CN113150346A - Double-layer polyelectrolyte membrane - Google Patents
Double-layer polyelectrolyte membrane Download PDFInfo
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- CN113150346A CN113150346A CN202110386515.XA CN202110386515A CN113150346A CN 113150346 A CN113150346 A CN 113150346A CN 202110386515 A CN202110386515 A CN 202110386515A CN 113150346 A CN113150346 A CN 113150346A
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Abstract
The invention belongs to the technical field of functional materials, and particularly relates to a double-layer polyelectrolyte membrane, a preparation method thereof and a nano-generator. The double-layer polyelectrolyte membrane comprises a first layer of polycation membrane and a second layer of polyanion membrane, wherein the first layer of polycation membrane and the second layer of polyanion membrane are arranged in a laminated mode, and the upper layer and the lower layer present oppositely charged migratable ions, so that the oppositely charged migratable ions can be promoted to directionally diffuse under the drive of the ion concentration difference to generate electric energy. And assembling the pair of conductive carbon rubber belt electrodes and the double-layer polyelectrolyte membrane by a sandwich-like structure to obtain a single generator. Due to the excellent mechanical flexibility and the cuttable characteristic of a single generator, the generator units can be integrated on a large scale through staggered ordered stacking by means of high-precision laser processing. The voltage output of the integrated device is linearly increased along with the number of the series units, and the electricity generation output of kilovolt is realized. The integrated generator can be further deformed through a paper folding technology, and the functions of miniaturization and selective power supply are achieved.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a double-layer polyelectrolyte membrane, in particular to a heterogeneous double-layer polyelectrolyte membrane, a preparation method thereof and a nano-generator.
Background
Lipid bilayers of asymmetric structure are present in many cytoplasmic membranes, such as the erythrocyte membrane. Neutral lipids (such as phosphatidylcholine) are distributed predominantly in the outer leaflet, while anionic lipids (such as phosphatidylserine) are distributed predominantly in the inner leaflet. The asymmetric charged lipid profile can induce transmembrane potentials on both sides of the bilayer membrane.
The research at present shows that oxygen-containing functional groups in the polyelectrolyte can efficiently adsorb water molecules and dissociate transferable ions, thereby changing the ionic conductance of the material. Therefore, the polyelectrolyte membrane has excellent responsiveness to moisture. However, currently, research on biomimetic heterostructure bi-layer polyelectrolyte membranes is still in the blank stage.
Disclosure of Invention
The invention aims to provide a double-layer polyelectrolyte membrane, based on the existing research, oxygen-containing functional groups in polyelectrolyte can efficiently adsorb water molecules and dissociate transferable ions, so that the ionic conductivity of the material is changed, and the nano-generator is prepared by utilizing the characteristic of the double-layer polyelectrolyte membrane.
The invention provides a double-layer polyelectrolyte membrane, which comprises a first layer of polycation membrane and a second layer of polyanion membrane, wherein the first layer of polycation membrane and the second layer of polyanion membrane are arranged in a laminated manner; the ratio of the thickness of the second layer of polyanionic membrane to the thickness of the first layer of polycationic membrane is 0.57-2.7.
The preparation method of the double-layer polyelectrolyte membrane provided by the invention comprises the following steps:
(1) pouring aqueous solution of polyanionic material with the concentration of 175-700mg/mL into a plastic culture dish, and then airing and drying the membrane at the drying temperature of 30-60 ℃ for 4-10 hours to obtain the polyanionic membrane;
(2) spraying a polycation material water solution with the concentration of 150-300 mg/mL on the surface of the polyanion membrane prepared in the step (1), and forming a polycation membrane on the surface of the polyanion membrane in situ to obtain a heterogeneous double-layer polyelectrolyte membrane, wherein the thickness of the double-layer polyelectrolyte membrane is 25-400 microns;
the nano generator provided by the invention comprises a pair of electrodes and a power generation layer, wherein the pair of electrodes and the power generation layer are stacked like a sandwich, the pair of electrodes are respectively arranged on the upper surface and the lower surface of the power generation layer, and the power generation layer is the double-layer polyelectrolyte membrane prepared by the invention.
