CN114221573A - Cellulose-based nano friction generator with high output performance and preparation method thereof - Google Patents
Cellulose-based nano friction generator with high output performance and preparation method thereof Download PDFInfo
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- 239000001913 cellulose Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920002749 Bacterial cellulose Polymers 0.000 claims abstract description 69
- 239000005016 bacterial cellulose Substances 0.000 claims abstract description 69
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims abstract description 57
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims abstract description 57
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
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- 239000000463 material Substances 0.000 abstract description 12
- 239000008367 deionised water Substances 0.000 abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 abstract description 8
- 239000002783 friction material Substances 0.000 abstract description 5
- 230000001276 controlling effect Effects 0.000 abstract description 2
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- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N1/00—Electrostatic generators or motors using a solid moving electrostatic charge carrier
- H02N1/04—Friction generators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the field of materials, and particularly relates to a cellulose-based friction nano-generator and a preparation method thereof. The invention provides a cellulose-based nano friction generator which comprises a positive electrode material, a negative electrode material and an electrode material, wherein the positive electrode material comprises bacterial cellulose and hydroxyethyl cellulose. The invention provides a cellulose-based positive electrode material for a friction and friction nano-generator for the first time, and also provides a method for improving the output performance of the friction nano-generator by regulating and controlling the surface work function of the friction material by a simple physical blending method for the first time. The nano friction generator anode film prepared by the invention is dissolved by using deionized water only in the preparation process, and has good biocompatibility and degradability; the introduced hydroxyethyl cellulose can reduce the surface work function of the bacterial cellulose film, and the output performance of the prepared friction nano-generator can be greatly improved while the advantages of the bacterial cellulose are kept.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a cellulose-based friction nano-generator and a preparation method thereof.
Background
The friction nano generator is a device capable of converting ubiquitous tiny low-frequency (<5Hz) mechanical energy into electric energy, and is prepared for the first time in 2012, and then has attracted wide attention of the scientific community. The triboelectric nanogenerator can realize conversion from mechanical energy to electric energy based on two classical physical phenomena of triboelectric generation and electrostatic induction. Since different materials have different electron affinity, triboelectric charging can occur when the materials are subjected to contact friction. Meanwhile, the larger the difference between the gain and loss electron capacities of the materials is, the more electrons are transferred in the contact separation process of the materials.
However, the existing friction nano-generator still faces many challenges, and the researchers focus on how to improve the output performance of the friction nano-generator. Currently, there is a lot of work in improving output performance: the surface contact area is improved by constructing a micro-nano structure on the surface of the friction material; the material has more differentiated electron gaining and losing capacity through chemical modification; and a conductive layer and an energy storage layer are introduced, so that the charge loss in the friction process is reduced, and the like. However, these modification methods themselves have many problems to be solved. For example, constructing a micro-nano structure on the surface of a material requires a professional instrument or long-time solvent etching; the chemical modification process is complex and is not suitable for large-scale production; the introduction of the conductive layer and the energy storage layer easily causes delamination of the friction material, which is not conducive to long-term use. Therefore, in view of the problems of the conventional modification methods, it is necessary to provide a simple and efficient method for improving the output performance.
In the aspect of material selection, the friction nano generator is considered to be possibly used in a large scale, and the friction nano generator cannot be recycled only by manpower after being out of service, so that a naturally degradable friction material is considered. Cellulose is the main component of plant cell wall, and is widely distributed in nature and widely available. Meanwhile, the cellulose has good biocompatibility, can be degraded in nature, and has wide application range and application prospect. Bacterial cellulose is a general name for synthesizing cellulose under specific environment by various microorganisms such as acetobacter, is industrially produced at present, has better guaranteed yield and performance, and is used in the fields of medical materials and cosmetics.
Although the bacterial cellulose has good mechanical properties and can be degraded in nature, the bacterial cellulose has a relatively high surface work function, so that electrons are difficult to lose in the friction process when the bacterial cellulose is used as a friction positive electrode material, and therefore the bacterial cellulose needs to be modified to improve the electron losing capability.
