CN113150314B - Composite gel electrolyte material with interpenetrating network porous structure, preparation and application thereof - Google Patents
Composite gel electrolyte material with interpenetrating network porous structure, preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a composite gel electrolyte material with an interpenetrating network porous structure, and preparation and application thereof, and the preparation method comprises the following steps: respectively dissolving cellulose nanofiber crystals and polyvinyl alcohol in an alkali solution and deionized water solution containing urea; uniformly mixing the two dispersion solutions, adding potassium hydroxide into the mixture, and performing vortex mixing; and heating and forming the mixture after 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 and short reaction time, and is suitable for batch production; the prepared composite gel electrolyte material has wide raw material sources and biodegradability, CNFs surface contains abundant hydroxyl groups, and can be used as a reinforcing agent and a crosslinking agent of PVA hydrogel to prepare the gel electrolyte with an interpenetrating network porous structure in a composite way, 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 great application prospect.
Description
Technical Field
The invention belongs to the technical field of chemical materials, relates to a composite gel electrolyte material with an interpenetrating network porous structure, a preparation method and application thereof, and in particular relates to a composite gel polymer electrolyte material with an interpenetrating network porous structure, which is green, efficient and good in electrochemical performance and is used in the energy storage field, and a preparation method and application thereof.
Background
The gel polymer electrolyte has the advantages of high conductivity of liquid electrolyte and high safety of solid polymer electrolyte to a certain extent, and is the electrolyte system with the most practical application value at present. Generally, gel polymer electrolytes can be classified into hydrogels and organogels, wherein organogel electrolytes are volatile and have a certain contamination property, which hinders their practical application. Compared with organic gel polymer electrolyte, the hydrogel electrolyte has higher ionic conductivity and mechanical property, is easy to process, has less pollution and is not easy to leak, and is favored by researchers in recent years. Among them, polyvinyl alcohol (PVA) hydrogel has the advantages of good film forming property and high safety performance as a polymer matrix, and is one of the most widely used hydrogel polymers at present. However, the ionic conductivity and mechanical properties of PVA hydrogel electrolyte are still limited, and it is difficult to meet the practical application requirements.
In this regard, researchers have improved ionic conductivity of PVA hydrogel electrolytes by hydrogen bonding and electrostatic interactions between materials, chemical crosslinking with nanofibers, and by physical and chemical crosslinking methods such as the addition of the redox active material potassium thiocyanate (KSCN) to PVA-KOH polymer gel electrolytes. However, these methods are not significant for improving ionic conductivity and mechanical properties of electrolyte membranes, and the crosslinking process is too complicated, so that researchers are required to develop simpler and more effective methods to further improve ionic conductivity and mechanical properties of polymer hydrogels.
Cellulose, which is one of the most important 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 transparent paper, hydrogel, aerogel and other products. In addition, because the surface of the cellulose contains abundant hydroxyl groups, the hydrogel taking the cellulose as a matrix is easy to form a hydrophilic framework and a microporous network structure, and the framework structure can stabilize an ion transmission channel and improve solvent competitiveness. The cellulose nanocrystalline CNFs and the polymer are selected to be compounded to prepare the hybrid hydrogel, so that the excellent mechanical property of the hydrogel can be endowed, and the problem of poor stability of the hydrogel can be solved.
Therefore, it is of great practical significance to develop a method for enhancing and crosslinking polyvinyl alcohol hydrogel by applying cellulose nanocrystals so as to improve the mechanical properties and ionic conductivity of the composite hydrogel electrolyte.
Disclosure of Invention
The invention aims to overcome the defect that the ionic conductivity and the mechanical property of the traditional PVA hydrogel electrolyte are still limited and are difficult to meet the actual application demands, and provides a method and a product for enhancing and crosslinking the polyvinyl alcohol hydrogel by using cellulose nanocrystals so as to improve the mechanical property and the ionic conductivity of the composite hydrogel electrolyte and application thereof.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the preparation method of the composite gel electrolyte material with the interpenetrating network porous structure comprises the following steps:
(1) Cellulose nanofiber Crystals (CNFs) are dissolved in an alkali solution containing urea to prepare cellulose nanofiber crystal dispersion liquid, and polyvinyl alcohol (PVA) is dissolved in deionized water solution to prepare polyvinyl alcohol dispersion liquid;
(2) Uniformly mixing cellulose nanofiber crystal dispersion liquid and polyvinyl alcohol dispersion liquid, adding potassium hydroxide into the mixture, and then carrying out vortex mixing;
(3) And heating and forming the mixture after vortex mixing to obtain the composite gel electrolyte material with the interpenetrating network porous structure.
