CN111082698B - Modified cellulose nanofibril-based flexible friction nano generator - Google Patents
Modified cellulose nanofibril-based flexible friction nano generator Download PDFInfo
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- CN111082698B CN111082698B CN202010009508.3A CN202010009508A CN111082698B CN 111082698 B CN111082698 B CN 111082698B CN 202010009508 A CN202010009508 A CN 202010009508A CN 111082698 B CN111082698 B CN 111082698B
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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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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
Abstract
The invention discloses a modified cellulose nano-fibril-based flexible friction nano-generator, which is prepared by taking cellulose nano-fibrils as raw materials, regulating surface functional groups of the cellulose nano-fibrils through simple and easy aminosilane modification from two aspects of friction polarity and hydrophobicity of the materials, increasing the surface charge of the material as a friction anode material, and improving the hydrophobicity of a cellulose nano-fibril film. The friction nano generator has good flexibility and humidity resistance, can still maintain the output performance at a higher level under the condition of high environmental humidity, basically keeps the open-circuit voltage unchanged after working for 10000 periods, and has good circulation stability.
Description
Technical Field
The invention belongs to the technical field of high-valued utilization of lignocellulose biomass, and particularly relates to a modified cellulose nanofibril-based flexible friction nano generator.
Background
The triboelectrification effect is one of the most common and overlooked phenomena in daily life. The Wangzhong forest team in 2012 realizes the effective collection and conversion of triboelectricity for the first time, and provides a concept of a friction nano-generator. The friction nano generator is a device for converting mechanical energy into electric energy by utilizing contact electrification and electrostatic induction coupling, and the generation and transfer of surface charges of the friction nano generator are key factors influencing the output performance of the friction nano generator. The regulation and control of the polarity of the friction material of the friction nano generator is the key for optimizing the performance of the friction nano generator, and the direction attracts extensive attention and exploration of scholars in recent years. Wangzhilin et al tested the triboelectric polarity of commonly used materials and classified them into triboelectric series from the most tribologically positive to the most tribologically negative. Theoretically, selecting a material as the triboelectric couple at the top and bottom of the triboelectric series, respectively, produces the maximum output power. However, the choice of positive grade material is very limited compared to the negative electrode material. Currently, the most commonly used positive electrode materials mainly include synthetic polymers such as metals (e.g., silver and copper), metal oxides (e.g., zinc oxide and indium tin oxide), and polyamides. Metals are easily oxidized or corroded in a severe environment, and long-term use of polymer-based friction materials easily causes environmental problems such as white pollution. Therefore, research on introducing novel environment-friendly materials is bound to become a new trend of future development of the friction nano-generator, and development of green and high-performance cathode materials is a major challenge of performance optimization of the friction nano-generator at present.
Cellulose is the most abundant natural polymer on earth. Compared with traditional polymers, the renewable, low cost, biodegradable and biocompatible properties of cellulose make it a clear advantage in the field of environmental protection. Especially, the emergence of cellulose nanofibril materials in recent years not only complies with the demand of new environmental protection materials, but also has higher strength advantage than common fiber materials, and is one of the most interesting and promising candidate green friction materials in recent years. More importantly, the surface of the cellulose nano-fibril has a large number of hydroxyl groups, has inherent advantages in chemical modification and does not need to be additionally pretreated. The surface modification of the cellulose nano-fibrils mainly comprises sulfonation, carboxylation, esterification, silanization, polymer graft copolymerization modification and the like. In order to obtain a high-performance friction cathode material and improve the stability and the endurance of a cellulose nanofibril-based friction nano generator device, from the viewpoint of changing the polarity of a functional group, functional groups with strong friction polarity, such as amino, nitro, trifluoromethyl and the like, are widely researched and grafted on the surface of the cellulose nanofibril. The environmental humidity is one of the key factors influencing the power generation performance of the friction nano generator, and for the friction material, the stronger the surface hydrophobic performance is, the smaller the influence of water vapor on the friction power generation effect is, and the more the improvement of the moisture resistance performance of the friction nano generator is facilitated.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a modified cellulose nanofibril-based flexible friction nano-generator, which takes cellulose nanofibrils as a raw material, and starts from the two aspects of friction polarity and hydrophobic property of the material, surface functional groups of the cellulose nanofibrils are adjusted through simple amino silane modification, the surface charge of the cellulose nanofibrils as a friction anode material is increased, and the hydrophobic property of the cellulose nanofibrils is improved.
