CN112480457A - Preparation method of ionic electroactive driver based on carboxylated bacterial cellulose - Google Patents
Preparation method of ionic electroactive driver based on carboxylated bacterial cellulose Download PDFInfo
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- 229920002749 Bacterial cellulose Polymers 0.000 title claims abstract description 89
- 239000005016 bacterial cellulose Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 32
- 239000002608 ionic liquid Substances 0.000 claims abstract description 31
- 230000001580 bacterial effect Effects 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 239000012528 membrane Substances 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- -1 1-ethyl-3-methylimidazole tetrafluoroborate Chemical compound 0.000 claims description 14
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 13
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 11
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- IRSVMGYCAXSOCN-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;methyl sulfate Chemical compound COS([O-])(=O)=O.CCCC[NH+]1CN(C)C=C1 IRSVMGYCAXSOCN-UHFFFAOYSA-N 0.000 claims 1
- ALGZQMQWKPQOER-UHFFFAOYSA-N 1-butyl-3-methyl-2H-imidazole cyanocyanamide Chemical compound N#CNC#N.CCCCN1CN(C)C=C1 ALGZQMQWKPQOER-UHFFFAOYSA-N 0.000 claims 1
- 229910052594 sapphire Inorganic materials 0.000 claims 1
- 239000010980 sapphire Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 239000003014 ion exchange membrane Substances 0.000 description 9
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920001746 electroactive polymer Polymers 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- ICIVTHOGIQHZRY-UHFFFAOYSA-N 1-butyl-3-methylimidazol-3-ium;cyanoiminomethylideneazanide Chemical compound [N-]=C=NC#N.CCCCN1C=C[N+](C)=C1 ICIVTHOGIQHZRY-UHFFFAOYSA-N 0.000 description 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229920000831 ionic polymer Polymers 0.000 description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- MEMNKNZDROKJHP-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;methyl sulfate Chemical compound COS([O-])(=O)=O.CCCCN1C=C[N+](C)=C1 MEMNKNZDROKJHP-UHFFFAOYSA-M 0.000 description 1
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
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- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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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
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- H01B1/124—Intrinsically conductive polymers
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Abstract
The invention belongs to the field of intelligent materials. The preparation method of the ionic type electroactive driver based on the carboxylated bacterial cellulose is low in cost, excellent in performance and good in reliability. The technical scheme is as follows: the preparation method of the ionic electroactive driver based on the carboxylated bacterial cellulose comprises the following steps: 1) preparing a bacterial cellulose dispersion liquid; 2) preparing a bacterial cellulose-polypyrrole dispersion liquid; 3) preparing a bacterial cellulose-polypyrrole-ionic liquid composite membrane; 4) and covering an electrode layer to prepare the bacterial cellulose-based ionic driver.
Description
Technical Field
The invention belongs to the field of intelligent materials, relates to an electroactive ionic polymer material, and particularly relates to a preparation method of an ionic electroactive driver based on carboxylated bacterial cellulose
Background
The electroactive polymer is a novel intelligent high polymer material, can change the internal structure under the action of an external electric field, generates mechanical responses in various forms such as stretching, bending, tightening or expansion, has extremely strong electrical and mechanical properties, and can simultaneously realize multiple functions such as driving, sensing and the like. Depending on the actuation mechanism, it can be classified into an electron type and an ion type. Among them, an Ionic Polymer Metal Composite (IPMC), which is a typical material among ionic electroactive polymers, is very widely used.
IPMC is generally a composite material obtained by depositing noble metals such as platinum, gold, etc. on the surface of an ion exchange membrane, and currently, the ion exchange membrane is mainly a Nafion perfluorosulfonic acid proton exchange membrane manufactured by dupont, usa. The actuation principle of IPMC is that under an applied voltage, water and cations in the ion exchange membrane move to the negative electrode, while anions move to the positive electrode. Since the cations are larger in volume than the anions, the negative electrode expands, the positive electrode contracts, and the IPMC macroscopically deflects toward the positive electrode.
