CN113150314A - Composite gel electrolyte material with interpenetrating network porous structure and preparation and application thereof - Google Patents
Composite gel electrolyte material with interpenetrating network porous structure and preparation and application thereof Download PDFInfo
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- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a composite gel electrolyte material with an interpenetrating network porous structure and preparation and application thereof, wherein the preparation method comprises the following steps: respectively dissolving cellulose nano-fiber crystals and polyvinyl alcohol in an aqueous alkali containing urea and a deionized water solution; uniformly mixing the two dispersion solutions, adding potassium hydroxide into the mixture, and then carrying out vortex mixing; and heating and forming the mixture after the vortex mixing to obtain the composite gel electrolyte material with the interpenetrating network porous structure. The preparation method has the advantages of simple process, low cost, easy product forming, short reaction time and suitability for batch production; the prepared composite gel electrolyte material has wide raw material sources and biodegradability, and the CNFs surface contains rich hydroxyl groups, and can be used as a reinforcing agent and a cross-linking agent of PVA hydrogel to prepare gel electrolyte with an interpenetrating network porous structure in a composite manner, so that the mechanical property and the ionic conductivity of the composite gel electrolyte are further improved, and the composite gel electrolyte material has a wide application prospect.
Description
Technical Field
The invention belongs to the technical field of chemical materials, and relates to a composite gel electrolyte material with an interpenetrating network porous structure, a preparation method and application thereof, in particular to a composite gel polymer electrolyte material with an interpenetrating network porous structure, which is used in the field of energy storage and has green, high efficiency and good electrochemical performance, and a preparation method and application thereof.
Background
The gel polymer electrolyte has the advantages of high conductivity of a liquid electrolyte and high safety of a solid polymer electrolyte to a certain extent, and is an electrolyte system with the most practical application value at present. Generally, gel polymer electrolytes can be divided into hydrogels and organogels, wherein the organogel electrolytes are volatile and have a certain polluting property, which hinders their practical use. Compared with an organic gel polymer electrolyte, the hydrogel electrolyte has higher ionic conductivity and mechanical property, is easy to process, less in pollution and difficult to leak, and is favored by researchers in recent years. Among them, polyvinyl alcohol (PVA) hydrogel as a polymer matrix has the advantages of good film forming property and high safety performance, and is one of the most widely used hydrogel polymers at present. However, the ionic conductivity and mechanical properties of the PVA hydrogel electrolyte are still limited, and it is difficult to meet the requirements of practical applications.
In response, researchers have improved ionic conductivity of PVA hydrogel electrolytes by physical and chemical crosslinking methods such as hydrogen bonding and electrostatic interaction between substances, chemical crosslinking with nanofibers, and addition of redox active substances such as potassium thiocyanate (KSCN) to PVA-KOH polymer gel electrolytes. However, these methods are not significant for improving the ionic conductivity and the mechanical properties of the electrolyte membrane, and the crosslinking process is too complicated, so there is a need for researchers to develop a simpler and more effective method to further improve the ionic conductivity and the mechanical properties of the polymer hydrogel.
Cellulose is one of the most main renewable and sustainable natural polymers, has the advantages of low density, high strength, good biocompatibility, low thermal expansion coefficient and the like, and is widely used as a reinforcing agent for preparing products such as transparent paper, hydrogel, aerogel and the like. In addition, because the surface of the cellulose contains abundant hydroxyl, the hydrogel taking the cellulose as a matrix is easy to form a hydrophilic framework and a micropore network structure, and the framework structure can stabilize an ion transmission channel and improve the solvent competitiveness. The cellulose nanocrystalline CNFs and the polymer are selected to be compounded to prepare the hybrid hydrogel, so that the hydrogel is endowed with excellent mechanical properties, and the problem of poor stability of the hydrogel can be solved.
Therefore, the development of a method for enhancing and crosslinking the polyvinyl alcohol hydrogel by using the cellulose nanocrystals so as to improve the mechanical property and the ionic conductivity of the composite hydrogel electrolyte is of practical significance.
Disclosure of Invention
The invention aims to overcome the defects that the existing PVA hydrogel electrolyte is still limited in ionic conductivity and mechanical property and is difficult to meet the requirements of practical application, and provides a method, a product and application for enhancing and crosslinking polyvinyl alcohol hydrogel by applying cellulose nanocrystals so as to improve the mechanical property and ionic conductivity of the composite hydrogel electrolyte.
In order to achieve the purpose, the invention provides the following technical scheme:
the preparation method of the composite gel electrolyte material with the interpenetrating network porous structure comprises the following steps:
(1) dissolving cellulose nano-fiber Crystals (CNFs) in aqueous alkali containing urea to prepare cellulose nano-fiber crystal dispersion, and dissolving polyvinyl alcohol (PVA) in deionized water solution to prepare polyvinyl alcohol dispersion;
(2) uniformly mixing the cellulose nano-fiber crystal dispersion liquid and the polyvinyl alcohol dispersion liquid, adding potassium hydroxide into the mixture, and then carrying out vortex mixing;
(3) and heating and forming the mixture after the vortex mixing to obtain the composite gel electrolyte material with the interpenetrating network porous structure.
Compared with the method for dispersing the cellulose nano-fiber crystals by using the aqueous solution, the method has the advantages that the aqueous solution containing urea is selected to dissolve the cellulose nano-fiber crystals, the surface of the cellulose nano-fiber crystals is obviously changed after the cellulose nano-fiber crystals are dissolved by the aqueous solution containing urea, hydrogen bonds in molecules and among molecules are weakened due to swelling of CNFs after alkali treatment, the surface area of fibers is increased, a rich reticular microporous structure is formed, micropores with smaller pore diameters are formed in the pores, the contact area of a diaphragm and electrolyte is enlarged by the structure, and ion transmission is increased; KOH is added in the step (2), so that the number and the mobility of charge carriers are greatly improved, and the conductivity can be further improved; the mixing mode of vortex mixing is selected, because the efficiency of gel coagulation depends on the probability of particle collision in the solution, the vortex flow formed by vortex reaction can effectively promote the diffusion and collision of particles in water, thus CNFs can be uniformly dispersed in a polymer network with inherent flexibility and intertwined with PVA chains, the mechanical property is enhanced while the extraordinary flexibility is endowed, and the internal cross-linked network pores are uniform to ensure the stability and high efficiency of ion transmission; and finally, the final molding is finished by adopting a heating molding mode, compared with the traditional gel molding methods such as a freeze-thaw method and the like, the operation is simple, the gel molding quality is good, and the industrialization can be realized by large-scale production.
The preparation method of the composite gel electrolyte material with the interpenetrating network porous structure enhances the mechanical stability and the ductility of the synthesized hydrogel through the physical entanglement and hydrogel bonding between PVA and cellulose chains. In addition, dynamic recombination of intermolecular hydrogen bond cleavage can further promote energy dissipation under stretching conditions and homogenization of polymer networks, thereby achieving excellent stretching properties. The excellent hyperstretchability and softness result from the cellulose and PVA assisted toughening and hydrogen bonding cross-linking mechanisms. In its network structure, although cellulose chains exhibit a relatively rigid structure, they are uniformly dispersed in a polymer network having intrinsic flexibility and intertwine with the PVA chains, imparting extraordinary flexibility. In addition, hydrogen bonds act as reversible cross-linking points that can dynamically break and reform during strain to dissipate mechanical energy. Rather than dissipating energy through the random coil structure of the entangled polymer chains, the dynamic process reorganizes the polymer chains, thereby rapidly and uniformly distributing the applied stress throughout the network. In addition, the method has the characteristics of simple process, short reaction time, low energy consumption, wide raw material source, environmental friendliness and low cost, and has a wide application prospect.
As a preferred technical scheme:
according to the preparation method of the composite gel electrolyte material with the interpenetrating network porous structure, the composite gel electrolyte material is internally provided with the three-dimensional network porous structure which is mutually communicated, and specifically, the three-dimensional network porous structure which is mutually communicated and has the pore diameter of 1-10um is internally provided. The CNFs contain rich hydrogen bonds on the surface, and the 3D pore structure skeleton formed by the mutual entanglement mechanism of molecular chains can be used as a reinforcing agent and a cross-linking agent of the composite gel electrolyte, so that the gel electrolyte material with an interpenetrating network porous structure can be formed after the CNFs are compounded with PVA, and excellent mechanical stability and ion conductivity are endowed to the CNFs. Many spider-web-like fiber webs were observed on the pore walls of the CNFs-PVA composite gel electrolyte, as compared to clean walls, and this structure maintained the stability of the large channels and promoted the improvement of the ionic conductivity.
The preparation method of the composite gel electrolyte material with the interpenetrating network porous structure comprises the following steps: sodium hydroxide, thiourea, urea and water are mixed according to the mass ratio of 7: 9: 9: 75 to obtain an alkaline solution containing urea;
before dissolving cellulose nano-fiber crystal in aqueous alkali containing urea, pre-freezing the aqueous alkali containing urea at-10 ℃;
the diameter of the cellulose nano-fiber crystal is 3-80 nm, the length of the cellulose nano-fiber crystal is more than 1um, the cellulose nano-fiber crystal needs to be quickly stirred for 5min when being dissolved in an aqueous alkali containing urea, and the cellulose nano-fiber crystal is placed for 2h at room temperature; the length-diameter ratio of the cellulose nanocrystals enables the composite gel electrolyte to have higher porosity and air permeability, is more favorable for the permeation of electrolyte, and has better mechanical properties;
the concentration of cellulose nano-fiber crystals in the cellulose nano-fiber crystal dispersion liquid is 1-10 wt%, and the cellulose nano-fiber crystal dispersion liquid is stored in a refrigerator at 4 ℃. Under the condition that the content of the cellulose nano-fiber crystals is too small, the overall pore diameter of the material is too large, so that more electrolyte cannot be adsorbed; when the content of the cellulose nano-fiber crystals is gradually increased, an interpenetrating network structure is formed among fibers in the material, so that the liquid absorption capacity is obviously improved; however, as the content of cellulose nanofiber crystals is further increased, the specific surface area of the composite gel electrolyte material is reduced, thereby causing the liquid absorption capacity of the electrolyte material to be continuously reduced.
The invention selects the aqueous alkali containing urea as the cellulose nano-fiber crystal solvent because strong hydrogen bonds exist between molecules and in the molecules of cellulose to cause the mutual constraint of molecular chains, and the cellulose has regular crystallization regions, so the cellulose can not be melted and is difficult to dissolve in common organic solvents, thereby seriously limiting the application of cellulose materials. The NaOH/urea/aqueous solution system is selected because the system is economical and environment-friendly compared with other systems (such as an amine oxide system, a DMAC/LiCl solvent system and ionic liquid) and the prepared cellulose solution is relatively stable.
According to the preparation method of the composite gel electrolyte material with the interpenetrating network porous structure, the molecular weight of the polyvinyl alcohol is 25000-150000; the concentration of polyvinyl alcohol in the polyvinyl alcohol dispersion liquid is 1-10 wt%; when the content of the hydrophilic polymer polyvinyl alcohol is gradually increased, the solubilization amount of the non-solvent is increased, the molecular block structure of the non-solvent is easier to form close packing, and the viscosity between the solvent and the non-solvent is hindered, so that the dynamic phase separation is difficult, and the viscosity of the casting solution is obviously increased, on the other hand, along with the addition of the polyvinyl alcohol, the thermodynamic stability of the whole gel system is reduced, the separation speed of the phase is increased, so that the phase separation is instantly generated, a large amount of non-solvent molecules are dissolved in water and can more quickly enter channels in the electrolyte material to form an interpenetrating porous structure, therefore, along with the increase of the content of the polyvinyl alcohol, the aperture of the electrolyte material is increased, more electrolyte fills micropores of the gel material, the liquid absorption rate of the material is also continuously increased, and along with the increase of the proportion of the polyvinyl alcohol, a large amount of macromolecules are enriched on the surface of the electrolyte material, the internal pore diameter of the electrolyte material is too large, so that more electrolyte cannot be stored, and the liquid absorption rate of the whole material is reduced;
the polyvinyl alcohol is dissolved in the deionized water solution, specifically, the polyvinyl alcohol is put into the deionized water solution and then stirred for 4-4.5 hours at the temperature of 45-50 ℃ and at the stirring speed of 50-500 r/min.
According to the preparation method of the composite gel electrolyte material with the interpenetrating network porous structure, the cellulose nano-fiber crystal dispersion liquid and the polyvinyl alcohol dispersion liquid are mixed according to the weight ratio of 0.3-1: 1, adding potassium hydroxide, and performing vortex mixing, wherein the mass ratio of the potassium hydroxide to the polyvinyl alcohol is (0.01-0.05): the vortex mixing is to place the mixture of the cellulose nano-fiber crystal dispersion liquid added with potassium hydroxide and the polyvinyl alcohol dispersion liquid on a hot plate at 70 ℃ and to magnetically stir the mixture overnight at a speed of 225r/min, but the vortex mixing is not limited thereto, and only one possible technical solution is provided herein, and the person skilled in the art can reasonably adjust the solution according to actual situations. The influence of the content of the polyvinyl alcohol on the tensile strength, deformation condition, casting solution viscosity, liquid absorption rate and the like of the diaphragm is comprehensively considered, so the proportion of the polyvinyl alcohol in the system must be strictly controlled. When the content of the polyvinyl alcohol is less, the overall liquid absorption rate and the pure water flux of the electrolyte material are poorer; when the content of the polyvinyl alcohol is too large, the viscosity of the electrolyte is too high, the film scraping is difficult to occur, and the pore diameter of the electrolyte material is too large to absorb sufficient electrolyte. When the content of the cellulose nano-fiber crystals is too high, a large amount of aggregation is generated in small pores by cellulose nano-fiber crystal molecular chains of the electrolyte material, so that partial micropores are deformed and collapsed, the porosity is reduced, and the liquid absorption capacity of the material is weakened. Therefore, after the mass ratio of the cellulose nano-fiber crystal dispersion liquid to the polyvinyl alcohol dispersion liquid is strictly adjusted, the weight ratio of the cellulose nano-fiber crystal dispersion liquid to the polyvinyl alcohol dispersion liquid is increased by 0.3-1: 1, the overall material performance is best.
In the preparation method of the composite gel electrolyte material with the interpenetrating network porous structure, the heating and molding of the mixture after the vortex mixing specifically means that the product after the vortex mixing is poured into a mold for heating and molding, the heating and molding temperature is 30-80 ℃, the heating and molding time is 10 min-1 h, and the mold is a polytetrafluoroethylene mold, a glass mold or a plastic mold.
According to the preparation method of the composite gel electrolyte material with the interpenetrating network porous structure, deionized water is used for washing and heating the formed product until the product is neutral, and then the product is soaked in 0.1-1 mol/L lithium salt solution for 5-10 hours in a vacuum glove box to obtain the composite gel electrolyte material with the interpenetrating network porous structure.
The preparation method of the composite gel electrolyte material with interpenetrating network porous structure comprises the following steps of preparing a lithium salt, wherein the lithium salt is at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bistrifluoromethylsulfonyl imide, lithium difluorosulfonyl imide, lithium dioxalate borate, lithium difluorooxalate borate, lithium trifluoromethanesulfonate and lithium bistrifluoromethylsulfonyl imide;
the solvent of the lithium salt solution is at least one of diethyl ether, ethanol, acetonitrile, tetrahydrofuran, malononitrile, succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, nonanedionitrile and decanedionitrile.
The invention also provides the composite gel electrolyte material with the interpenetrating network porous structure prepared by the preparation method of the composite gel electrolyte material with the interpenetrating network porous structure. According to the invention, by controlling the content of the nano-cellulose dispersion liquid, the mass ratio of the polymer, the reaction temperature and the reaction time, the composite gel electrolyte with different mechanical properties, self-healing capability and electric conduction capability can be obtained.
In addition, the composite gel electrolyte material with the interpenetrating network porous structure prepared by the preparation method of the composite gel electrolyte material with the interpenetrating network porous structure is applied to preparation of conductive materials, sensing materials and super capacitor diaphragms.