The double-layer polyelectrolyte membrane provided by the invention has the advantages that:
the double-layer polyelectrolyte membrane consists of a first layer formed by a polycation membrane and a second layer formed by a polyanion membrane. The two layers above and below the double-layer polyelectrolyte membrane present oppositely charged mobile ions (such as hydrogen ions and chloride ions), so that the oppositely charged mobile ions can be driven to directionally diffuse under the drive of the ion concentration difference, and electric energy can be generated. And assembling the pair of conductive carbon rubber belt electrodes and the double-layer polyelectrolyte membrane by a sandwich-like structure to obtain a single generator. Due to the excellent mechanical flexibility and cuttable characteristics of the single generator, the generator units can be integrated on a large scale through staggered ordered stacking by means of laser processing. The voltage output of the integrated device is linearly increased along with the number of the series units, and the electricity generation output of kilovolt is realized. The integrated generator can be further deformed through a paper folding technology, and the functions of miniaturization and selective power supply are achieved.
Drawings
The foregoing aspects of the invention are explained in the description of the embodiments with reference to the following drawings, in which:
FIG. 1 is a schematic structural view of a two-layer polyelectrolyte membrane according to the present invention.
Fig. 2 is a schematic structural diagram of a nano-generator according to the present invention.
FIG. 3 is a graph of voltage generated by a nanogenerator according to one embodiment of the invention at 25% relative humidity and 25 ℃.
Fig. 4 is a schematic structural diagram of a large-scale nano-generator array according to the present invention.
Fig. 5 is a schematic structural diagram of the staggered sequential stacking proposed by the present invention.
In fig. 1 to 5, 1 is a first polycation membrane, 2 is a second polyanion membrane, 3 is a power generation layer composed of 1 and 2 together, 4 is an upper electrode layer, 5 is a lower electrode layer, 6 is an ammeter for a power generation signal to be tested, 7 is a plurality of upper electrode array layers, 8 is a plurality of power generation layer arrays, and 9 is a plurality of lower electrode array layers.
In fig. 5, D is the offset distance between the upper electrode array and the lower electrode array, and D is the offset distance between the upper electrode array and the power generating array.
Detailed Description
The double-layer polyelectrolyte membrane disclosed by the invention has a structure shown in figure 1, and comprises a first polycation membrane 1 and a second polyanion membrane 2, wherein the first polycation membrane and the second polyanion membrane are stacked, and the ratio of the thickness of the second polyanion membrane to the thickness of the first polycation membrane is 0.57-2.7.
In the double-layer polyelectrolyte membrane, the thickness of the first layer of polycation membrane is 7.6-121.2 micrometers, and the thickness of the second layer of polyanion membrane is 17.4-278.8 micrometers. Wherein the polycation membrane is polydiallyldimethylammonium chloride or polyallylamine hydrochloride. Wherein the polyanion membrane is polystyrene sulfonic acid, polystyrene sodium sulfonate or perfluorosulfonic acid.
The preparation method of the double-layer polyelectrolyte membrane provided by the invention comprises the following steps:
(1) pouring aqueous solution of polyanionic material with the concentration of 175-700mg/mL into a plastic culture dish, and then airing and drying the membrane at the drying temperature of 30-60 ℃ for 4-10 hours to obtain the polyanionic membrane;
(2) spraying a polycation material water solution with the concentration of 150-300 mg/mL on the surface of the polyanion membrane prepared in the step (1), and forming a polycation membrane on the surface of the polyanion membrane in situ to obtain a heterogeneous double-layer polyelectrolyte membrane, wherein the thickness of the double-layer polyelectrolyte membrane is 25-400 microns;
the structure of the nano-generator provided by the invention is shown in fig. 2, and the nano-generator comprises a pair of electrodes and a power generation layer, wherein the pair of electrodes, namely an upper electrode layer 3, a lower electrode layer 4 and the power generation layer 5, are stacked in a sandwich manner, and the power generation layer 5 is a double-layer polyelectrolyte membrane consisting of a first layer of polycation membrane 1 and a second layer of polyanion membrane 2 prepared by the method. The pair of electrodes is made of conductive carbon adhesive tapes.
