CN115832333A - Fibroin/silver nanowire/polypyrrole film with energy storage and biodegradability, preparation method and application thereof - Google Patents
Fibroin/silver nanowire/polypyrrole film with energy storage and biodegradability, preparation method and application thereof Download PDFInfo
- Publication number
- CN115832333A CN115832333A CN202211382520.4A CN202211382520A CN115832333A CN 115832333 A CN115832333 A CN 115832333A CN 202211382520 A CN202211382520 A CN 202211382520A CN 115832333 A CN115832333 A CN 115832333A
- Authority
- CN
- China
- Prior art keywords
- fibroin
- agnw
- energy storage
- biodegradability
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 58
- 108010022355 Fibroins Proteins 0.000 title claims abstract description 38
- 239000002042 Silver nanowire Substances 0.000 title claims abstract description 27
- 238000004146 energy storage Methods 0.000 title claims abstract description 26
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 5
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims description 37
- 239000012528 membrane Substances 0.000 claims description 27
- 239000011521 glass Substances 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims 5
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 238000006722 reduction reaction Methods 0.000 abstract description 4
- 231100001231 less toxic Toxicity 0.000 abstract description 2
- 239000007777 multifunctional material Substances 0.000 abstract description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- 239000004020 conductor Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 108090000669 Annexin A4 Proteins 0.000 description 2
- 102100034612 Annexin A4 Human genes 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000005660 hydrophilic surface Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 102100034613 Annexin A2 Human genes 0.000 description 1
- 108090000668 Annexin A2 Proteins 0.000 description 1
- 206010061818 Disease progression Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 108010059712 Pronase Proteins 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- BQRGNLJZBFXNCZ-UHFFFAOYSA-N calcein am Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(CN(CC(=O)OCOC(C)=O)CC(=O)OCOC(C)=O)=C(OC(C)=O)C=C1OC1=C2C=C(CN(CC(=O)OCOC(C)=O)CC(=O)OCOC(=O)C)C(OC(C)=O)=C1 BQRGNLJZBFXNCZ-UHFFFAOYSA-N 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 230000004663 cell proliferation Effects 0.000 description 1
- 230000003833 cell viability Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 208000037976 chronic inflammation Diseases 0.000 description 1
- 230000006020 chronic inflammation Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005750 disease progression Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- XJMOSONTPMZWPB-UHFFFAOYSA-M propidium iodide Chemical compound [I-].[I-].C12=CC(N)=CC=C2C2=CC=C(N)C=C2[N+](CCC[N+](C)(CC)CC)=C1C1=CC=CC=C1 XJMOSONTPMZWPB-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000029663 wound healing Effects 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A fibroin/silver nanowire/polypyrrole film with energy storage and biodegradability, a preparation method and application thereof belong to the technical field of multifunctional material preparation. According to the invention, agNWs network is embedded into a silk protein film, and polypyrrole is chemically deposited on the silk protein film to prepare a partially biodegradable air cathode material which has electrocatalytic activity on oxygen reduction reaction; coverage of polypyrrole on SF/AgNW also improves biocompatibility and is less toxic. The electrode prepared by the invention has good degradation performance and good energy storage effect, has good potential and application feasibility for developing degradable energy storage equipment, and provides a feasible way for constructing an implanted electrode with high energy storage capacity.
Description
Technical Field
The invention belongs to the technical field of multifunctional material preparation, and particularly relates to a fibroin/silver nanowire/polypyrrole film with energy storage and biodegradability, a preparation method, a flexible electrode prepared based on the film, and a degradable magnesium-air battery prepared from the flexible electrode. The electrode prepared by the invention has good degradation performance and good energy storage effect, and has good potential and application feasibility for developing degradable energy storage equipment.
Background
Biodegradable implantable medical bionics has gained more attention from biomedicine to microelectromechanical systems. These devices can be gradually eliminated after use as needed, eliminating the potential for secondary surgery and the chronic inflammation associated with permanent implants. These biodegradable electronic devices can satisfy a variety of medical applications: such as wound healing monitoring, disease progression tracking, drug release, and cardiovascular stimulators.