In the prior art, no report is available about the application of a composite membrane prepared by compounding bacterial cellulose and hydroxyethyl cellulose to a positive electrode material of a friction nano generator.
Disclosure of Invention
Aiming at the existing problems of a friction nano-generator and bacterial cellulose, the invention provides a preparation method of a pure cellulose-based friction nano-generator.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the invention is to provide a cellulose-based nano friction generator, which comprises a positive electrode material, a negative electrode material and an electrode material, wherein the positive electrode material comprises bacterial cellulose and hydroxyethyl cellulose.
Further, in the friction generator, the ratio of the bacterial cellulose to the hydroxyethyl cellulose is as follows: 40-90 parts of bacterial cellulose and 10-60 parts of hydroxyethyl cellulose.
Further, the positive electrode material is a bacterial cellulose/hydroxyethyl cellulose composite film obtained by compounding bacterial cellulose and hydroxyethyl cellulose and then forming a film.
Further, the thickness of the bacterial cellulose/hydroxyethyl cellulose composite membrane is 0.015-0.060 mm; so that the finally obtained friction nano generator has good output performance and good mechanical property.
Further, the bacterial cellulose/hydroxyethyl cellulose composite membrane is prepared by the following method: uniformly stirring hydroxyethyl cellulose, bacterial cellulose and water to obtain a mixture aqueous solution; and (3) forming a film by using the obtained mixture water solution to obtain the bacterial cellulose/hydroxyethyl cellulose composite film.
Further, the preparation method of the bacterial cellulose/hydroxyethyl cellulose composite membrane comprises the following steps: firstly, uniformly stirring and mixing a hydroxyethyl cellulose aqueous solution and a bacterial cellulose aqueous solution to obtain a mixture aqueous solution; then the mixture water solution is filtered to prepare a composite membrane; and finally drying to obtain the bacterial cellulose/hydroxyethyl cellulose composite membrane.
Further, the mass concentration of the hydroxyethyl cellulose aqueous solution is 0.5 g/L-3.0 g/L.
Further, the mass concentration of the bacterial cellulose water solution is 0.57-1.29 g/L.
Further, the hydroxyethyl cellulose aqueous solution and the bacterial cellulose aqueous solution are uniformly mixed by ultrasonic stirring.
Further, in the friction generator, the negative electrode material and the electrode material are selected from the negative electrode material and the electrode material of the existing friction generator, for example, the negative electrode material can be a polyvinylidene fluoride film, and the electrode material can be a copper adhesive tape.
The second technical problem to be solved by the present invention is to provide a preparation method of the cellulose-based nano friction generator, wherein the preparation method comprises: respectively connecting the positive electrode material and the negative electrode material with electrode materials to obtain a friction positive electrode film and a friction negative electrode film; then the positive surfaces of the friction positive electrode film and the friction negative electrode film are oppositely pasted; and finally, packaging with an insulating material.
The third technical problem to be solved by the present invention is to provide a method for improving the surface work function of bacterial cellulose, wherein the method comprises: hydroxyethyl cellulose is added into the bacterial cellulose.
Further, in the method for improving the surface work function of the bacterial cellulose, the ratio of the bacterial cellulose to the hydroxyethyl cellulose is as follows: 40-90 parts of bacterial cellulose and 10-60 parts of hydroxyethyl cellulose.
In the invention, the surface work function is a physical quantity for measuring the difficulty of electron at the Fermi level on the surface of the solid to escape from the solid, when the surface work function is larger, the surface of the solid can show the attraction capacity to the electron, and when the surface work function is smaller, the electron on the surface of the solid is easier to escape;
the invention has the beneficial effects that:
the invention provides a cellulose-based positive electrode material for a friction and friction nano-generator for the first time, and also provides a method for improving the output performance of the friction nano-generator by regulating and controlling the surface work function of the friction material by a simple physical blending method for the first time. The nano friction generator anode film prepared by the invention is dissolved by using deionized water only in the preparation process, and has good biocompatibility and degradability; the introduced hydroxyethyl cellulose can reduce the surface work function of the bacterial cellulose film, and the output performance of the prepared friction nano-generator can be greatly improved while the advantages of the bacterial cellulose are kept.