The heterogeneous double-layer polyelectrolyte membrane prepared by the method has the maximum size of 0.067 square meters. The polycation membrane is poly diallyl dimethyl ammonium chloride (PDDA) or polyallylamine hydrochloride (PAH). The polyanion membrane is polystyrene sulfonic acid (PSS), sodium polystyrene sulfonate (PSSNa) or perfluorosulfonic acid (Nafion).
The present invention will be described in detail below with reference to the accompanying drawings and examples.
The charged lipid profile induces a transmembrane potential across the bilayer membrane. Based on the concept of bionic design, if a layer of polycation membrane is reconstructed on the surface of a layer of polyanion membrane, heterogeneous distribution of migratable ions (such as hydrogen ions and chloride ions) with opposite charges can be obtained, therefore, the hydrogen ions and the chloride ions can diffuse in opposite directions in the material under the driving of ion concentration difference gradient, and the polymer chain skeleton cannot migrate due to large volume, so that current can be formed in an external circuit and potential difference can be formed at two ends of the material along with the migration of free ions with opposite charges, and electric energy can be generated externally.
The heterogeneous two-layer polyelectrolyte membrane of the embodiment of the invention is formed by a first layer and a second layer which are integrated, wherein the first layer is formed by a polycation membrane and the second layer is formed by a polyanion membrane. The two layers above and below the double-layer polyelectrolyte membrane present oppositely charged mobile ions (such as hydrogen ions and chloride ions), so that the oppositely charged mobile ions can be driven to directionally diffuse under the drive of the ion concentration difference, and electric energy can be generated. And assembling the pair of conductive carbon rubber belt electrodes and the double-layer polyelectrolyte membrane by a sandwich-like structure to obtain a single generator. Due to the excellent mechanical flexibility and cuttable characteristics of the single generator, the generator units can be integrated on a large scale through staggered ordered stacking by means of laser processing. The voltage output of the integrated device is linearly increased along with the number of the series units, and the electricity generation output of kilovolt is realized. The integrated generator can be further deformed through a paper folding technology, and the functions of miniaturization and selective power supply are achieved.
By adopting the preparation method provided by the embodiment of the invention, the heterogeneous double-layer polyelectrolyte membrane with large area, mechanical flexibility, foldability, cuttability and strong power generation capability can be obtained by a simple membrane airing and spraying method, and the preparation method is simple and convenient, can be continuous and has the potential of large-scale production.
According to the nano generator provided by the embodiment of the invention, the heterogeneous polyelectrolyte membrane is used as the electricity generating layer and the pair of electrodes are assembled into the sandwich structure, so that the nano generator can generate open-circuit voltage and short-circuit current in an air environment, the electricity generating signal has excellent stability, the whole electricity generating process does not cause environmental pollution, and the nano generator can be repeatedly used. It will be appreciated by those skilled in the art that the features and advantages described above for the heterogeneous, bilayer polyelectrolyte membrane, remain applicable to the nanogenerator.
The nano generator can be stacked by a plurality of sandwiches, and relates to an integrated technology of staggered and orderly stacking. The nano generator unit has the characteristics of excellent mechanical flexibility, cuttability, large-area preparation and the like, so that the electrodes and the electricity generating materials can be automatically processed into an array by adopting ultraviolet laser. Firstly, the electrodes and the electricity generating array are obtained in a large scale by means of laser processing, and the structure of the electrode and the electricity generating array is shown in fig. 4, wherein 6 in fig. 4 is a plurality of upper electrode array layers, 7 is a plurality of electricity generating layer arrays, and 8 is a plurality of lower electrode array layers. And stacking the power generation array on the lower electrode array, and stacking the upper electrode array on the power generation array to obtain the large-scale integrated nano generator.
And performing staggered and ordered stacking on the obtained upper electrode array, the power generation array and the lower electrode array, wherein a schematic diagram of the staggered and ordered stacking is shown in fig. 5, D is a staggered distance between the upper electrode array and the lower electrode array, and D is a staggered distance between the upper electrode array and the power generation array. The ratio of D to D is 3-5.
The staggered ordered stacking technology of the embodiment of the invention can realize large-scale effective integration of the nano generator. And based on the advantages of continuous voltage output, simple device structure and high-precision laser processing of the generator unit, the integrated generator can realize high voltage output.
