 60 ℃ to obtain a uniform polymer matrix solution;
(2) Taking 0.0505g of polyethylene oxide (PEO) with a molecular weight of 600000 to dissolve in the polymer matrix solution of step (2), stirring for 2h in a constant temperature stirrer with a rotation speed of 500rpm and a temperature of 60 ℃ to obtain a stable polymer slurry, ensuring solid content (PVDF-HFP: PEO = 5;
(3) Pouring the polymer slurry prepared in the step (2) into a mold, carrying out vacuum drying at 60 ℃ for 24 hours, and curing to obtain a polymer film with the thickness of 25 micrometers;
(5) Is prepared byThe polymer film of (2) was punched into a sheet, put into an Ar-atmosphere glove box, and immersed in 1MLiPF 6 (EC: DMC: EMC = 1.
Comparative example 3
(1) Dispersing Cellulose Nano Fiber (CNFs) dry powder in water, continuously adding water to dilute until the solid content is 1% -5%, and stirring in a high-speed grinding machine at the speed of 2000-4000 rpm for 1-2 h at the temperature of 20-30 ℃; putting a silane coupling agent into a beaker, adding deionized water and methanol, magnetically stirring at 25 ℃ and hydrolyzing the silane coupling agent for 1-2 h; dropwise adding the hydrolyzed silane coupling agent into diluted CNFs water diluent, stirring and reacting for 1-2 h at the temperature of 20-30 ℃ at the speed of 2000-3000 rpm, carrying out vacuum filtration on the reacted mixed solution through a 0.45-micron water-based filter membrane, washing twice with methanol, washing once with water, removing the methanol and unreacted silane coupling agent, centrifuging for three times by using a high-speed centrifuge (the rotating speed is 10000-20000 rpm, the centrifuging time is 3-5 min), removing residual solvent, putting into a 100-DEG C vacuum drying oven, and drying for 12h to obtain the silane coupling agent modified CNFs dry powder.
(2) Dissolving 0.9970g of silane coupling agent modified CNFs dry powder in 99.7000mL of absolute ethanol, stirring for 12h in a constant-temperature stirrer with the rotation speed of 500rpm and the temperature of 25 ℃, and preparing 10mg/mL of cellulose nanofiber dispersion;
(3) Dissolving 1.0080g of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) with the molecular weight of 455000 in 13.3000mL of acetone, and stirring for 1h in a constant-temperature stirrer with the rotation speed of 500rpm and the temperature of 60 ℃ to obtain a uniform polymer matrix solution;
(4) Mixing and stirring 9.9800mL of the cellulose nanofiber dispersion solution with the concentration of 10mg/mL prepared in the step (2) and the polymer matrix solution obtained in the step (2) to form stable polymer slurry, wherein the solid content is ensured (PVDF-HFP: CNFs = 100;
(5) Pouring the polymer slurry prepared in the step (4) into a mould, carrying out vacuum drying for 24 hours at 60 ℃, and curing to obtain a polymer film with the thickness of 40 micrometers;
(6) Punching the obtained polymer film into thin sheet, and placing in Ar atmosphereIn a glove box, 1MLiPF is immersed 6 (EC: DMC: EMC = 1.
Comparative example 4
(1) A commercial PP separator was punched into a thin sheet, which was put into an Ar-atmosphere glove box and immersed in 1MLiPF 6 (EC: DMC: EMC = 1).
Test example 1
The thicknesses and liquid absorption rates of the gel electrolyte membranes prepared in examples 1 to 5 and comparative examples 1 to 4 are shown in table 1.
TABLE 1
Test example 2
EIS of the gel electrolyte membranes prepared in comparative example 1 and comparative examples 1 to 4, the results are shown in fig. 3, and fig. 3 shows: the ionic conductivity of the gel electrolyte membrane prepared in example 1 was as high as 1.33X 10 -3 S·cm -1 Compared with a gel electrolyte membrane obtained by modifying the gel electrolyte membrane by using the PEO or the CNFs singly, the gel electrolyte membrane has more excellent ion conduction effect, and the ion conductivity almost reaches the level of liquid electrolyte.
Test example 3
The cycle test results of the lithium symmetric battery including the gel electrolyte membrane prepared in example 1 are shown in fig. 4, and fig. 4 shows: at 0.2mA/cm 2 And (3) under the current density, 1500 circles are circulated, and the polarization voltage is stabilized below 0.05V.
Test example 4
The gel electrolyte membranes prepared in example 1 and comparative examples 1 to 3 and the LFP lithium iron phosphate cathode and the lithium sheet cathode were assembled into lithium batteries, respectively, and the lithium batteries were tested to have specific capacity at voltage of 2.5 to 4.0V at a rate of 0.1C and at voltage of 5 th cycle, and the results are shown in fig. 5, which is a graph in fig. 5: the specific capacities of PVDF-HFP @ PEO @ CNFs, PVDF-HFP @ PEO and PVDF-HFP @ CNFs are 158.8mAh/g, 149.3mAh/g, 150.1mAh/g and 155.1mAh/g respectively.