The technical problem to be solved by the invention is realized by the following technical scheme:
a modified cellulose nanofibril-based flexible friction nano-generator is prepared by taking cellulose nanofibrils as a raw material, carrying out chemical modification treatment on the cellulose nanofibrils by utilizing 3- (2-aminoethylamino) propyl methyldimethoxysilane to obtain a modified cellulose nanofibril film material, and assembling the modified cellulose nanofibril film and a fluorinated ethylene propylene film as a positive friction material and a negative friction material respectively.
The chemical modification treatment comprises the following steps:
the method comprises the following steps: adding 3- (2-aminoethylamino) propyl methyldimethoxysilane with the mass fraction of 5% into absolute ethyl alcohol, and stirring at normal temperature to obtain hydrolysate;
step two: and (3) adding cellulose nanofibrils into the hydrolysate obtained in the step one, carrying out ultrasonic treatment after vigorous stirring, and then placing the hydrolysate in a constant-temperature water bath at 80 ℃ for heating, stirring and reacting for 8-10 hours.
The cellulose nano-fibrils are prepared by mechanically grinding grass raw materials, and the width of the cellulose nano-fibrils is 20-200 nm.
The dosage of the 3- (2-aminoethylamino) propyl methyldimethoxysilane is 5-10 wt% relative to the cellulose nanofibrils.
The contact angle of the cellulose nano-fibril after chemical modification treatment by 3- (2-aminoethylamino) propyl methyldimethoxysilane is controlled to be 100-120 degrees.
The output voltage of the modified cellulose nanofibril-based flexible friction nano-generator is as high as 195-200V, and the voltage is still 192-196V after 10000 cycles of operation.
The invention firstly hydrolyzes amino silane, and the generated silanol monomer or oligomer is physically adsorbed on the hydroxyl of the cellulose nano-fibril through the action of hydrogen bond. Then, under heating conditions, moisture between the cellulose nanofibrils and silanol is removed at high temperature, at which time hydrogen bonds between the cellulose nanofibrils and silanol can be converted into stable covalent bonds. Meanwhile, residual silanol groups in the fibers can be further condensed with each other to form a polysiloxane structure. According to the invention, the prepared composite material has higher flexibility and humidity resistance by controlling the introduction amount of the 3- (2-aminoethylamino) propyl methyldimethoxysilane, and the prepared flexible cellulose nanofibril film and the flexible fluorinated ethylene propylene film can be assembled into a flexible friction nano generator. According to the invention, the surface free energy of the film is effectively reduced by modifying the cellulose nanofibrils with aminosilane, the introduction of amino functional groups not only improves the friction positive polarity of the cellulose nanofibrils, but also gives hydrophobic property to the surface of the material, and the influence of water vapor on the friction performance of the surface of the material is reduced.
The invention has the following beneficial effects:
(1) The preparation method of the invention has simple operation and low cost.
(2) The invention selects the cellulose nano-fibril as the raw material, has low cost and easy obtainment of the raw material, is an environment-friendly material, is non-toxic and harmless, and is beneficial to environmental protection and waste treatment.
(3) The friction nano-generator prepared by the invention has good flexibility and humidity resistance, the output performance can still be maintained at a higher level under the condition of high environmental humidity, the output voltage is up to 195-200V, the voltage is still maintained at 192-196V after 10000 cycles of operation, the open-circuit voltage is basically unchanged, and the friction nano-generator has good cycling stability.