The following describes embodiments of the present invention:
example 1
In this example, a heterogeneous dual-layer polyelectrolyte membrane was prepared, specifically including the following steps:
(1) polyanion material poly (4-styrene sulfonic acid) (PSS) with molecular weight of 75000 is prepared into 500mg/ml water solution, the water solution is poured into a plastic culture dish with the diameter of 9 mm, then the plastic culture dish is placed into a baking oven with the temperature of 45 ℃, air blast drying is carried out for 4 hours, and the polyanion membrane, the polystyrene sulfonic acid membrane (PSS), with the thickness of 70 microns, can be obtained,
(2) and (2) spraying a polycation material aqueous solution on the surface of the polyanion membrane prepared in the step (1), and spraying an aqueous solution with the molecular weight of 100,000 polydiallyldimethylammonium chloride (PDDA) of 200mg/mL on the surface of the polystyrene sulfonic acid membrane (PSS) prepared in the step (1) in an air environment, so that a layer of PDDA membrane can be formed on the surface of the PSS membrane in situ, wherein the thickness of the PDDA membrane is 30 micrometers.
(3) The obtained heterogeneous double-layer polyelectrolyte membrane has good mechanical flexibility and foldability, and the thickness is 100 microns.
Example 2
(1) Polyanion material sodium polystyrene sulfonate (PSSNa) with the molecular weight of 500,000 is prepared into 700mg/ml aqueous solution, the aqueous solution is poured into a plastic culture dish with the diameter of 9 mm, and then the plastic culture dish is placed into a baking oven with the temperature of 60 ℃ and is dried by air blowing for 10 hours, so that the polyanion membrane, namely the polystyrene sulfonic acid membrane (PSSNa), with the thickness of 278.8 micrometers can be obtained.
(2) Spraying a polycation material aqueous solution on the surface of the polyanion film prepared in the step (1), and spraying an aqueous solution with the molecular weight of 18,000 polyallylamine hydrochloride (PAH) of 150mg/mL on the surface of the polystyrene sulfonic acid film (PSSNa) prepared in the step (1) in an air environment, so that a layer of PAH film can be formed in situ on the surface of the PSSNa film, and the thickness of the PAH film is 7.6 micrometers.
(3) The resulting heterogeneous bilayer polyelectrolyte membrane was 286.4 microns thick.
Example 3
(1) Preparing polyanionic material perfluorosulfonic acid (Nafion) into 200mg/ml aqueous solution, pouring the aqueous solution into a plastic culture dish with the diameter of 9 mm, then placing the culture dish into a 30 ℃ oven, and drying the culture dish by blowing for 4 hours to obtain the polyanionic membrane perfluorosulfonic acid (Nafion) with the thickness of 40 microns.
(2) And (2) spraying a polycation material aqueous solution on the surface of the polyanion membrane prepared in the step (1), and spraying an aqueous solution with the molecular weight of 100,000 polydiallyldimethylammonium chloride (PDDA) of 200mg/mL on the surface of the perfluorosulfonic acid membrane (Nafion) prepared in the step (1) in an air environment, so that a layer of PDDA membrane can be formed in situ on the surface of the Nafion membrane, and the thickness of the PDDA membrane is 30 micrometers.
(3) The thickness of the final heterogeneous bilayer polyelectrolyte membrane was 70 microns.
Example 4
In this example, the resulting nanogenerator based on heterogeneous bilayer polyelectrolyte membranes was prepared. The method comprises the following specific steps:
(1) cutting a 7321 type conductive carbon adhesive tape into a size of 1 × 2 cm, one piece serving as a lower electrode and the other piece serving as an upper electrode;
(2) the prepared heterogeneous double-layer polyelectrolyte membrane (PDDA-PSS) is cut into 1 multiplied by 1 cm in size to serve as a power generation layer, then the power generation layer is clamped between an upper electrode and a lower electrode, a nano generator similar to a sandwich structure is assembled, and meanwhile good contact between the power generation layer and the electrodes is guaranteed.