In addition, the preparation method of the pure cellulose-based friction nano-generator is simple, the preparation process is environment-friendly and pollution-free, and no other organic solvent is added in the whole process because the friction anode film layer is prepared by dissolving only deionized water; therefore, the biocompatibility of the bacterial cellulose is retained to a great extent, the degradability of the composite membrane is very good, the composite membrane can be widely used in nature, the environment is not polluted, and the biocompatibility and the degradability of the composite membrane enable the composite membrane to have the potential of being applied to the surface of a human body or even in the human body and have extremely high application value.
Description of the drawings:
FIG. 1 is a schematic diagram of a manufacturing process of cellulose-based friction nano-generators of examples 1 to 4 and comparative examples 1 to 2 of the present invention.
FIG. 2 is a graph showing changes in work function of cellulose-based positive electrode materials obtained in examples 1 to 4 of the present invention and comparative examples 1 to 2.
Fig. 3a, 3b, 3c and 3d are graphs of short-circuit current output performance, open-circuit voltage output performance, output performance of the amount of transferred charge per friction process of the cellulose-based friction nano-generator obtained in examples 1 to 4 of the present invention and comparative examples 1 to 2, and output power of example 4 under different external resistances, respectively.
FIG. 4 is a graph showing tensile mechanical properties of cellulose-based positive electrode materials obtained in examples 1 to 4 of the present invention and comparative examples 1 to 2.
Detailed Description
The invention indicates that hydroxyethyl cellulose (HEC) is introduced into Bacterial Cellulose (BC) for the first time, and the addition of the hydroxyethyl cellulose can obviously reduce the surface work function of the bacterial cellulose, so that the output performance of the friction nano-generator prepared by the composite film obtained by suction filtration is obviously improved.
The following examples are given to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Examples 1 to 4:
1) respectively weighing 16.36g (example 1), 14.55g (example 2), 10.91g (example 3) and 7.27g (example 4) of bacterial cellulose dispersion liquid (the bacterial cellulose dispersion liquid is purchased from Qihong science and technology, the actual content of the bacterial cellulose in the bacterial cellulose dispersion liquid is 0.55 percent, and the dispersing agent is water) in a beaker, and then respectively adding 70ml of deionized water;
2) 10mg (example 1), 20mg (example 2), 40mg (example 3) and 60mg (example 4) of hydroxyethylcellulose powder were weighed into a beaker, and then dissolved in 20ml of deionized water in a 50 ℃ water bath;
3) respectively adding the hydroxyethyl cellulose aqueous solution obtained in the step 2) into the bacterial cellulose aqueous solution obtained in the step 1) according to the mass ratio, stirring for 10min on a stirring table by using a magnetic stirrer, and then ultrasonically dispersing for 20min in an ultrasonic cleaner; the mass ratio of the actual bacterial cellulose in the bacterial cellulose dispersion liquid to the hydroxyethyl cellulose powder is respectively as follows: 90: 10 (example 1, written BH10), 80: 20 (example 2, written BH20), 60: 40 (example 3, written BH40), 40: 60 (example 4, written BH60) corresponding to the mass of the bacterial cellulose dispersion and the mass of the cellulose powder, respectively: 16.36g and 10mg (example 1), 14.55g and 20mg (example 2), 10.91g and 40mg (example 3), 7.27g and 60mg (example 4); ensuring that the total mass of the actual bacterial cellulose and the hydroxyethyl cellulose in the aqueous solution of each group of the mixture is 100 mg;
4) carrying out suction filtration on the mixture aqueous solution obtained in the step (3), and carrying out vacuum filtration by adopting a PVDF filter membrane with the diameter of 5cm and the pore diameter of 0.22 mu m; 30ml of mixed solution used in each suction filtration, namely 90ml of mixture water solution is subjected to suction filtration for 3 times;
5) drying the suction filtration film obtained in the step (4) at room temperature of 25 ℃;
6) cutting the dried film obtained in the step (5) into squares of 2cm x 2cm, and directly sticking the squares on a copper adhesive tape to prepare a friction anode film;
7) the other pole material is polyvinylidene fluoride film, which is cut into 2cm by 2cm square, and is directly pasted on the copper adhesive tape to prepare the friction negative pole film;
8) and (3) sticking the front surfaces of the friction anode membrane and the friction cathode membrane oppositely, wherein the middle part is separated by 2cm, packaging the outer layer by using a polyimide film, and preparing the mixed cellulose friction nano generator.