Energy harvesting devices that generate electricity from biomechanical motion, biofuels and salinity gradients provide a new biodegradable energy source, but still present a number of challenges due to low and erratic energy output. Therefore, these techniques need to be integrated with the energy storage device to compensate for its intermittency. A biocompatible and biodegradable power source is a desirable choice to drive these biodegradable electronic devices. Implanted magnesium air bio-cells offer a viable solution because of their benign bio-function and availability of high energy density. They may rely on oxygen contained in the body fluid to generate a voltage between the anode and the cathode. Cathode materials as catalysts for Oxygen Reduction Reaction (ORR), a key challenge in achieving high performance biodegradable magnesium-air biocells is the development of air cathode materials with desirable electrochemical and biodegradable properties.
Silver (Ag) is considered to be non-toxic as a bio-inert noble metal, and is used as an electrode for bioelectronic devices. Implantable Ag electrodes are widely used as biosensing materials for continuous glucose monitoring and determination of zinc ions in cell culture solutions. Silver nanomaterials have the further benefit that they are broad spectrum antimicrobials and are widely used in wound care products. Silver nanowire (AgNWs) networks can form a reliable, stretchable, transparent conductive layer that can be embedded in various polymers. AgNWs are induced into a biocompatible matrix, so that the in vitro and in vivo toxicity of silver is greatly reduced.
Disclosure of Invention
The invention aims to provide a fibroin/silver nanowire/polypyrrole film with energy storage and biodegradability, a preparation method, a flexible electrode based on the film and a degradable magnesium-air battery prepared from the flexible electrode.
In the present invention, a biocompatible conductor is prepared by embedding an AgNWs network into a fibroin film (SF) to construct an air cathode. Silk is a natural biodegradable protein fiber, and fibroin films have been used as biomatrix in the manufacture of bio-integrated electronic devices, implantable therapeutic devices, and transient electronic devices. By chemical deposition of polypyrrole (PPy) on fibroin films, partially biodegradable air cathode materials can be prepared, with electrocatalytic activity towards Oxygen Reduction Reaction (ORR). The advantage of electrochemical polymerization over chemical oxidation is that clean conductive polymers with controlled thickness and surface roughness are produced by controlling the amount of charge consumed and/or the electrochemical technique used. For this purpose, PPy was electrochemically deposited on AgNW networks embedded in fibroin films. The coverage of PPy on SF/AgNW can improve biocompatibility and is less toxic than previously reported silk-AgNW composites. The electrode prepared by the invention has good degradation performance and good energy storage effect, has good potential and application feasibility for developing degradable energy storage equipment, and provides a feasible way for constructing an implanted electrode with high energy storage capacity.
The invention relates to a preparation method of a fibroin/silver nanowire/polypyrrole film with energy storage and biodegradability, which comprises the following steps:
(1) Ultrasonically cleaning a glass slide by deionized water, acetone and isopropanol for 3-8 minutes respectively, and then treating by ultraviolet ozone (PSD Pro series) for 25-35 minutes;
(2) Dispersing the silver nanowires (AgNWs) in isopropanol (0.2-0.3 mg mL) -1 ) Spin-coating the glass slide obtained in the step (1) to prepare an AgNW coating, then drying the glass slide with the AgNW coating at room temperature, and annealing at 145-155 ℃ for 25-35 minutes to reduce the surface resistance of the coating, wherein the thickness of the obtained AgNW coating is 15-30 microns;
(3) Mixing fibroin aqueous solution (0.5-1.2 mg mL) -1 ) Dropped on a glass slide with AgNW coating (0.3-0.8 mL cm) -2 ) And air-drying at room temperature; after water in the fibroin solution is evaporated, the AgNW is embedded into a fibroin film, and the thickness of the fibroin film is 50-60 mu m;
(4) Treating the glass slide obtained in the step (3) with 99% methanol by volume for 1.5-2.5 hours to induce and form a silk II (beta-sheet) structure; the SF/AgNW composite membrane was again treated with oxygen plasma for 8-15 minutes to create a hydrophilic surface, and then treated at 0 deg.C with 0.5mA cm from acetonitrile solution containing 0.05-0.2M pyrrole and 0.05-0.2M pTSA (dopant) -2 The PPy is electrodeposited on an SF/AgNW composite membrane to obtain an SF/AgNW/PPy composite membrane, the SF/AgNW/PPy composite membrane is washed by deionized water to remove loosely combined PPy particles or other residues, and finally the PPy/AgNW/PPy composite membrane is dried in vacuum at 50-60 ℃ for 20-30 hours, so that the fibroin/silver nanowire/polypyrrole membrane (SF/AgNW/PPy) with energy storage and biodegradability is obtained. A PPy film was synthesized on stainless steel mesh (instead of SF/AgNW composite film) using the same conditions as a control.