In the embodiment, the nano generator is placed in an air environment (the relative humidity is 25 percent and the temperature is 25 ℃), two ends of the nano generator are connected with a Catherine test instrument, and the instrument records generated electrical signals in real time. The heterogeneous double-layer polyelectrolyte membrane has good hydrophilicity, and can continuously adsorb water vapor molecules from the air environment, so that functional groups in the material are induced to dissociate. Wherein the PSS layer has sulfonic acid functional group, which can dissociate electropositive hydrogen ion after absorbing water molecule, and the PDDA layer has ammonium functional group, which can dissociate electronegative chloride ion after absorbing water molecule. Since heterogeneous distribution of mobile ions of opposite charge may form an ion concentration gradient, free ions may diffuse from high concentration to low concentration under the action of the concentration gradient, specifically hydrogen ions may migrate from the PSS layer to the PDDA layer, while chloride ions may migrate from the PDDA layer to the PSS layer. The directional migration of ions may induce the generation of electrical signals. The nano generator can generate an open-circuit voltage of about 0.95V, and after the nano generator is continuously operated for about 258 hours, the open-circuit voltage retention rate is 67%, so that good stability is shown. As shown in fig. 3.
Although embodiments of the present invention have been shown and described, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and those skilled in the art can make changes, modifications, substitutions and alterations to the above embodiments within the scope of the present invention and still cover the scope of the present invention.
Claims (7)
1. A double-layer polyelectrolyte membrane is characterized in that the double-layer polyelectrolyte membrane comprises a first layer of polycation membrane and a second layer of polyanion membrane, wherein the first layer of polycation membrane and the second layer of polyanion membrane are arranged in a laminated manner; the ratio of the thickness of the second layer of polyanionic membrane to the thickness of the first layer of polycationic membrane is 0.57-2.7.
2. The bi-layer polyelectrolyte membrane according to claim 1, wherein the thickness of the first layer polycation membrane is 7.6 to 121.2 microns and the thickness of the second layer polyanion membrane is 17.4 to 278.8 microns.
3. The bi-layer polyelectrolyte membrane according to claim 1, wherein the polycation membrane is poly (diallyldimethylammonium chloride) or poly (allylamine hydrochloride).
4. The dual-layer polyelectrolyte membrane according to claim 1, wherein said polyanionic membrane is polystyrene sulfonic acid, sodium polystyrene sulfonate, or perfluorosulfonic acid.
5. A method for preparing the bi-layer polyelectrolyte membrane according to claim 1, characterized in that the method comprises the steps of:
(1) pouring aqueous solution of polyanionic material with the concentration of 175-700mg/mL into a plastic culture dish, and then airing and drying the membrane at the drying temperature of 30-60 ℃ for 4-10 hours to obtain the polyanionic membrane;
(2) and (2) spraying a polycation material water solution with the concentration of 150-300 mg/mL on the surface of the polyanion membrane prepared in the step (1), and forming the polycation membrane on the surface of the polyanion membrane in situ to obtain a heterogeneous double-layer polyelectrolyte membrane, wherein the thickness of the double-layer polyelectrolyte membrane is 25-400 microns.
6. The nanometer generator is characterized by comprising a pair of electrodes and a power generation layer, wherein the pair of electrodes and the power generation layer are stacked like a sandwich, the pair of electrodes are respectively arranged on the upper surface and the lower surface of the power generation layer, and the power generation layer is a double-layer polyelectrolyte film.
7. The nanogenerator of claim 6, wherein the material of the electrodes is conductive carbon tape.
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| CN115479407A (en) * | 2022-08-17 | 2022-12-16 | 北京金茂绿建科技有限公司 | Preparation method of air source heat pump system |
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| CH703869A2 (en) * | 2010-09-22 | 2012-03-30 | Inst Chemii Fizycznej Polskiej Akademii Nauk | Modifying polycarbonate surface, comprises applying a first modifying solution comprising polymer containing polymer chains with amino groups, and then a second modifying solution comprising polyelectrolyte, on a surface |
| CN103349917A (en) * | 2013-07-26 | 2013-10-16 | 北京工业大学 | Method for microwave intensifying layer-by-layer assembly polyelectrolyte multi-layer composite film |
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