(4) According to the invention, the cellulose nano-fibrils are used for replacing the traditional high polymer material as the matrix, so that the environment-friendly cellulose nano-fibril based flexible friction nano-generator is demonstrated, and a new thought is provided for further expanding the selection range of friction anode materials.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A modified cellulose nanofibril-based flexible friction nano-generator is specifically prepared by the following steps:
the cellulose nano-fibrils with the width of 200nm prepared by mechanically grinding the grass raw materials are chemically modified by adopting 3- (2-aminoethylamino) propyl methyldimethoxysilane: adding 5% by mass of 3- (2-aminoethylamino) propyl methyldimethoxysilane into absolute ethyl alcohol, stirring at normal temperature to obtain a hydrolysate, adding cellulose nanofibrils into the hydrolysate, carrying out intensive stirring, carrying out ultrasonic treatment, and then placing the hydrolysate into a water bath kettle with the constant temperature of 80 ℃ for heating and stirring reaction for 10 hours, wherein the amount of the 3- (2-aminoethylamino) propyl methyldimethoxysilane is 5wt% relative to the cellulose nanofibrils, and the modified cellulose nanofibril film material with the contact angle of 100 degrees is obtained. The modified cellulose nanofibril film and the fluorinated ethylene propylene film are respectively used as a positive friction material and a negative friction material to assemble the flexible friction nano generator.
The output voltage of the flexible friction nano generator prepared by the embodiment is up to 195V, and the voltage is still 192V after 10000 cycles of operation.
Example 2
A modified cellulose nanofibril-based flexible friction nano-generator is specifically prepared by the following steps:
the cellulose nano-fibrils with the width of 100nm prepared by mechanically grinding the grass raw materials are chemically modified by adopting 3- (2-aminoethylamino) propyl methyldimethoxysilane: adding 5% by mass of 3- (2-aminoethylamino) propyl methyldimethoxysilane into absolute ethyl alcohol, stirring at normal temperature to obtain a hydrolysate, adding cellulose nanofibrils into the hydrolysate, violently stirring, carrying out ultrasonic treatment, and then placing the hydrolysate into a water bath kettle with a constant temperature of 80 ℃ for heating and stirring reaction for 9 hours, wherein the dosage of the 3- (2-aminoethylamino) propyl methyldimethoxysilane is 8wt% relative to the cellulose nanofibrils, so as to obtain the modified cellulose nanofibril film material with the contact angle of 110 degrees. The modified cellulose nanofibril film and the fluorinated ethylene propylene film are respectively used as positive and negative friction materials to assemble the flexible friction nano generator.
The output voltage of the flexible friction nano generator prepared by the embodiment is up to 198V, and the voltage is still kept at 195V after 10000 cycles of operation.
Example 3
A modified cellulose nanofibril-based flexible friction nano-generator is specifically prepared by the following steps:
the cellulose nano-fibrils with the width of 20nm prepared by mechanically grinding the grass raw materials are chemically modified by adopting 3- (2-aminoethylamino) propyl methyldimethoxysilane: adding 5% by mass of 3- (2-aminoethylamino) propyl methyldimethoxysilane into absolute ethyl alcohol, stirring at normal temperature to obtain a hydrolysate, adding cellulose nanofibrils into the hydrolysate, violently stirring, carrying out ultrasonic treatment, and then placing the hydrolysate into a water bath kettle with a constant temperature of 80 ℃ for heating, stirring and reacting for 8 hours, wherein the using amount of the 3- (2-aminoethylamino) propyl methyldimethoxysilane is 10wt% relative to the cellulose nanofibrils, so as to obtain the modified cellulose nanofibril film material with the contact angle of 120 degrees. The modified cellulose nanofibril film and the fluorinated ethylene propylene film are respectively used as positive and negative friction materials to assemble the flexible friction nano generator.
The output voltage of the flexible friction nano generator prepared by the embodiment is up to 200V, and the voltage is kept at 196V after 10000 cycles of operation.