Preparation of a degradable magnesium-air battery: the cell was fabricated using magnesium alloy (AZ 31) as an anode (10 mm × 10 mm) and the SF/AgNW/PPy composite membrane prepared according to the present invention as a cathode (10 mm × 10 mm) in a single cell with 20 ml of PBS electrolyte and tested using a cell testing apparatus (fresh Electronic Co). It is electrostatically discharged to a cutoff cell voltage of 1.0V at room temperature.
Drawings
FIG. 1: growth timing curve for PPy;
FIG. 2: scanning electron microscope images (a and b) of different magnifications of the SF/AgNW composite membrane and (c and d) of different magnifications of the conductive surface of the SF/AgNW/PPy composite membrane;
FIG. 3: fourier transform infrared spectra of a fibroin film (Silk film), a methanol-treated SF/AgNW composite film, a SF/AgNW/PPy composite film, and a PPy film.
FIG. 4 is a schematic view of: SF/AgNW/composite film and SF/AgNW/Ppy composite film in N 2 Cyclic voltammogram in saturated PBS solution, scan rate 20mV s -1 ；
FIG. 5: electrochemical impedance spectroscopy of SF/AgNW composite membranes in PBS solution.
FIG. 6: electrochemical impedance spectrum of SF/AgNW/PPy composite membrane in PBS solution.
FIG. 7: the electrostatic discharge curves of the Mg-air bio-cell consisting of SF/AgNW/Ppy composite membrane at different current densities (inset: discharge curve of Mg-air cell using Stainless Steel Mesh Cathode) as control).
FIG. 8: cell compatibility photographs of a Silk protein film (Silk film), an SF/AgNW composite film and an SF/AgNW/Ppy composite film;
FIG. 9: at 1.0mg mL -1 Degradation mass change curve of fibroin film and SF/AgNW/PPy composite film cultured in protease solution.
Figure 1 shows that there is initially a spike due to charging of the double layer and oxidation of the monomer, followed by a slow drop in potential as polymer growth progresses, with the open circuit voltage approaching a stable potential of 0.76V (open circuit voltage of the cell on the ordinate);
fig. 2 shows that AgNWs are randomly distributed on the SF surface and buried inside the matrix, forming an interconnected AgNW network (fig. 2 a). The nanowires have an average diameter of 50-60 nm and a length of 10-20 μm (FIG. 2 b). After electrochemical polymerization of the pyrrole, the AgNW network became thicker and denser (fig. 2 c). The PPy nanoparticles not only wrapped around the AgNW, but also filled the open spaces between the AgNW networks (fig. 2 d).
FIG. 3 shows a fibroin film at 1650cm -1 And 1540cm -1 Shows a prominent peak, which is characteristic of the silk protein I conformation (random coil and alpha-helix). The methanol-treated SF/AgNW composite showed a typical silk protein II structure at 1620cm -1 And 1525cm -1 There is a strong peak. The SF/AgNW/PPy composite membrane shows the characteristic wide absorption of PPy, comprising-1288 cm -1 Various stretching modes of (C-N), and about 1152 and 1016cm -1 Different C-H bending modes. The SF/AgNW/PPy composite membrane clearly shows a typical band for PPy and silk protein II conformations.
FIG. 4 evaluation of the electrochemical properties of SF/AgNW and SF/AgNW/PPy composite membranes using Cyclic Voltammetry (CV), which was performed at 20mV s in a PBS solution saturated with nitrogen -1 Is performed at the scanning rate of (1). The figure shows that this film exhibits well-defined redox peaks centered at-0.23V and 0.22V, which can be attributed to the formation and reduction of silver chloride (0.14M Cl in PBS) - )。
The SF/AgNW conductor shown in fig. 5 has a lower intersection with the X-axis at high frequencies, showing a smaller uncompensated bulk resistance. Furthermore, the half circle of the SF/AgNW conductor was observed to be small, indicating that its charge transfer resistance was small. Both electrodes showed good fitting results. The RS and Rct of the SF/AgNW conductor were 12.4 Ω and 14.4 Ω, respectively.