Comparative example 1
1) Weighing 18.18g of bacterial cellulose dispersion liquid (the bacterial cellulose dispersion liquid is purchased from Qihong science and technology, the actual bacterial cellulose content in the bacterial cellulose dispersion liquid is 0.55 percent, and the dispersing agent is water) in a beaker, and then adding 90ml of deionized water; then stirring the mixture for 10min by using a magnetic stirrer on a stirring table, and then ultrasonically dispersing the mixture for 20min in an ultrasonic cleaner;
2) vacuum filtering 30ml of the bacterial cellulose aqueous solution obtained in the step (1), namely filtering 90ml of the mixture aqueous solution for 3 times, and selecting a PVDF filter membrane with the diameter of 5cm and the pore diameter of 0.22 mu m;
3) drying the suction filtration membrane obtained in the step (2) at room temperature of 25 ℃;
4) cutting the dried suction filtration membrane obtained in the step (3) into a square with the size of 2cm x 2cm, and then directly sticking the square to a copper adhesive tape to prepare a friction positive electrode membrane, which is marked as BH 0;
5) the other pole material is polyvinylidene fluoride film, which is cut into 2cm by 2cm square, and is directly pasted on the copper adhesive tape to prepare the friction negative pole film;
6) and (3) oppositely pasting the positive friction electrode film obtained in the step (4) and the negative friction electrode film obtained in the step (5), wherein the middle of the positive friction electrode film is separated by 2cm, packaging the outer layer of the positive friction electrode film with a polyimide film, and preparing the pure bacterial cellulose friction nano generator.
Comparative example 2
1) Weighing 100mg of hydroxyethyl cellulose powder, adding the hydroxyethyl cellulose powder into a beaker, adding 18ml of deionized water for dissolving, and performing the dissolving process in a 50 ℃ water bath kettle;
2) pouring the hydroxyethyl cellulose aqueous solution obtained in the step (1) into a watch glass for pouring to form a film;
3) putting the watch glass in the step (2) into a high-temperature oven at 60 ℃ for drying;
4) cutting the pure hydroxyethyl cellulose film dried in the step (3) into a square of 2cm by 2cm, and directly sticking the square on a copper adhesive tape to prepare a friction positive electrode film, which is marked as HEC;
5) the other pole material is polyvinylidene fluoride film, which is cut into 2cm by 2cm square, and is directly pasted on the copper adhesive tape to prepare the friction negative pole film;
6) and (3) oppositely sticking the positive friction electrode film obtained in the step (4) and the negative friction electrode film obtained in the step (5), wherein the middle of the positive friction electrode film is separated by 2cm, packaging the outer layer by using a polyimide film, and preparing the pure hydroxyethyl cellulose friction nano generator.
Fig. 1 shows the preparation processes of the cellulose-based friction positive electrode thin films of examples 1 to 4 and comparative examples 1 to 2, and it can be seen that in the whole preparation process, only deionized water is used as a solvent without introducing other organic solvents, and substances polluting the environment are not generated in the preparation process.
FIG. 2 shows the results of the surface work functions of the cellulose-based friction positive electrode films of examples 1 to 4 and comparative examples 1 to 2 with different contents of hydroxyethyl cellulose, and it can be seen from FIG. 2 that the surface work function of the film is gradually reduced with the increase of the amount of hydroxyethyl cellulose; therefore, when the composite film is used as a positive electrode material, the charge transfer in the friction process is facilitated due to the reduction of the surface work function.
Fig. 3 shows the output performance results of the friction nano-generator prepared by the cellulose-based friction positive electrode films of examples 1 to 4 and comparative examples 1 to 2 with different hydroxyethyl cellulose contents, and it can be seen from fig. 3 that the output performance of the nano-friction generator increases with the increase of the hydroxyethyl cellulose content and reaches the highest value when 60% hydroxyethyl cellulose is added.
FIG. 4 shows the mechanical property results of cellulose-based friction positive electrode films of examples 1 to 4 and comparative examples 1 to 2 with different contents of hydroxyethyl cellulose; as can be seen from fig. 4, the stretching performance of the system tends to decrease gradually as the content of HEC in the film increases.
In addition, in the experiment, carboxymethyl cellulose and hydroxypropyl methyl cellulose are respectively introduced into bacterial cellulose to prepare the friction positive electrode film; however, it was found that the addition of these celluloses did not lower the surface work function thereof, and thus the output performance of the triboelectric generator produced when it was used as a positive electrode material was not good.
The above description is only for the specific implementation method of the present invention, but the protection scope of the present invention is not limited thereto, and any equivalent modifications and substitutions made by those skilled in the related art within the technical scope of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A cellulose-based nano friction generator comprises a positive electrode material, a negative electrode material and an electrode material, and is characterized in that the components of the positive electrode material comprise bacterial cellulose and hydroxyethyl cellulose.
2. The cellulose-based nano-friction generator according to claim 1, wherein the friction generator has a ratio of bacterial cellulose to hydroxyethyl cellulose of: 40-90 parts of bacterial cellulose and 10-60 parts of hydroxyethyl cellulose.
3. The cellulose-based nano-friction generator according to claim 1 or 2, wherein the positive electrode material is a bacterial cellulose/hydroxyethyl cellulose composite film obtained by compounding bacterial cellulose and hydroxyethyl cellulose and then forming a film.
4. The cellulose-based nano-friction generator according to any one of claims 1 to 3, wherein the thickness of the bacterial cellulose/hydroxyethyl cellulose composite film is 0.015 to 0.060 mm.
5. The cellulose-based nano-friction generator according to any one of claims 1 to 4, wherein the bacterial cellulose/hydroxyethyl cellulose composite membrane is prepared by the following method: uniformly stirring hydroxyethyl cellulose, bacterial cellulose and water to obtain a mixture aqueous solution; and (3) forming a film by using the obtained mixture water solution to obtain the bacterial cellulose/hydroxyethyl cellulose composite film.
6. The cellulose-based nano-friction generator according to claim 5, wherein the preparation method of the bacterial cellulose/hydroxyethyl cellulose composite membrane comprises: firstly, uniformly stirring and mixing a hydroxyethyl cellulose aqueous solution and a bacterial cellulose aqueous solution to obtain a mixture aqueous solution; then the mixture water solution is filtered to prepare a composite membrane; and finally drying to obtain the bacterial cellulose/hydroxyethyl cellulose composite membrane.
7. The cellulose-based nano-friction generator according to claim 6, wherein the mass concentration of the hydroxyethyl cellulose aqueous solution is 0.5g/L to 3.0 g/L;
further, the mass concentration of the bacterial cellulose water solution is 0.57-1.29 g/L.
8. The method for preparing the cellulose-based nano-friction generator according to any one of claims 1 to 7, comprising the following steps: respectively connecting the positive electrode material and the negative electrode material with electrode materials to obtain a friction positive electrode film and a friction negative electrode film; then the positive surfaces of the friction positive electrode film and the friction negative electrode film are oppositely pasted; and finally, packaging with an insulating material.
9. A method for improving the surface work function of bacterial cellulose is characterized by comprising the following steps: hydroxyethyl cellulose is added into the bacterial cellulose.
10. The method for improving the work function of the surface of the bacterial cellulose as claimed in claim 9, wherein the ratio of the bacterial cellulose to the hydroxyethyl cellulose is: 40-90 parts of bacterial cellulose and 10-60 parts of hydroxyethyl cellulose.
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