Comparative example 1
Different from the embodiment 3, when the width of the cellulose nano-fibril is 250nm and other conditions are not changed, the output voltage of the prepared flexible friction nano-generator is 188V, and the voltage is 181V after 10000 cycles of operation.
Comparative example 2
Unlike example 3, 3- (2-aminoethylamino) propylmethyldimethoxysilane was used in an amount of 4.5wt% relative to the cellulose nanofibrils, and when all other conditions were unchanged, the flexible friction nanogenerator was produced with an output voltage of 161V and a voltage of 149V after 10000 cycles of operation.
Comparative example 3
Different from the example 3, the dosage of the 3- (2-aminoethylamino) propyl methyldimethoxysilane is 13.2wt% relative to the cellulose nanofibrils, and when the other conditions are not changed, the output voltage of the flexible friction nano generator is 201V, and the voltage after 10000 cycles of operation is 190V.
Claims (6)
1. A modified cellulose nanofibril-based flexible friction nanogenerator is characterized in that: the method comprises the steps of taking cellulose nanofibrils as a raw material, carrying out chemical modification treatment on the cellulose nanofibrils by utilizing 3- (2-aminoethylamino) propyl methyldimethoxysilane to obtain a modified cellulose nanofibril film material, and assembling the modified cellulose nanofibril film and a fluorinated ethylene propylene film as a positive friction material and a negative friction material respectively to form the flexible friction nano generator.
2. The modified cellulose nanofibril-based flexible triboelectric nanogenerator of claim 1, wherein: the chemical modification treatment comprises the following steps:
the method comprises the following steps: adding 3- (2-aminoethylamino) propyl methyldimethoxysilane with the mass fraction of 5% into absolute ethyl alcohol, and stirring at normal temperature to obtain hydrolysate;
step two: and (3) adding cellulose nanofibrils into the hydrolysate obtained in the step one, carrying out ultrasonic treatment after vigorous stirring, and then placing the hydrolysate in a constant-temperature water bath at 80 ℃ for heating, stirring and reacting for 8-10 hours.
3. The modified cellulose nanofibril-based flexible triboelectric nanogenerator of claim 1, wherein: the cellulose nano-fibrils are prepared by mechanically grinding grass raw materials, and the width of the cellulose nano-fibrils is 20-200 nm.
4. The modified cellulose nanofibril-based flexible triboelectric nanogenerator of claim 1, wherein: the dosage of the 3- (2-aminoethylamino) propyl-methyldimethoxysilane is 5-10 wt% relative to the cellulose nanofibrils.
5. The modified cellulose nanofibril-based flexible triboelectric nanogenerator of claim 1, wherein: the contact angle of the cellulose nano-fibril after chemical modification treatment by 3- (2-aminoethylamino) propyl methyldimethoxysilane is controlled to be 100-120 degrees.
6. The modified cellulose nanofibril-based flexible triboelectric nanogenerator of claim 1, wherein: the output voltage of the flexible friction nano generator is as high as 195-200V, and the voltage is still maintained at 192-196V after 10000 cycles of operation.
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| CN109626316A (en) * | 2018-12-17 | 2019-04-16 | 广西大学 | A kind of D structure graphene nano power generator and preparation method thereof |
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| US10277147B2 (en) * | 2016-06-09 | 2019-04-30 | Wisconsin Alumni Research Foundation | Triboelectric nanogenerators based on chemically treated cellulose |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106146901A (en) * | 2016-08-04 | 2016-11-23 | 安徽博大纤维素科技有限公司 | The preparation method of the cellulose additive of dermatine pliability can be improved |
| CN109626316A (en) * | 2018-12-17 | 2019-04-16 | 广西大学 | A kind of D structure graphene nano power generator and preparation method thereof |
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| 丝胶和壳聚糖改善再生纸强度的研究;孙金煜等;《化工新型材料》;20180915(第09期);全文 * |
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