Compared with the use of aqueous solution to disperse cellulose nanofiber crystals, the surface of the cellulose nanofiber crystals is obviously changed after the cellulose nanofiber crystals are dissolved by the aqueous solution containing urea, and the cellulose nanofiber crystals are characterized in that the CNFs after alkali treatment swell, so that intramolecular and intermolecular hydrogen bonds are weakened, the surface area of the fibers is increased, a richer netlike micropore structure is formed, micropores with smaller pore diameters are formed in the pores, the contact area of a diaphragm and electrolyte is enlarged, and ion transmission is increased; the KOH is added in the step (2), so that the quantity and 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 collision of particles in solution, vortex flow formed by vortex reaction can effectively promote the diffusion and collision of particles in water, so that CNFs can be uniformly dispersed in a polymer network with internal flexibility and intertwined with PVA chains, extraordinary flexibility is endowed, mechanical properties are enhanced, and the internal cross-linked network pores uniformly ensure the stability and high efficiency of ion transmission; finally, the final forming is finished by adopting a heating forming mode, and compared with the traditional gel forming methods such as a freeze thawing method, the method is simple to operate, has good gel forming quality and can realize industrialization in large-scale production.
According to the preparation method of the composite gel electrolyte material with the interpenetrating network porous structure, the mechanical stability and the ductility of the synthesized hydrogel are enhanced through physical entanglement and hydrogel bonding between PVA and cellulose chains. In addition, the dynamic recombination of intermolecular hydrogen bond cleavage can further promote energy dissipation under stretching conditions and homogenization of the polymer network, thereby obtaining excellent stretching properties. The excellent superextensibility and softness result from the mechanisms of cellulose and PVA-assisted toughening and hydrogen bonding. In its network structure, although cellulose chains exhibit a relatively rigid structure, they are uniformly dispersed in a polymer network having inherent flexibility and intertwined with PVA chains, imparting exceptional flexibility. In addition, hydrogen bonds act as reversible crosslinking points that can be broken and recombined dynamically during strain to dissipate mechanical energy. Instead of a random coil structure that dissipates energy through breakage of the entangled polymer chains, the dynamic process reorganizes the polymer chains so that the applied stresses are rapidly and evenly distributed throughout the network. In addition, the method has the characteristics of simple process, short reaction time, low energy consumption, wide raw material sources, environmental friendliness and low cost, and has a great application prospect.
As a preferable technical scheme:
the preparation method of the composite gel electrolyte material with the interpenetrating network porous structure comprises the steps that the interior of the composite gel electrolyte material is of a three-dimensional network porous structure which is mutually communicated, and specifically, the interior of the composite gel electrolyte material is of a three-dimensional network porous structure which is mutually communicated and has a pore diameter of 1-10 um. The 3D pore structure skeleton formed by the aid of an intertwining mechanism among molecular chains can serve as a reinforcing agent and a crosslinking 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 provided. Many web-like webs were observed on the pore walls of CNFs-PVA composite gel electrolytes compared to clean walls, which structure maintained stability of large channels and promoted improvement of 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, and preparing an alkaline solution containing urea;
pre-freezing the alkali solution containing urea at-10 ℃ before dissolving cellulose nanofiber crystals in the alkali solution containing urea;
the diameter of the cellulose nanofiber crystal is 3-80 nm, the length is more than 1um, the cellulose nanofiber crystal is rapidly stirred for 5min when dissolved in an alkali solution containing urea, and the cellulose nanofiber crystal is placed at room temperature for 2h; the length-diameter ratio of the cellulose nanocrystalline enables the composite gel electrolyte to have higher porosity and air permeability, is more beneficial to 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 1-10wt%, and the cellulose nano-fiber crystal dispersion liquid is stored in a refrigerator at 4 ℃. Under the condition that the content of cellulose nano fiber crystal is too small, the whole pore diameter of the material is too large, so that more electrolyte cannot be adsorbed; when the content of cellulose nano fiber crystal is gradually increased, interpenetrating network structure is formed among fibers in the material, and the liquid absorbing capacity is obviously improved; however, as the content of cellulose nanofiber crystals further increases, the specific surface area of the composite gel electrolyte material decreases, thereby causing the liquid absorbing capacity of the electrolyte material to be continuously reduced.
The invention selects the alkaline solution containing urea as the cellulose nano-fiber crystal solvent, because strong hydrogen bonds exist between molecules and in molecules of cellulose to cause mutual constraint of molecular chains, and the cellulose has a regular crystallization area, the cellulose can not be melted and is indissoluble in common organic solvents, and the application of cellulose materials is severely limited. The NaOH/urea/water solution system was chosen because it is economical and environmentally friendly and the resulting cellulose solution is relatively stable compared to other systems (e.g. amine oxide systems, DMAC/LiCl solvent systems, ionic liquids).
The preparation method of the composite gel electrolyte material with the interpenetrating network porous structure comprises the step of preparing the composite gel electrolyte material with the interpenetrating network porous structure, wherein the molecular weight of the polyvinyl alcohol is 25000-150000; the concentration of the polyvinyl alcohol in the polyvinyl alcohol dispersion liquid is 1-10wt%; when the content of the hydrophilic polymer polyvinyl alcohol is increased gradually, the solubilizing amount of the non-solvent is increased, the molecular block structure of the non-solvent is easier to form close packing, the viscosity of the solvent and the non-solvent is blocked, difficulty is brought to dynamic phase separation, the viscosity of the casting solution is obviously increased, on the other hand, as the polyvinyl alcohol is added, the thermodynamic stability of the whole gel system is reduced, the phase separation speed is accelerated, so that the phase separation is instantaneously carried out, a large number of non-solvent molecules are dissolved in water and can enter channels inside the electrolyte material more quickly, an interpenetrating porous structure is formed, therefore, as the content of the polyvinyl alcohol is increased, the pore size of the electrolyte material is increased, more electrolyte fills pores of the gel material, the liquid absorption rate of the material is also increased continuously, as the proportion of the polyvinyl alcohol is increased, a large number of high molecules are enriched on the surface of the electrolyte material, the internal pore size of the electrolyte material is overlarge, more electrolyte is not enough to store, 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 stirred for 4 to 4.5 hours at the stirring speed of 50 to 500r/min at the temperature of 45 to 50 ℃ after being put into the deionized water solution.
The preparation method of the composite gel electrolyte material with the interpenetrating network porous structure comprises the steps of mixing 0.3-1 of cellulose nanofiber crystal dispersion liquid and polyvinyl alcohol dispersion liquid: 1, adding potassium hydroxide after mixing in a mass ratio, and carrying out vortex mixing, wherein the mass ratio of the potassium hydroxide to the polyvinyl alcohol is 0.01-0.05: 1, the vortex mixing is to place the mixture of cellulose nanofiber crystal dispersion liquid and polyvinyl alcohol dispersion liquid added with potassium hydroxide on a hot plate at 70 ℃ and magnetically stir overnight at the speed of 225r/min, the vortex mixing of the invention is not limited to the above, only one feasible technical scheme is given here, and the reasonable adjustment can be carried out by the person skilled in the art according to the actual situation. The influences of the content of the polyvinyl alcohol on the tensile strength, the deformation condition, the viscosity of the casting solution, the liquid absorption rate and the like of the diaphragm are comprehensively considered, so that the proportion of the polyvinyl alcohol in the system must be strictly controlled. When the polyvinyl alcohol content is low, the overall liquid absorption and pure water flux of the electrolyte material are poor; when the content of the polyvinyl alcohol is too large, the viscosity of the electrolyte is too high, the situation that the film is difficult to scrape occurs, and the pore diameter of the electrolyte material is too large, so that the sufficient electrolyte is not easy to absorb. When the content of cellulose nano-fiber crystals is too high, a great amount of cellulose nano-fiber crystal molecular chains of the electrolyte material are gathered in small pores, so that part of micropores are deformed and collapsed, the porosity is reduced, and the liquid absorption capability of the material is weakened. Therefore, after strictly preparing the mass ratio of the cellulose nanofiber crystal dispersion liquid to the polyvinyl alcohol dispersion liquid, the mass ratio of the cellulose nanofiber crystal dispersion liquid to the polyvinyl alcohol dispersion liquid is 0.3-1: the overall material performance is optimal at 1.
The preparation method of the composite gel electrolyte material with the interpenetrating network porous structure comprises the steps of heating and forming a mixture after vortex mixing, namely pouring a product after vortex mixing into a mold for heating and forming, wherein the heating and forming temperature is 30-80 ℃, the heating and forming time is 10 min-1 h, and the mold is a polytetrafluoroethylene mold, a glass mold or a plastic mold.