Fig. 6 shows that the bulk resistance and the charge transfer resistance of the SF/AgNW/PPy composite film were about 36.7 Ω and 96.2 Ω, respectively.
FIG. 7 is a graph to demonstrate that the PPy cathode in the battery system can be used as O 2 Reduced catalyst, a blank stainless steel mesh was used as a control. During discharge, the cell voltage dropped sharply to around 1.0V, which is 10 μ A cm in comparison with the cell with a PPy cathode -2 The high voltage of 1.35V provided at the same discharge current is in sharp contrast.
FIG. 8 Co-staining with calcein-AM and propidium iodide shows that these samples have high cell viability within seven days, hADSCs diffuse well, showing a regular spindle shape. It showed good cell proliferation during the seven day culture.
FIG. 9 to evaluate biodegradation, SF/AgNW/PPy composite membrane and fibroin membrane (SF) were exposed to protease XIV solution (1 mg/ml) as controls. All samples degraded in the enzyme solution, as can be seen from the sustained weight loss. Specifically, the weight loss of the SF/AgNW/Ppy composite film was 13%, which was lower than the weight loss (21%) of the fibroin film (SF) in the first 24 hours.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the content of the present invention is not limited to the following examples, and should not be construed as limiting the scope of the present invention.
Example 1: preparation method of film with energy storage and biodegradation properties
(1) Ultrasonically cleaning a glass slide by using deionized water, acetone and isopropanol for 5 minutes respectively, and then treating the glass slide by using ultraviolet ozone (PSD Pro series) for 30 minutes;
(2) An isopropanol dispersion (0.25 mg mL) of silver nanowires (AgNWs) -1 ) Spin-coating the glass slide obtained in the step (1) to prepare an AgNW coating, then drying the glass slide with the AgNW coating at room temperature, and annealing at 150 ℃ for 30 minutes to reduce the surface resistance of the coating; the thickness of the obtained AgNW coating was 25 μm;
(3) Mixing fibroin aqueous solution (0.8 mg mL) -1 ) Drop on glass slide with AgNW coating (0.5 mL cm) -2 ) And air-drying at room temperature; after water in the fibroin solution was evaporated, agnws were embedded in a fibroin film with a thickness of 55 μm;
(4) Sputtering a film with the thickness of 20nm on the AgNW coating to improve the electrochemical stability of the AgNW, and drying to obtain an SF/AgNW composite film on the surface of a glass slide;
(5) Treating the glass slide obtained in the step (4) with 99% methanol by volume for 2 hours to induce the formation of a silk II (beta-sheet) structure; the SF/AgNW composite membrane was again treated with oxygen plasma for 10 minutes to produce a hydrophilic surface, and then from an acetonitrile solution containing 0.1M pyrrole and 0.1M pTSA (dopant) at 0 ℃ at 0.5mA cm -2 The PPy is electrodeposited on the SF/AgNW composite membrane to obtain SF/AgNAnd cleaning the W/PPy composite membrane by using deionized water to remove loosely combined PPy particles or other residues, and finally performing vacuum drying at 55 ℃ for 25 hours to obtain the fibroin/silver nanowire/polypyrrole film (SF/AgNW/PPy) with energy storage and biodegradability. A PPy membrane was synthesized on a stainless steel mesh (instead of the SF/AgNW composite membrane) using the same conditions as a control.
Example 2: preparation of a degradable magnesium-air battery:
the degradable magnesium-air cell was fabricated with a magnesium alloy (AZ 31) anode (10 mm × 10 mm) and a SF/AgNW/PPy composite membrane cathode (10 mm × 10 mm) in a single cell with 20 ml of PBS electrolyte and tested using a cell testing apparatus (Neware Electronic Co). It is electrostatically discharged to a cut-off cell voltage of 1.0V at room temperature.