Test example 5
The battery cycle performance test of the lithium battery assembled by using LFP lithium iron phosphate as the positive electrode and the lithium plate as the negative electrode and the gel electrolyte membrane of example 1 shows that the results are shown in fig. 6, and fig. 6 shows: under the multiplying power of 1C within the voltage range of 2.5-4.0V, after circulating for 500 circles, the capacity retention rate is 92.3% when the initial capacity is 149 mAh/g.
Test example 6
The battery cycle performance test of the lithium battery assembled with graphite as the positive electrode and the lithium sheet as the negative electrode and the gel electrolyte membrane of example 1 is shown in fig. 7, and fig. 7 shows: in the voltage range of 0.01-3.0V and under the multiplying power of 1C, after circulating for 400 circles, the capacity retention rate of the initial capacity 324mAh/g is 95.6%.
In addition, unless otherwise specified, any range recited herein includes any subrange defined by the endpoints and any value therebetween, and any subrange defined by the endpoints or any value therebetween; the purity of the solvent used in the invention is more than or equal to 99.9 percent; the chemical reagents used in the examples of the present invention, unless otherwise specified, are commercially available in a conventional manner.
As can be seen from the above examples and comparative examples, the preparation method of the present invention has the following beneficial effects:
(1) The gel electrolyte membrane material obtained by the method has a three-dimensional porous network structure for rapidly conducting lithium ions, and the thickness of the gel electrolyte membrane is 40-60 mu m;
(2) The gel electrolyte membrane material obtained by the invention is soaked in 1M LiPF 6 (EC: DMC: EMC =1 6 The liquid absorption rate of the electrolyte is improved to 432 percent, and the liquid retention rate in 8h after liquid absorption is still as high as 415 percent;
(3) Soaking the gel electrolyte membrane material obtained by the invention in 1M soaked LiPF 6 Activating for 1-2 h in electrolyte, assembling button cell by using stainless steel sheet instead of electrode, and testing its lithium ion conductivity to be 1.3X 10 in electrochemical workstation -3 S·cm -1 . The gel electrolyte membrane material has excellent ionic conductivity;
(4) Soaking the gel electrolyte membrane material obtained by the invention in 1M soaked LiPF 6 Activating for 1-2 h in the electrolyte, assembling a button lithium symmetric battery by adopting a lithium sheet, and testing the button lithium symmetric battery at an electrochemical workstation with the current density of 0.2mA/cm 2 And circulating for 1500h, wherein the polarization voltage is less than 50mV. The gel electrolyte membrane material has a certain obvious inhibiting effect on lithium dendrites, so that the battery has a good service life;
(5) The gel electrolyte membrane material obtained by the invention is soaked in 1M soaking LiPF 6 Activating for 1-2 h in the electrolyte, assembling the button cell by using lithium iron phosphate as a positive electrode and a lithium sheet as a negative electrode, and performing stable charge-discharge cycle for 500 circles at 1C rate to obtain a capacity retention rate of 92.3%; graphite is used as a positive electrode, a lithium sheet is used as a negative electrode to assemble the button cell, the charge-discharge cycle is stable for 400 circles under the multiplying power of 1C, and the capacity retention rate is 95.6%. The gel electrolyte membrane is adapted to commercial anode and cathode materials, so that the battery has good cycling stability;
(6) The method has low cost and simple process, and is suitable for large-scale industrial production.
The production method according to A1, wherein the thickness of the gel electrolyte membrane is 40 to 60 μm. A10, the preparation method of A1, wherein the mixed hydrolysis is performed for 1 to 4 hours at a temperature of between 25 and 50 ℃ under magnetic stirring. A11, the preparation method of A1, wherein the mixing and stirring are carried out for 1 to 2 hours at a temperature of between 20 and 50 ℃ and a rotating speed of between 2000 and 4000 rpm. The preparation method according to A1, wherein the step of washing and drying includes: vacuum filtering with water filter membrane, washing twice with methanol and once with water to remove methanol and unreacted silane coupling agent, and drying in vacuum drying oven at 50-100 deg.C for 12-24 hr. A13, the preparation method as A1, wherein the ultrasonic dispersion under the ice bath condition is ultrasonic treatment for 1-3 h in an ice bath ultrasonic low-temperature tank with the ultrasonic power of 450W and the ultrasonic frequency of 50 kHz-60 kHz. A14 the production method according to A1, wherein the stirring at a constant temperature is performed at a rotation speed of 300 to 500rpm at 20 to 50 ℃. A15 the process according to A1, wherein the heating and stirring are carried out at 50 to 80 ℃ and at a rotation speed of 300 to 500rpm for 1 to 2 hours. A16, the preparation method as described in A1, wherein the activation time is 1 h-8 h. The preparation method according to the above a17, wherein the step of curing and molding comprises: the polymer electrolyte slurry was cast into a mold, followed by vacuum drying. A18 and the preparation method of A17, wherein the vacuum drying is performed for 12 to 24 hours at 60 to 100 ℃.