The preparation method of the composite gel electrolyte material with the interpenetrating network porous structure comprises the steps of washing a product prepared by heating and forming by using deionized water until the product is neutral, and soaking the product in a lithium salt solution with the concentration of 0.1-1 mol/L 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 the interpenetrating network porous structure comprises the steps that lithium salt is at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium dioxalate borate, lithium difluorooxalate borate, lithium trifluoromethylsulfonate and lithium bis (trifluoromethylsulfonyl) imide;
the solvent of the lithium salt solution is at least one of diethyl ether, ethanol, acetonitrile, tetrahydrofuran, malononitrile, succinonitrile, glutaronitrile, adiponitrile, pimelic dinitrile, suberonitrile, nonyldinitrile and decyldinitrile.
The invention also provides the interpenetrating network porous structure composite gel electrolyte material prepared by the interpenetrating network porous structure composite gel electrolyte material preparation method. The invention can obtain the composite gel electrolyte with different mechanical properties, different self-healing capacity and different electric conductivity by controlling the content of the nano cellulose dispersion liquid, the mass ratio of the polymer, the reaction temperature and the reaction time.
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 the preparation of conductive materials, sensing materials and super capacitor diaphragms.
The beneficial effects are that:
(1) The preparation method of the composite gel electrolyte material with the interpenetrating network porous structure has the advantages of simplicity, low cost, easy product forming and short reaction time, and is suitable for batch production;
(2) The interpenetrating network porous structure composite gel electrolyte material has wide raw material sources and biodegradability, CNFs surface contains abundant hydroxyl groups, can be used as a reinforcing agent and a cross-linking agent of PVA hydrogel to prepare the interpenetrating network porous structure gel electrolyte by compounding, further improves the mechanical property and the ion conductivity of the composite gel electrolyte, and has great application prospects in the fields of lithium ion power batteries, sensing materials, super capacitor diaphragms and the like.
Drawings
FIG. 1 is a scanning electron microscope photograph of a composite gel electrolyte material of an interpenetrating network porous structure of the invention.
Detailed Description
In order to make the technical solution and advantages of the embodiments of the present invention more clear, the technical solution of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The following examples are illustrative of the invention and 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, then pre-freezing at-10 ℃, adding 1g of CNFs (with the diameter of 3-80 nm and the length of more than 1 um) into 49g of the prepared alkali solution containing urea, rapidly stirring for 5min, standing for 2h at room temperature to obtain a transparent cellulose solution with the concentration of 2wt%, storing in a refrigerator at 4 ℃, adding 1g of PVA (with the molecular weight of 25000-150000) into 49g of deionized water, and stirring for 4 h at 45 ℃ 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) Pouring the composite product prepared in the step (2) into a polytetrafluoroethylene mould, heating and forming for 20min at 50 ℃, washing the formed product to be neutral by deionized water, and then soaking the formed product in a lithium hexafluorophosphate solution (the solvent is diethyl ether) with the concentration of 0.1mol/L in a vacuum glove box for 5h to obtain the interpenetrating network porous structure composite gel electrolyte material.
The scanning electron microscope photograph of the prepared composite gel electrolyte material with the interpenetrating network porous structure is shown in figure 1, and the inside of the composite gel electrolyte material is a three-dimensional (3D) network porous structure which is mutually communicated and has the pore diameter of 1-10 mu m. The internal structure is formed because the CNFs surface contains abundant hydrogen bonds, and the formed 3D pore structure skeleton can be used as a reinforcing agent and a crosslinking agent of the composite gel electrolyte by means of an intertwining mechanism among molecular chains, 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 provided. Many web-like webs were observed on the pore walls of CNFs-PVA composite gel electrolytes compared to clean walls, which structure maintained stability of large channels and promoted improvement of 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, then pre-freezing at-10 ℃, adding 1g of CNFs (with the diameter of 3-80 nm and the length of more than 1 um) into 24g of the prepared alkali solution containing urea, rapidly stirring for 5min, standing for 2h at room temperature to obtain a transparent cellulose solution with the concentration of 4wt%, storing in a refrigerator with the temperature of 4 ℃, adding 1g of PVA (with the molecular weight of 25000-150000) into 49g of deionized water, and stirring for 4 h at 45 ℃ 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) Pouring the composite product prepared in the step (2) into a polytetrafluoroethylene mould, heating and forming for 20min at 50 ℃, washing the formed product to be neutral by deionized water, and then soaking the formed product in 0.5mol/L lithium tetrafluoroborate solution (ethanol is used as a solvent) for 5h in a vacuum glove box to obtain the interpenetrating network porous structure composite gel electrolyte material.
After testing the prepared composite gel electrolyte material with interpenetrating network porous structure, the composite gel electrolyte material has 2X 10 at room temperature -3 ms·cm -1 While the ionic conductivity of PVC hydrogels under the same conditions is 1×10 -3 ms·cm -1 . Analysis shows thatThe existence of cellulose nano-fiber obviously improves the mechanical property of the polymer, widens the pore canal of the polymer, and improves the ion 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, then pre-freezing at-10 ℃, adding 1g of CNFs (with the diameter of 3-80 nm and the length of more than 1 um) into 49g of the prepared alkali solution containing urea, rapidly stirring for 5min, standing for 2h at room temperature to obtain a transparent cellulose solution with the concentration of 2wt%, storing in a refrigerator at 4 ℃, adding 1g of PVA (with the molecular weight of 25000-150000) into 24g of deionized water, and stirring for 4 h at 45 ℃ 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) Pouring the composite product prepared in the step (2) into a polytetrafluoroethylene mould, heating and forming for 20min at 50 ℃, washing the formed product to be neutral by deionized water, and then soaking in 1mol/L lithium perchlorate solution (acetonitrile as solvent) for 5h in a vacuum glove box to obtain the interpenetrating network porous structure composite gel electrolyte material.
The test shows that the coulombic efficiency at different multiplying factors is stable when the battery returns to 0.5C multiplying factor, and the discharging-charging voltage platform is almost unchanged at 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, then pre-freezing at-10 ℃, adding 1g of CNFs (with the diameter of 3-80 nm and the length of more than 1 um) into 49g of the prepared alkali solution containing urea, rapidly stirring for 5min, standing for 2h at room temperature to obtain a transparent cellulose solution with the concentration of 2wt%, storing in a refrigerator at 4 ℃, adding 1g of PVA (with the molecular weight of 25000-150000) into 49g of deionized water, and stirring for 4 h at 45 ℃ 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) Pouring the composite product prepared in the step (2) into a polytetrafluoroethylene mould, heating and forming for 20min at 50 ℃, washing the formed product to be neutral by deionized water, and then soaking the formed product in a 0.1mol/L lithium bis (trifluoromethylsulfonyl) imide solution (tetrahydrofuran is used as a solvent) in a vacuum glove box for 10h to obtain the interpenetrating network porous structure composite gel electrolyte material.
And the EIS curve, the polarization curve and the corresponding power density of the prepared interpenetrating network porous structure composite gel electrolyte material after the initial and 100 times of stretching/releasing test are characterized, and the 500% stretching/releasing 100 times of cycling stability is reflected by 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, then pre-freezing at-10 ℃, adding 1g of CNFs (with the diameter of 3-80 nm and the length of more than 1 um) into 49g of the prepared alkali solution containing urea, rapidly stirring for 5min, standing for 2h at room temperature to obtain a transparent cellulose solution with the concentration of 2wt%, storing in a refrigerator at 4 ℃, adding 1g of PVA (with the molecular weight of 25000-150000) into 49g of deionized water, and stirring for 4 h at 45 ℃ 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) Pouring the composite product prepared in the step (2) into a polytetrafluoroethylene mould, heating and forming for 20min at 50 ℃, washing the formed product to be neutral by deionized water, and then soaking the formed product in 0.1mol/L lithium bis (fluorosulfonyl) imide solution (the solvent is malononitrile) in a vacuum glove box for 8h to obtain the interpenetrating network porous structure composite gel electrolyte material.
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, then pre-freezing at-10 ℃, adding 1g of CNFs (with the diameter of 3-80 nm and the length of more than 1 um) into 49g of the prepared alkali solution containing urea, rapidly stirring for 5min, standing for 2h at room temperature to obtain a transparent cellulose solution with the concentration of 2wt%, storing in a refrigerator at 4 ℃, adding 1g of PVA (with the molecular weight of 25000-150000) into 49g of deionized water, and stirring for 4 h at 45 ℃ 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) Pouring the composite product prepared in the step (2) into a polytetrafluoroethylene mould, heating and forming for 20min at 50 ℃, washing the formed product to be neutral by deionized water, and then soaking the formed product in a 0.3mol/L lithium dioxalate borate solution (the solvent is octadinitrile) in a vacuum glove box for 5h to obtain the interpenetrating network porous structure composite gel electrolyte material.
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 mass production; the prepared composite gel electrolyte material with the interpenetrating network porous structure has wide raw material sources and biodegradability, CNFs surface contains abundant 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 compounding way, so that the mechanical property and the ion 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, super capacitor diaphragms and the like.
While particular embodiments of the present invention have been described above, it will be understood by those skilled in the art that these are by way of example only and that various changes or modifications may be made to these embodiments without departing from the principles and spirit of the invention.
Claims (8)
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 fibers with the diameter of 3-80 nm and the length of more than 1um in an alkali solution containing urea to prepare cellulose nano fiber dispersion liquid, wherein the concentration of the cellulose nano fibers in the cellulose nano fiber dispersion liquid is 1-10wt%, and dissolving polyvinyl alcohol in deionized water to prepare polyvinyl alcohol dispersion liquid, wherein the concentration of the polyvinyl alcohol in the polyvinyl alcohol dispersion liquid is 1-10wt%;
wherein: the preparation method of the alkaline solution containing urea comprises the following steps: sodium hydroxide, thiourea, urea and water are mixed according to the mass ratio of 7:9:9:75, and preparing an alkaline solution containing urea;
(2) Mixing the cellulose nanofiber dispersion liquid and the polyvinyl alcohol dispersion liquid according to a ratio of 0.3-1: 1, adding potassium hydroxide into the mixture after uniformly mixing the mixture in mass ratio, and then carrying out vortex mixing, wherein the mass ratio of the potassium hydroxide to the polyvinyl alcohol is 0.01-0.05: 1, a step of;
(3) Heating and forming the mixture after vortex mixing, washing a product prepared by heating and forming by using deionized water until the product is neutral, and soaking the product in a vacuum glove box for 5-10 hours in a lithium salt solution with the concentration of 0.1-1 mol/L to obtain the composite gel electrolyte material with the interpenetrating network porous structure;
wherein: the temperature of the heating forming is 30-80 ℃, and the time of the heating forming is 10 min-1 h;
the solvent of the lithium salt solution is at least one of diethyl ether, ethanol, acetonitrile, tetrahydrofuran, malononitrile, succinonitrile, glutaronitrile, adiponitrile, pimelic dinitrile, suberonitrile, nonyldinitrile and decyldinitrile.
2. The method of preparing an interpenetrating network porous structured composite gel electrolyte material according to claim 1, wherein the urea-containing alkaline solution is pre-frozen at-10 ℃ before the cellulose nanofibers are dissolved in the urea-containing alkaline solution.
3. The method for preparing 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, and the step of dissolving the polyvinyl alcohol in the deionized water solution is specifically to stir the polyvinyl alcohol at a stirring rate of 50-500 r/min for 4-4.5 hours at 45-50 ℃ after the polyvinyl alcohol is put into the deionized water solution.
4. The method for preparing the interpenetrating network porous structured composite gel electrolyte material according to claim 1, wherein the vortex mixing means that a mixture of cellulose nanofiber dispersion liquid and polyvinyl alcohol dispersion liquid added with potassium hydroxide is placed on a hot plate at 70 ℃ and magnetically stirred at a speed of 225r/min overnight.
5. The method for preparing the composite gel electrolyte material with the interpenetrating network porous structure according to claim 1, wherein the step of performing the heating forming on the mixture after vortex mixing is specifically to pour a product after vortex mixing into a mold for heating forming, and the mold is a glass mold or a plastic mold.
6. The method for preparing the composite gel electrolyte material with the interpenetrating network porous structure according to claim 1, wherein the lithium salt is at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bistrifluoromethylsulfonyl imide, lithium bistrifluorosulfonyl imide, lithium dioxalate borate, lithium difluorooxalato borate, lithium trifluoromethane sulfonate and lithium bistrifluoromethylsulfonyl imide.
7. The interpenetrating network porous composite gel electrolyte material prepared by the preparation method of the interpenetrating network porous composite gel electrolyte material according to any one of claims 1 to 6.
8. The use of the interpenetrating network porous structured composite gel electrolyte material prepared by the preparation method of the interpenetrating network porous structured composite gel electrolyte material of any one of claims 1 to 6 for preparing conductive materials, sensing materials and super capacitor diaphragms.
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