However, the Nafion ion exchange membrane in the IPMC is high in price and low in yield; and the operation in air quickly loses a large amount of moisture, resulting in deterioration of driving performance. Precious metals such as gold, platinum, etc. deposited thereon further increase the cost of IPMC, and the metal electrode has poor adhesion and is subject to breakage after a period of operation. Due to the above disadvantages, the IPMC driver has a small deflection displacement, a low output force, and a poor response speed.
Bacterial cellulose is a special green cellulose, which is widely present in nature and abundant in content. The bacterial cellulose-based electrokinetic driving material has a compact reticular structure, strong mechanical property, good biocompatibility and degradability. After being oxidized by the TEMPO method, carboxyl groups are generated, and due to the electrostatic repulsion action and the hydrogen bond action among ions, the carboxylated bacterial cellulose can be well dispersed in water, thereby having important significance on the mechanical property and the crystallinity of a formed film.
No studies have been reported on carboxylated bacterial cellulose-based ionic driver materials.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provide a preparation method of an ionic type electroactive driver based on carboxylated bacterial cellulose, which has low cost, excellent performance and good reliability.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the ionic electroactive driver based on the carboxylated bacterial cellulose comprises the following steps:
1) preparation of bacterial cellulose Dispersion
Adding a proper amount of deionized water into the bacterial cellulose, and uniformly stirring to prepare a bacterial cellulose suspension. Oxidizing the bacterial cellulose by using a TEMPO oxidation method, filtering and oscillating to obtain a uniformly dispersed bacterial cellulose dispersion liquid;
2) preparation of bacterial cellulose-polypyrrole Dispersion
Adding polypyrrole (PPy) into the bacterial cellulose dispersion liquid by using a chemical oxidation polymerization method;
3) preparing a bacterial cellulose-polypyrrole-ionic liquid composite membrane:
adding ionic liquid into the dispersion liquid obtained in the step 2, fully stirring, carrying out vacuum bubble pumping, pouring into a mold, and drying to obtain a bacterial cellulose-polypyrrole-ionic liquid composite film;
4) coating an electrode layer to prepare a bacterial cellulose-based ionic driver
Coating a high-conductivity substance PEDOT, namely PSS (PEDOT is a polymer of EDOT (3, 4-ethylene dioxythiophene monomer), PSS is polystyrene sulfonate) on the prepared bacterial cellulose-PPy-ionic liquid composite membrane, and drying to obtain a bacterial cellulose base ionic driver (CBC-PPy-IL); the ratio of PEDOT to PSS is 5: 7-9.
Further, in the step 1), the weight content of the bacterial cellulose in the bacterial cellulose suspension is 1% -3%.
Further, the TEMPO oxidation process in step 1) is: adding sodium bromide and 2,2,6, 6-tetramethylpiperidine-1-oxygen free radical into suspension containing bacterial cellulose, adding sodium hypochlorite solution while stirring for reaction, and simultaneously adding sodium hydroxide solution to keep the pH value to 10-10.5; after the reaction is finished, adding a hydrogen chloride solution to adjust the pH value to 7;
wherein the weight proportions of the bacterial cellulose, the 2,2,6, 6-tetramethylpiperidine-1-oxygen free radical, the sodium bromide and the sodium hypochlorite are as follows in sequence: 50-80:1:5-8: 150-;
the mass fraction of the sodium hypochlorite solution is 12%; the concentration of the hydrogen chloride solution was 0.5 mol/L.
Further, the chemical oxidative polymerization method in the step 2) is as follows: taking bacterial cellulose dispersion, adding ferric chloride and pyrrole while stirring, and keeping the reaction for 30min under slow stirring;
wherein the weight proportions of the bacterial cellulose, the ferric chloride and the pyrrole are as follows in sequence: 1:0.8-1.2:0.5-2.5.
Further, the ionic liquid in the step 3) is [ EMIM][BF4](1-Ethyl-3-methylimidazolium tetrafluoroborate), [ BMIM][BF4](1-butyl-3-methylimidazolium tetrafluoroborate), [ HMIM][BF4](1-hexyl-3-methylimidazolium tetrafluoroborate), [ BMIM][DCA](1-butyl-3-methylimidazolium dicyanamide salt), [ BMIM][MeSO4]One of (1-butyl-3-methylimidazolium methyl sulfate); wherein the ratio of the bacterial cellulose to the ionic liquid is 1-3: 1.
Further, the vacuum bubble pumping process in the step 3) is continuously carried out for 3-5 times, each time lasts for 10-15 min, the drying temperature is 55-65 ℃, and the time is 10-12 hours.
Further, the drying temperature in the step 4) is 25-50 ℃, and the time is 2 hours.
Further, the concentration of the sodium hydroxide is 0.5 mol/L.
Compared with the prior art, the invention has the following advantages:
1. the bacterial cellulose is special green cellulose which widely exists in nature, is rich in content, has a compact reticular structure, strong mechanical property, good biocompatibility and degradability. Therefore, the invention adopts the bacterial cellulose as the substrate, and has low cost and good reliability.
2. The invention adopts TEMPO oxidation method to oxidize bacterial cellulose. Bacterial cellulose is difficult to dissolve in water due to the compact structure, and after being oxidized by using a TEMPO/NaBr/NaClO system, carboxyl functional groups are generated on the surface. By utilizing the electrostatic repulsion between carboxylate ions, the carboxylated bacterial cellulose can be well dispersed in water.
3. According to the invention, PPy is added into the bacterial cellulose containing carboxyl functional groups, and the PPy and the ionic liquid are subjected to cross-linking and ion interaction, so that the interface compatibility, the mechanical property and the electrochemical property of the ion exchange membrane are enhanced.
4. The invention adopts PEDOT and PSS materials as electrode materials, has the advantages of high conductivity, good thermal stability, strong adhesiveness and the like, and obviously improves the defects of high price and easy breakage of the traditional IPMC electrode materials.
5. The preparation method has simple process conditions, and adopts a vacuum drying method to remove air bubbles in the ion exchange membrane, so that the finally prepared driver is uniform, stable in work and excellent in performance. Has the advantages of simple operation and easy popularization.
6. The invention prepares ionic electroactive polymer with excellent comprehensive performance, and relates to a driver by taking the ionic electroactive polymer as a substrate. The defects of high cost and poor performance of the traditional polymer driver are mainly overcome, and popularization and application of the intelligent material are facilitated.
Drawings
FIG. 1 is an actuation schematic diagram of a driver based on a carboxylated bacterial cellulose-polypyrrole-ionic liquid composite membrane (in the diagram, A is an uncharged state, and B is an applied voltage state).
FIG. 2 is a surface SEM image of carboxylated bacterial cellulose-polypyrrole.
Fig. 3 is a surface SEM image of the carboxylated bacterial cellulose-polypyrrole-ionic liquid composite membrane.
Fig. 4 is an exemplary diagram of the driving displacement of the driver at DC 1.5V (as can be seen, the lower portion of the driver is deflected to the left).
Detailed Description
The present invention will be described in further detail with reference to embodiments shown in the drawings.
The driver is prepared by taking carboxylated bacterial cellulose, PPy and ionic liquid as an ion exchange membrane, immersing the ion exchange membrane into a PEDOT (power system stability) PSS solution, and attaching an electrode material to the surface of the ion exchange membrane.
Example 1
The preparation method of the ionic electroactive driver based on the carboxylated bacterial cellulose comprises the following steps:
1) preparing a carboxylated bacterial cellulose dispersion liquid:
adding 2g of bacterial cellulose into 100ml of deionized water and uniformly stirring;
oxidation of bacterial cellulose: taking the suspension, adding 0.016g of TEMPO (2, 2,6, 6-4 methylpiperidine-1-oxyl), 0.1g of NaBr (sodium bromide) and 3.1g of NaClO (sodium hypochlorite) solution with the mass fraction of 12%, and then adding 0.5mol/L of NaOH (sodium hydroxide) solution to maintain the pH value at 10.5; when the pH value is not further reduced (indicating the end of the reaction), 0.5mol/L HCl (hydrogen chloride) solution is added to adjust the pH value to 7; and centrifuging the obtained suspension for several times by using deionized water to obtain the bacterial cellulose dispersion.
2) Preparing a carboxylated bacterial cellulose-polypyrrole dispersion liquid:
the above bacterial cellulose dispersion was added with 1.0g of FeCl3 and 1ml of pyrrole under stirring, and the reaction was maintained for 30min under slow stirring. The product was then taken up on filter paper using a reduced pressure buchner funnel and washed several times with deionized water. Adding the mixture into 100ml of deionized water, and stirring for 2 hours to prepare the bacterial cellulose-polypyrrole dispersion liquid.
3) Preparation of carboxylated bacterial cellulose-polypyrrole-ionic liquid composite membrane
Adding 0.5g of ionic liquid [ EMIM ] [ BF4] into the dispersion liquid obtained in the step 2), stirring for 1h, pouring into a polytetrafluoroethylene mold, and placing in a vacuum drying oven to extract bubbles. And then pouring the composite membrane into a polytetrafluoroethylene mould for drying treatment, wherein the set temperature is 55 ℃, and the drying time is 11 hours, so as to obtain the bacterial cellulose-polypyrrole-ionic liquid composite membrane.
5) Coating an electrode layer to prepare a bacterial cellulose-based ionic driver
And (3) immersing the bacterial cellulose-polypyrrole-ionic liquid composite membrane obtained in the step 3) into a PEDOT (PSS) solution for 10min, taking out, and drying at 45 ℃ for 2h to obtain the bacterial cellulose-based ionic driver.
Example 2
The preparation method of the ionic electroactive driver based on the carboxylated bacterial cellulose comprises the following steps:
1) preparing a carboxylated bacterial cellulose dispersion liquid:
adding 1g of bacterial cellulose into 100ml of deionized water and uniformly stirring;
oxidation of bacterial cellulose: taking the suspension, adding 0.99g of NaBr solution, 0.014g of TEMPO solution and 3.0g of NaClO solution with the mass fraction of 12% into the suspension, and then adding 0.5mol/L of NaOH solution to maintain the pH value at 10.4; when the pH value is not further reduced, adding 0.5mol/L HCl solution to adjust the pH value to 7; and centrifuging the obtained suspension for several times by using deionized water to obtain the bacterial cellulose dispersion.
2) Preparing a carboxylated bacterial cellulose-polypyrrole dispersion liquid:
the above bacterial cellulose dispersion was added with 0.95g of FeCl3 and 1ml of pyrrole while stirring, and the reaction was maintained for 30min with slow stirring. The product was then taken up on filter paper using a reduced pressure buchner funnel and washed several times with deionized water. Adding the mixture into 100ml of deionized water, and stirring for 2 hours to prepare the bacterial cellulose-polypyrrole dispersion liquid.
3) Preparation of carboxylated bacterial cellulose-polypyrrole-ionic liquid composite membrane
Adding 0.5g of ionic liquid [ BMIM ] [ DCA ] into the dispersion liquid obtained in the step 2), stirring for 1h, pouring into a polytetrafluoroethylene mold, and placing in a vacuum drying oven to extract air bubbles. And then pouring the composite membrane into a polytetrafluoroethylene mould for drying treatment, setting the temperature to be 55 ℃, and drying for 12 hours to obtain the bacterial cellulose-polypyrrole-ionic liquid composite membrane.
5) Coating an electrode layer to prepare a bacterial cellulose-based ionic driver
And (3) immersing the bacterial cellulose-polypyrrole-ionic liquid composite membrane obtained in the step 3) into a PEDOT (PSS) solution for 10min, taking out, and drying at 40 ℃ for 2h to obtain the bacterial cellulose-based ionic driver.
Example 3
The preparation method of the ionic electroactive driver based on the carboxylated bacterial cellulose comprises the following steps:
1) preparing a carboxylated bacterial cellulose dispersion liquid:
adding 1g of bacterial cellulose into 100ml of deionized water and uniformly stirring;
oxidation of bacterial cellulose: taking the suspension, adding 0.11g of NaBr solution, 0.018g of TEMPO and 3.1g of NaClO solution with the mass fraction of 12 percent, and then adding 0.5mol/L of NaOH solution to maintain the pH value at 10.6; when the pH value is not further reduced, adding 0.5mol/L HCl solution to adjust the pH value to 7; and centrifuging the obtained suspension for several times by using deionized water to obtain the bacterial cellulose dispersion.
2) Preparing a carboxylated bacterial cellulose-polypyrrole dispersion liquid:
the above bacterial cellulose dispersion was added with 1.05g of FeCl3 and 1ml of pyrrole under stirring, and the reaction was maintained for 30min under slow stirring. The product was then taken up on filter paper using a reduced pressure buchner funnel and washed several times with deionized water. Adding the mixture into 100ml of deionized water, and stirring for 2 hours to prepare the bacterial cellulose-polypyrrole dispersion liquid.
3) Preparation of carboxylated bacterial cellulose-polypyrrole-ionic liquid composite membrane
Adding 0.5g of ionic liquid [ BMIM ] to the dispersion obtained in step 2)][MeSO4]Stirring for 1h, pouring into a polytetrafluoroethylene mold, and placing in a vacuum drying oven to extract bubbles. And then pouring the composite membrane into a polytetrafluoroethylene mould for drying treatment, setting the temperature at 60 ℃, and drying for 11 hours to obtain the bacterial cellulose-polypyrrole-ionic liquid composite membrane.
5) Coating an electrode layer to prepare a bacterial cellulose-based ionic driver
And (3) immersing the bacterial cellulose-polypyrrole-ionic liquid composite membrane obtained in the step 3) into a PEDOT (PSS) solution for 10min, taking out, and drying at 50 ℃ for 1.8h to obtain the bacterial cellulose-based ionic driver.
Thirdly, performance test:
SEM test
The surface of the carboxylated bacterial cellulose-polypyrrole obtained in example 1 was tested, and the test results are shown in fig. 2, which shows a porous structure; a surface SEM image of the carboxylated bacterial cellulose-polypyrrole-ionic liquid composite membrane is shown in fig. 3, which shows an ionic crosslinked network structure.
2. Response testing
The ionic electroactive driver based on carboxylated bacterial cellulose obtained in the test example has an excitation response under DC 1.5V, and the driving test result is shown in FIG. 4.
The ionic electroactive driver based on the carboxylated bacterial cellulose, which is obtained by the invention, oxidizes the bacterial cellulose by using a TEMPO method, so that carboxyl functional groups are generated on the surface of the bacterial cellulose. And the electrostatic repulsion between carboxylate ions is utilized to change the structure of the original bacterial cellulose which is tightly gathered and entangled. The carboxylated bacterial cellulose can be well dispersed in water. The driver with excellent performance and stable work is obtained by taking bacterial cellulose containing carboxyl functional groups as a matrix, adding PPy and ionic liquid to generate a crosslinking effect.
Finally, the above examples are only intended to illustrate the technical solution of the present invention and not to be construed as nature, and although the present invention has been described in detail with reference to the examples, those skilled in the art of the present invention can modify the technical idea of the present invention in various forms and all such modifications are intended to be included in the scope of the claims of the present invention.
Claims (8)
1. The preparation method of the ionic electroactive driver based on the carboxylated bacterial cellulose comprises the following steps:
1) preparation of bacterial cellulose Dispersion
Adding a proper amount of deionized water into the bacterial cellulose, and uniformly stirring to prepare a bacterial cellulose suspension;
oxidizing the bacterial cellulose by using a TEMPO oxidation method, filtering and oscillating to obtain a uniformly dispersed bacterial cellulose dispersion liquid;
2) preparation of bacterial cellulose-polypyrrole Dispersion
Adding polypyrrole into the bacterial cellulose dispersion liquid by using a chemical oxidation polymerization method;
3) preparing a bacterial cellulose-polypyrrole-ionic liquid composite membrane:
adding ionic liquid into the dispersion liquid obtained in the step 2, fully stirring, carrying out vacuum bubble pumping, pouring into a mold, and drying to obtain a bacterial cellulose-polypyrrole-ionic liquid composite film;
4) coating an electrode layer to prepare a bacterial cellulose-based ionic driver
PSS (patterned sapphire substrate) which is a high-conductivity substance is coated on the prepared bacterial cellulose-PPy-ionic liquid composite membrane, and the bacterial cellulose-based ionic driver is obtained after drying; the ratio of PEDOT to PSS is 5: 7-9.
2. The method for preparing ionic electroactive driver based on carboxylated bacterial cellulose as claimed in claim 1, wherein: in the step 1), the weight content of the bacterial cellulose in the bacterial cellulose suspension is 1-3%.
3. The method for preparing ionic electroactive driver based on carboxylated bacterial cellulose as claimed in claim 2, wherein: the TEMPO oxidation method in the step 1) comprises the following steps: adding sodium bromide and 2,2,6, 6-tetramethylpiperidine-1-oxygen free radical into suspension containing bacterial cellulose, adding sodium hypochlorite solution while stirring for reaction, and simultaneously adding sodium hydroxide solution to keep the pH value to 10-10.5; after the reaction is finished, adding a hydrogen chloride solution to adjust the pH value to 7;
wherein the weight proportions of the bacterial cellulose, the 2,2,6, 6-tetramethylpiperidine-1-oxygen free radical, the sodium bromide and the sodium hypochlorite are as follows in sequence: 50-80:1:5-8: 150-;
the mass fraction of the sodium hypochlorite solution is 12%; the concentration of the hydrogen chloride solution was 0.5 mol/L.
4. The method for preparing ionic electroactive driver based on carboxylated bacterial cellulose as claimed in claim 3, wherein: the chemical oxidative polymerization method in the step 2) comprises the following steps: taking bacterial cellulose dispersion, adding ferric chloride and pyrrole while stirring, and keeping the reaction for 30min under slow stirring;
wherein the weight proportions of the bacterial cellulose, the ferric chloride and the pyrrole are as follows in sequence: 1:0.8-1.2:0.5-2.5.
5. The method for preparing ionic electroactive driver based on carboxylated bacterial cellulose as claimed in claim 4, wherein: the ionic liquid in the step 3) is one of 1-ethyl-3-methylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole tetrafluoroborate, 1-hexyl-3-methylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole dicyanamide salt and 1-butyl-3-methylimidazole methyl sulfate; wherein the ratio of the bacterial cellulose to the ionic liquid is 1-3: 1.
6. The method for preparing ionic electroactive driver based on carboxylated bacterial cellulose as claimed in claim 5, wherein: the vacuum bubble-pumping process in the step 3) is continuously carried out for 3-5 times, each time lasts for 10-15 min, the drying temperature is 55-65 ℃, and the time is 10-12 h.
7. The method for preparing ionic electroactive driver based on carboxylated bacterial cellulose as claimed in claim 6, wherein: the drying temperature in the step 4) is 25-50 ℃, and the time is 2 hours.
8. The method for preparing ionic electroactive driver based on carboxylated bacterial cellulose as claimed in claim 7, wherein: the concentration of the sodium hydroxide is 0.5 mol/L.
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