Has the advantages that:
(1) the preparation method of the composite gel electrolyte material with the interpenetrating network porous structure is simple, low in cost, easy to form, short in reaction time and suitable for batch production;
(2) the composite gel electrolyte material with the interpenetrating network porous structure has wide raw material sources and biodegradability, and the CNFs surface contains rich hydroxyl groups, and can be used as a reinforcing agent and a cross-linking agent of PVA hydrogel to prepare the gel electrolyte with the interpenetrating network porous structure in a composite manner, so that the mechanical property and the ionic conductivity of the composite gel electrolyte are further improved, and the composite gel electrolyte material has great application prospects in the fields of lithium ion power batteries, sensing materials, supercapacitor diaphragms and the like.
Drawings
Fig. 1 is a scanning electron micrograph of the interpenetrating network porous structure composite gel electrolyte material of the present invention.
Detailed Description
In order to make the technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
A preparation method of a composite gel electrolyte material with an interpenetrating network porous structure comprises the following steps:
(1) sodium hydroxide, thiourea, urea and water are mixed according to the mass ratio of 7: 9: 9: 75 to obtain an aqueous alkali containing urea, pre-freezing at-10 ℃, adding 1g of CNFs (the diameter is 3-80 nm, and the length is more than 1um) into 49g of the prepared aqueous alkali containing urea, quickly stirring for 5min, standing at room temperature for 2h to obtain a transparent cellulose solution with the concentration of 2 wt%, storing in a refrigerator at 4 ℃, adding 1g of PVA (the molecular weight is 25000-150000) into 49g of deionized water, and stirring at 45 ℃ for 4 h to obtain a polyvinyl alcohol solution with the concentration of 2 wt%;
(2) mixing 12g of cellulose solution and 40g of polyvinyl alcohol solution, adding 10mg of KOH, and carrying out vortex mixing;
(3) and (3) pouring the composite product prepared in the step (2) into a polytetrafluoroethylene mold, heating and molding for 20min at 50 ℃, washing the molded product to be neutral by using deionized water, and then soaking the molded product in a 0.1mol/L lithium hexafluorophosphate solution (the solvent is diethyl ether) in a vacuum glove box for 5h to obtain the composite gel electrolyte material with the interpenetrating network porous structure.
The scanning electron microscope photo of the prepared interpenetrating network porous structure composite gel electrolyte material is shown in figure 1, and it can be seen from the figure that the interior of the material is a three-dimensional (3D) network porous structure which is communicated with each other and has a pore diameter of 1-10 μm. The inner structure of the gel electrolyte material is formed because the CNFs contain abundant hydrogen bonds on the surface, and the 3D pore structure skeleton formed by the mutual entanglement mechanism of molecular chains can be used as a reinforcing agent and a cross-linking agent of the composite gel electrolyte, so that the gel electrolyte material with an interpenetrating network porous structure can be formed after the gel electrolyte material is compounded with PVA, and excellent mechanical stability and ion conductivity are endowed to the gel electrolyte material. Many spider-web-like fiber webs were observed on the pore walls of the CNFs-PVA composite gel electrolyte, as compared to clean walls, and this structure maintained the stability of the large channels and promoted the improvement of the ionic conductivity.
Example 2
A preparation method of a composite gel electrolyte material with an interpenetrating network porous structure comprises the following steps:
(1) sodium hydroxide, thiourea, urea and water are mixed according to the mass ratio of 7: 9: 9: 75 to obtain an aqueous alkali containing urea, pre-freezing at-10 ℃, adding 1g of CNFs (the diameter is 3-80 nm, and the length is more than 1um) into 24g of the prepared aqueous alkali containing urea, quickly stirring for 5min, standing at room temperature for 2h to obtain a transparent cellulose solution with the concentration of 4 wt%, storing in a refrigerator at 4 ℃, adding 1g of PVA (the molecular weight is 25000-150000) into 49g of deionized water, and stirring at 45 ℃ for 4 h to obtain a polyvinyl alcohol solution with the concentration of 2 wt%;
(2) mixing 20g of cellulose solution and 40g of polyvinyl alcohol solution, adding 10mg of KOH, and carrying out vortex mixing;
(3) and (3) pouring the composite product prepared in the step (2) into a polytetrafluoroethylene mold, heating and molding for 20min at 50 ℃, washing the molded product to be neutral by using deionized water, and then soaking the molded product in a 0.5mol/L lithium tetrafluoroborate solution (ethanol is used as a solvent) in a vacuum glove box for 5h to obtain the composite gel electrolyte material with the interpenetrating network porous structure.
After testing the prepared composite gel electrolyte material with interpenetrating network porous structure, it was found to have 2 × 10 at room temperature-3ms·cm-1While the ionic conductivity of the PVC hydrogel under the same conditions is 1X 10-3ms·cm-1. Analysis shows that the existence of the cellulose nanofiber obviously improves the mechanical property of the polymer, widens the pore channel of the polymer and further improves the ionic conductivity.
Example 3
A preparation method of a composite gel electrolyte material with an interpenetrating network porous structure comprises the following steps:
(1) sodium hydroxide, thiourea, urea and water are mixed according to the mass ratio of 7: 9: 9: 75 to obtain an aqueous alkali containing urea, pre-freezing at-10 ℃, adding 1g of CNFs (the diameter is 3-80 nm, and the length is more than 1um) into 49g of the prepared aqueous alkali containing urea, quickly stirring for 5min, standing at room temperature for 2h to obtain a transparent cellulose solution with the concentration of 2 wt%, storing in a refrigerator at 4 ℃, adding 1g of PVA (the molecular weight is 25000-150000) into 24g of deionized water, and stirring at 45 ℃ for 4 h to obtain a polyvinyl alcohol solution with the concentration of 4 wt%;
(2) mixing 25g of cellulose solution and 25g of polyvinyl alcohol solution, adding 10mg of KOH, and carrying out vortex mixing;
(3) and (3) pouring the composite product prepared in the step (2) into a polytetrafluoroethylene mold, heating and molding for 20min at 50 ℃, washing the molded product to be neutral by using deionized water, and then soaking the molded product in a 1mol/L lithium perchlorate solution (the solvent is acetonitrile) in a vacuum glove box for 5h to obtain the composite gel electrolyte material with the interpenetrating network porous structure.
Tests show that the coulombic efficiency under different multiplying powers is high, when the multiplying power returns to 0.5C, the performance of the battery is stable, and a discharge-charge voltage platform is almost kept unchanged under the current density.
Example 4
A preparation method of a composite gel electrolyte material with an interpenetrating network porous structure comprises the following steps:
(1) sodium hydroxide, thiourea, urea and water are mixed according to the mass ratio of 7: 9: 9: 75 to obtain an aqueous alkali containing urea, pre-freezing at-10 ℃, adding 1g of CNFs (the diameter is 3-80 nm, and the length is more than 1um) into 49g of the prepared aqueous alkali containing urea, quickly stirring for 5min, standing at room temperature for 2h to obtain a transparent cellulose solution with the concentration of 2 wt%, storing in a refrigerator at 4 ℃, adding 1g of PVA (the molecular weight is 25000-150000) into 49g of deionized water, and stirring at 45 ℃ for 4 h to obtain a polyvinyl alcohol solution with the concentration of 2 wt%;
(2) mixing 20g of cellulose solution and 40g of polyvinyl alcohol solution, adding 10mg of KOH, and carrying out vortex mixing;
(3) and (3) pouring the composite product prepared in the step (2) into a polytetrafluoroethylene mold, heating and molding for 20min at 50 ℃, washing the molded product to be neutral by using deionized water, and then soaking the molded product in a 0.1mol/L lithium bis (trifluoromethyl) sulfimide solution (the solvent is tetrahydrofuran) in a vacuum glove box for 10h to obtain the composite gel electrolyte material with the interpenetrating network porous structure.
The EIS curve, the polarization curve and the corresponding power density of the prepared composite gel electrolyte material with the interpenetrating network porous structure at the initial stage of the stretching/releasing test and after 100 times are characterized, and the cycle stability of 500% stretching/releasing for 100 times is reflected through a constant current discharging/charging test.
Example 5
A preparation method of a composite gel electrolyte material with an interpenetrating network porous structure comprises the following steps:
(1) sodium hydroxide, thiourea, urea and water are mixed according to the mass ratio of 7: 9: 9: 75 to obtain an aqueous alkali containing urea, pre-freezing at-10 ℃, adding 1g of CNFs (the diameter is 3-80 nm, and the length is more than 1um) into 49g of the prepared aqueous alkali containing urea, quickly stirring for 5min, standing at room temperature for 2h to obtain a transparent cellulose solution with the concentration of 2 wt%, storing in a refrigerator at 4 ℃, adding 1g of PVA (the molecular weight is 25000-150000) into 49g of deionized water, and stirring at 45 ℃ for 4 h to obtain a polyvinyl alcohol solution with the concentration of 2 wt%;
(2) mixing 12g of cellulose solution and 40g of polyvinyl alcohol solution, adding 20mg of KOH, and carrying out vortex mixing;
(3) and (3) pouring the composite product prepared in the step (2) into a polytetrafluoroethylene mold, heating and molding for 20min at 50 ℃, washing the molded product to be neutral by using deionized water, and then soaking the molded product in a 0.1mol/L lithium bis (fluorosulfonyl) imide solution (the solvent is malononitrile) in a vacuum glove box for 8h to obtain the composite gel electrolyte material with the interpenetrating network porous structure.
Example 6
A preparation method of a composite gel electrolyte material with an interpenetrating network porous structure comprises the following steps:
(1) sodium hydroxide, thiourea, urea and water are mixed according to the mass ratio of 7: 9: 9: 75 to obtain an aqueous alkali containing urea, pre-freezing at-10 ℃, adding 1g of CNFs (the diameter is 3-80 nm, and the length is more than 1um) into 49g of the prepared aqueous alkali containing urea, quickly stirring for 5min, standing at room temperature for 2h to obtain a transparent cellulose solution with the concentration of 2 wt%, storing in a refrigerator at 4 ℃, adding 1g of PVA (the molecular weight is 25000-150000) into 49g of deionized water, and stirring at 45 ℃ for 4 h to obtain a polyvinyl alcohol solution with the concentration of 2 wt%;
(2) mixing 12g of cellulose solution and 40g of polyvinyl alcohol solution, adding 10mg of KOH, and carrying out vortex mixing;
(3) and (3) pouring the composite product prepared in the step (2) into a polytetrafluoroethylene mold, heating and molding for 20min at 50 ℃, washing the molded product to be neutral by using deionized water, and then soaking the molded product in a 0.3mol/L lithium bis (oxalato) borate solution (the solvent is octanedionitrile) in a vacuum glove box for 5h to obtain the composite gel electrolyte material with the interpenetrating network porous structure.
Proved by verification, the preparation method of the composite gel electrolyte material with the interpenetrating network porous structure is simple, low in cost, easy to form, short in reaction time and suitable for batch production; the prepared composite gel electrolyte material with the interpenetrating network porous structure has wide raw material sources and biodegradability, and the CNFs surface contains rich hydroxyl groups, and can be used as a reinforcing agent and a cross-linking agent of PVA hydrogel to prepare the gel electrolyte with the interpenetrating network porous structure in a composite manner, so that the mechanical property and the ionic conductivity of the composite gel electrolyte are further improved, and the composite gel electrolyte material has great application prospects in the fields of lithium ion power batteries, sensing materials, supercapacitor diaphragms and the like.
Although specific embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these embodiments are merely illustrative and various changes or modifications may be made without departing from the principles and spirit of the invention.
Claims (10)
1. The preparation method of the composite gel electrolyte material with the interpenetrating network porous structure is characterized by comprising the following steps:
(1) dissolving cellulose nano-fiber crystals in aqueous alkali containing urea to prepare cellulose nano-fiber crystal dispersion, and dissolving polyvinyl alcohol in deionized water solution to prepare polyvinyl alcohol dispersion;
(2) uniformly mixing the cellulose nano-fiber crystal dispersion liquid and the polyvinyl alcohol dispersion liquid, adding potassium hydroxide into the mixture, and then carrying out vortex mixing;
(3) and heating and forming the mixture after the vortex mixing to obtain the composite gel electrolyte material with the interpenetrating network porous structure.