In the description of the present specification, the terms "connected", "fixed", and the like are to be construed broadly unless otherwise explicitly specified or limited. Furthermore, the terms "upper", "lower", "inner", "outer", "top", "bottom", and the like indicate orientations or positional relationships that are based on the orientations or positional relationships shown in the drawings, merely to facilitate description of the invention and to simplify the description, and do not indicate or imply that the referenced devices or units must have a particular orientation, be constructed in a particular orientation, and be constructed in a particular manner of operation, and thus, are not to be construed as limiting the invention.
In the description herein, the description of the terms "one embodiment," "some embodiments," "specific embodiments," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
In the description provided herein, numerous specific details are set forth. It is understood, however, that embodiments of the invention may be practiced without these specific details. In some instances, well-known methods, structures and techniques have not been shown in detail in order not to obscure an understanding of this description.
Similarly, it should be appreciated that in the foregoing description of exemplary embodiments of the invention, various features of the invention are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure and aiding in the understanding of one or more of the various inventive aspects. However, the disclosed method should not be interpreted as reflecting an intention that: that the invention as claimed requires more features than are expressly recited in each claim. Thus, the claims following the detailed description are hereby expressly incorporated into this detailed description, with each claim standing on its own as a separate embodiment of this invention.
Furthermore, those skilled in the art will appreciate that while some embodiments described herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments.
While the invention has been described with respect to a limited number of embodiments, those skilled in the art, having benefit of this description, will appreciate that other embodiments can be devised which do not depart from the scope of the invention as disclosed herein. Furthermore, it should be noted that the language used in the specification has been principally selected for readability and instructional purposes, and may not have been selected to delineate or circumscribe the inventive subject matter. Accordingly, many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the appended claims. The present invention has been disclosed in an illustrative rather than a restrictive sense with respect to the scope of the invention, as defined in the appended claims.
Claims (10)
1. A method of preparing a gel electrolyte membrane comprising:
providing a diluent containing 1-10% of natural polysaccharide polymer by mass, then mixing and hydrolyzing a silane coupling agent, deionized water and methanol, then dropwise adding the mixture into the diluent, mixing and stirring, and washing and drying to obtain the silane coupling agent modified natural polysaccharide polymer;
dissolving the silane coupling agent modified natural polysaccharide polymer in a first solvent, performing ultrasonic dispersion under an ice bath condition, and then stirring at constant temperature to obtain a solution of the natural polysaccharide polymer;
dissolving polyvinylidene fluoride-hexafluoropropylene in a second solvent, adding polyoxyethylene, and heating and stirring to obtain a mixed solution;
mixing the solution of the natural polysaccharide polymer with the mixed solution, and heating and stirring to obtain polymer electrolyte slurry;
and solidifying and molding the polymer electrolyte slurry, and then immersing the polymer electrolyte slurry into electrolyte in an inert gas atmosphere for activation to obtain the gel electrolyte membrane.
2. The process according to claim 1, wherein the natural polysaccharide polymer is one or a combination of any of cellulose, chitosan, guar gum, β -cyclodextrin and gum arabic.
3. The method according to claim 1, wherein the electrolyte solute is one or a combination of any of lithium bis (oxalato) borate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium hexafluorophosphate, lithium perchlorate and lithium difluoro (oxalato) borate.
4. The production method according to claim 1, wherein the mass ratio of the natural polysaccharide polymer, the polyethylene oxide, and the polyvinylidene fluoride-hexafluoropropylene in the polymer electrolyte slurry is 0.01 to 0.1.
5. The preparation method according to claim 1, wherein the first solvent is one or a combination of any of deionized water, ethanol, ethylene glycol, propylene glycol, isopropanol, acetone, N-methylpyrrolidone and N, N-dimethylformamide.
6. The preparation method according to claim 1, wherein the second solvent is one or a combination of any of NMP, DMF, ethanol, acetonitrile, isopropanol and acetone.
7.The production method according to claim 1, wherein the relative molecular mass of the polyvinylidene fluoride-hexafluoropropylene is 3 x 10 5 ～6×10 5 。
8. The production method according to claim 1, wherein the polyethylene oxide has a relative molecular mass of 6 x 10 5 ～1×10 6 。
9. A gel electrolyte membrane produced by the production method according to any one of claims 1 to 8.
10. A lithium ion battery comprising a positive electrode, a negative electrode, and the gel electrolyte membrane according to any one of claims 9 or the gel electrolyte membrane produced by the production method according to any one of claims 1 to 8, the gel electrolyte membrane being located between the positive electrode and the negative electrode.
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| CN116826160B (en) * | 2023-07-28 | 2024-07-02 | 江苏北星新材料科技有限公司 | Polyolefin-based composite gel polymer electrolyte and preparation method thereof |
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