Claims (7)
1. A preparation method of a silk protein/silver nanowire/polypyrrole film with energy storage and biodegradability comprises the following steps:
(1) Ultrasonically cleaning a glass slide by using deionized water, acetone and isopropanol for 3-8 minutes respectively, and then treating the glass slide by using ultraviolet ozone for 25-35 minutes;
(2) Spin-coating an isopropanol dispersion solution of silver nanowires AgNWs on the glass slide obtained in the step (1) to prepare an AgNW coating, then drying the glass slide with the AgNW coating at room temperature, and annealing at 145-155 ℃ for 25-35 minutes to reduce the surface resistance of the coating, wherein the thickness of the obtained AgNW coating is 15-30 microns;
(3) Dropping the fibroin aqueous solution on a glass slide with an AgNW coating, and airing at room temperature; after water in the fibroin solution is evaporated, the AgNW is embedded into a fibroin film, and the thickness of the fibroin film is 50-60 mu m;
(4) Treating the glass slide obtained in the step (3) with 99% by volume of methanol for 1.5 to 2.5 hours, treating the SF/AgNW/Au composite membrane with oxygen plasma for 8 to 15 minutes, and then treating the treated glass slide with 0.5mA cm of 0.2M PPy and 0.05 to 0.2M pTSA in acetonitrile solution at 0 DEG C -2 Current density ofAnd electrodepositing the PPy on an SF/AgNW/Au composite membrane to obtain an SF/AgNW/Au/PPy composite membrane, washing with deionized water to remove loosely combined PPy particles or other residues, and finally, drying in vacuum at 50-60 ℃ for 20-30 hours to obtain the fibroin/silver nanowire/gold/polypyrrole film with energy storage and biodegradability.
2. The method for preparing the fibroin/silver nanowire/polypyrrole film with energy storage and biodegradability according to claim 1, wherein the steps of: in the isopropanol dispersion liquid of the silver nanowires in the step (2), the concentration of the silver nanowires is 0.2-0.3 mg mL -1 。
3. The method for preparing the fibroin/silver nanowire/polypyrrole film with energy storage and biodegradability according to claim 1, wherein the steps of: in the step (3), the concentration of the fibroin in the fibroin aqueous solution is 0.5-1.2 mg mL -1 The dosage of the fibroin aqueous solution dropped on the glass slide glass with the AgNW coating is 0.3-0.8 mL cm -2 。
4. A fibroin/silver nanowire/polypyrrole film with energy storage and biodegradability is characterized in that: is prepared by the process of any one of claims 1 to 3.
5. The use of the fibroin/silver nanowire/polypyrrole film with energy storage and biodegradability of claim 4 in the preparation of flexible electrodes.
6. The use of the fibroin/silver nanowire/polypyrrole film with energy storage and biodegradability of claim 4 in the preparation of degradable magnesium-air battery.
7. The application of the fibroin/silver nanowire/polypyrrole film with energy storage and biodegradability in the preparation of the degradable magnesium-air battery according to claim 6, wherein: the cell was fabricated in a single-compartment cell with PBS electrolyte using magnesium alloy as the anode and SF/AgNW/Au/PPy composite membrane as the cathode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211382520.4A CN115832333A (en) | 2022-11-07 | 2022-11-07 | Fibroin/silver nanowire/polypyrrole film with energy storage and biodegradability, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211382520.4A CN115832333A (en) | 2022-11-07 | 2022-11-07 | Fibroin/silver nanowire/polypyrrole film with energy storage and biodegradability, preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115832333A true CN115832333A (en) | 2023-03-21 |
Family
ID=85526813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211382520.4A Pending CN115832333A (en) | 2022-11-07 | 2022-11-07 | Fibroin/silver nanowire/polypyrrole film with energy storage and biodegradability, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115832333A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103762014A (en) * | 2013-12-24 | 2014-04-30 | 苏州大学 | Flexible and transparent electrode film based on silk fibroin and manufacturing method and application thereof |
| CN104328473A (en) * | 2014-10-09 | 2015-02-04 | 东华大学 | Method for preparation of polypyrrole surface modified polymer conductive material by electrochemical deposition technology |
| CN110891619A (en) * | 2017-07-12 | 2020-03-17 | 贡比涅技术大学 | Fibroin-containing fibrous polymeric materials and polymeric scaffolds comprising the same |
| CN111029162A (en) * | 2019-12-30 | 2020-04-17 | 中国科学院合肥物质科学研究院 | Graphene/polypyrrole composite electrode material, preparation and application thereof in super capacitor |