2. The method for preparing the composite gel electrolyte material with the interpenetrating network porous structure according to claim 1, wherein the composite gel electrolyte material has an interconnected three-dimensional network porous structure inside.
3. The method for preparing the composite gel electrolyte material with the interpenetrating network porous structure according to claim 1, wherein the method for preparing the aqueous alkali containing urea comprises the following steps: sodium hydroxide, thiourea, urea and water are mixed according to the mass ratio of 7: 9: 9: 75 to obtain an alkaline solution containing urea;
before dissolving cellulose nano-fiber crystal in aqueous alkali containing urea, pre-freezing the aqueous alkali containing urea at-10 ℃;
the diameter of the cellulose nanofiber crystal is 3-80 nm, and the length of the cellulose nanofiber crystal is greater than 1 um;
the concentration of the cellulose nano-fiber crystals in the cellulose nano-fiber crystal dispersion liquid is 1-10 wt%.
4. The preparation method of the composite gel electrolyte material with the interpenetrating network porous structure according to claim 1, wherein the molecular weight of the polyvinyl alcohol is 25000-150000; the concentration of polyvinyl alcohol in the polyvinyl alcohol dispersion liquid is 1-10 wt%;
the polyvinyl alcohol is dissolved in the deionized water solution, specifically, the polyvinyl alcohol is put into the deionized water solution and then stirred for 4-4.5 hours at the temperature of 45-50 ℃ and at the stirring speed of 50-500 r/min.
5. The preparation method of the composite gel electrolyte material with the interpenetrating network porous structure according to claim 1, wherein the ratio of the cellulose nano-fiber crystal dispersion liquid to the polyvinyl alcohol dispersion liquid is 0.3-1: 1, adding potassium hydroxide, and performing vortex mixing, wherein the mass ratio of the potassium hydroxide to the polyvinyl alcohol is (0.01-0.05): 1, the vortex mixing means that the mixture of the cellulose nano-fiber crystal dispersion liquid added with the potassium hydroxide and the polyvinyl alcohol dispersion liquid is placed on a hot plate at 70 ℃ and is magnetically stirred at the speed of 225r/min overnight.
6. The preparation method of the composite gel electrolyte material with the interpenetrating network porous structure according to claim 1, wherein the step of heating and molding the mixture after the vortex mixing is to pour the product after the vortex mixing into a mold for heating and molding, wherein the heating and molding temperature is 30-80 ℃, the heating and molding time is 10 min-1 h, and the mold is a polytetrafluoroethylene mold, a glass mold or a plastic mold.
7. The preparation method of the composite gel electrolyte material with the interpenetrating network porous structure according to claim 6, wherein the product obtained by washing and heating the formed product with deionized water is neutral, and the product is soaked in 0.1-1 mol/L lithium salt solution in a vacuum glove box for 5-10 hours to obtain the composite gel electrolyte material with the interpenetrating network porous structure.
8. The method of preparing the interpenetrating network porous structure composite gel electrolyte material according to claim 7, wherein the lithium salt is at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bistrifluoromethylsulfonyl imide, lithium difluorosulfonyl imide, lithium dioxalate borate, lithium difluorooxalate borate, lithium trifluoromethanesulfonate, and lithium bistrifluoromethylsulfonyl imide;
the solvent of the lithium salt solution is at least one of diethyl ether, ethanol, acetonitrile, tetrahydrofuran, malononitrile, succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, nonanedionitrile and decanedionitrile.
9. The composite gel electrolyte material with the interpenetrating network porous structure prepared by the preparation method of the composite gel electrolyte material with the interpenetrating network porous structure according to any one of claims 1 to 8.
10. The use of the composite gel electrolyte material with interpenetrating network porous structure prepared by the preparation method of the composite gel electrolyte material with interpenetrating network porous structure according to any one of claims 1 to 8.
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