| CN111939318A (en) * | 2020-08-23 | 2020-11-17 | 苏州宣医智慧医疗科技有限公司 | Preparation method of reduced graphene oxide silk fibroin composite membrane |
-
2022
- 2022-11-07 CN CN202211382520.4A patent/CN115832333A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103762014A (en) * | 2013-12-24 | 2014-04-30 | 苏州大学 | Flexible and transparent electrode film based on silk fibroin and manufacturing method and application thereof |
| CN104328473A (en) * | 2014-10-09 | 2015-02-04 | 东华大学 | Method for preparation of polypyrrole surface modified polymer conductive material by electrochemical deposition technology |
| CN110891619A (en) * | 2017-07-12 | 2020-03-17 | 贡比涅技术大学 | Fibroin-containing fibrous polymeric materials and polymeric scaffolds comprising the same |
| CN111029162A (en) * | 2019-12-30 | 2020-04-17 | 中国科学院合肥物质科学研究院 | Graphene/polypyrrole composite electrode material, preparation and application thereof in super capacitor |
| CN111939318A (en) * | 2020-08-23 | 2020-11-17 | 苏州宣医智慧医疗科技有限公司 | Preparation method of reduced graphene oxide silk fibroin composite membrane |
Non-Patent Citations (1)
| Title |
|---|
| XIAOTENG JIA等: ""Toward Biodegradable Mg–Air Bioelectric Batteries Composed of Silk Fibroin–Polypyrrole Film"", 《ADVANCED FUNCTIONAL MATERIALS》, vol. 26, no. 9, 27 February 2016 (2016-02-27), pages 1454 - 1462, XP072410000, DOI: 10.1002/adfm.201503498 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sim et al. | Biomolecule based fiber supercapacitor for implantable device | |
| Lee et al. | Facile fabrication of a fully biodegradable and stretchable serpentine-shaped wire supercapacitor | |
| Wang et al. | Enhanced cell proliferation by electrical stimulation based on electroactive regenerated bacterial cellulose hydrogels | |
| An et al. | A wearable second skin‐like multifunctional supercapacitor with vertical gold nanowires and electrochromic polyaniline | |
| Jiang et al. | Three-dimensional printing and injectable conductive hydrogels for tissue engineering application | |
| Xie et al. | Electroresponsive and cell-affinitive polydopamine/polypyrrole composite microcapsules with a dual-function of on-demand drug delivery and cell stimulation for electrical therapy | |
| Peng et al. | Multi-functional electrospun nanofibres for advances in tissue regeneration, energy conversion & storage, and water treatment | |
| El Ichi et al. | Bioelectrodes modified with chitosan for long-term energy supply from the body | |
| Li et al. | One-step synthesis of graphene/polypyrrole nanofiber composites as cathode material for a biocompatible zinc/polymer battery | |
| Ismail et al. | Sensing characteristics of a conducting polymer/hydrogel hybrid microfiber artificial muscle | |
| JP4451929B2 (en) | Neural stimulation using electrically conductive polymers | |
| Zhou et al. | Humidity-sensitive, shape-controllable, and transient zinc-ion batteries based on plasticizing gelatin-silk protein electrolytes | |
| Du et al. | Design of high conductive and piezoelectric poly (3, 4-ethylenedioxythiophene)/chitosan nanofibers for enhancing cellular electrical stimulation | |
| Martin | Molecular design, synthesis, and characterization of conjugated polymers for interfacing electronic biomedical devices with living tissue | |
| Chae et al. | Electrode materials for biomedical patchable and implantable energy storage devices | |
| Hosseini et al. | Challenge between sequence presences of conductive additives on flexibility, dielectric and supercapacitance behaviors of nanofibrillated template of bacterial cellulose aerogels | |
| Green et al. | Novel neural interface for implant electrodes: improving electroactivity of polypyrrole through MWNT incorporation | |
| WO2008000045A1 (en) | Nanostructured composites | |
| Yan et al. | Electrochemical synthesis of chitosan/silver nanoparticles multilayer hydrogel coating with pH-dependent controlled release capability and antibacterial property | |
| Yang et al. | Conductive polymer hydrogels crosslinked by electrostatic interaction with PEDOT: PSS dopant for bioelectronics application | |
| Xiao et al. | Incorporation of collagen in poly (3, 4‐ethylenedioxythiophene) for a bifunctional film with high bio‐and electrochemical activity | |
| CN110896607B (en) | Surface super-capacitance modified material and preparation method and application thereof | |
| Larson et al. | Enhanced actuation performance of silk-polypyrrole composites | |
| Fan et al. | Modified PEDOT by benign preparing N-doped reduced graphene oxide as potential bio-electrode coating material | |
| Sharma et al. | Conducting polymer hydrogels and their applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |