CN112457531A - Flexible conductive composite film and preparation method thereof - Google Patents
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Abstract
The invention provides a flexible conductive composite film and a preparation method thereof, which are mainly formed by compounding bacterial cellulose, polypyrrole and a single-walled carbon nanotube material and belong to the field of electrochemistry. The BC/PPy/SWCNTs composite membrane is prepared by mainly adding BC nanofiber suspension into mixed liquor A mixed with hydrochloric acid and ferric chloride, adding PPy monomer after ultrasonic treatment, mixing to obtain BC/PPy composite slurry, adding single-walled carbon nanotubes and the like according to a certain volume ratio after dialysis by a dialysis bag, stirring, and performing suction filtration to form a membrane. The invention not only meets the requirements of flexible electronic equipment on elastic stretching and bending of materials, but also has the advantages of stable material structure, high conductivity, large capacitance value, simple and easy preparation method, and great application prospect and market value.
Description
The present application is a divisional application of the following applications: application No. 201810315070.4; application date 2018.04.10; the invention relates to a novel flexible conductive composite film and a preparation method thereof
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to a flexible conductive composite film and a preparation method thereof.
Background
Bacterial cellulose (hereinafter referred to as BC) is a porous reticular nano-scale biopolymer synthesized by microbial fermentation, and the interconnected superfine structure of the bacterial cellulose gives sufficient porosity and specific surface area to BC, so that the BC can be used as a base material for supporting other functional materials. BC a polysaccharide of formula (C) linked by beta-1, 4-glycosidic bonds6H10O5) And n, a large number of hydroxyl groups exist on the surface, and the BC has high hydrophilicity and water holding capacity due to abundant hydrogen bonds and three-dimensional structures. BC has high crystallinity (60-90%) and high degree of polymerization (2000-. The BC also has good biocompatibility. However, pure BC lacks conductivity, and conductivity can be imparted to BC by introducing carbon materials, conductive polymers, and the like, including conductive polymers, graphene and graphene oxide, carbon nanotubes, carbon nanofibers, and the like, into the BC matrix by in situ synthesis, doping, mixing, or coating. Although traditional conductive materials such as metal conductors (Cu, Ag and the like) have higher conductivity, the traditional conductive materials cannot meet the requirements of flexible electronic equipment on elastic stretching and bending of the materials and cannot meet the requirements of electrochemical devices such as fuel cells, ion batteries, flexible supercapacitors and the like on conductive electrode materials, so that the preparation of the flexible conductive materials is the development of timesThe trend of (c).
Since the 70's of the 20 th century, conductive polymers (ECPs) have attracted attention as flexible electrodes due to their excellent conductivity, controllable synthesis processes, and low density. Among ECPs, polypyrrole (hereinafter abbreviated as PPy) has characteristics of high conductivity, good stability, reversible redox property, simple and convenient synthesis, no toxicity, and the like, and has a very attractive application prospect in the fields of batteries, capacitors, electromagnetic shielding, photoelectric devices, biotechnology, and the like, and thus is regarded by researchers. In 2011, the conductive polymer composite material is prepared by in-situ oxidative polymerization of pyrrole (Py monomer) on a BC polymer matrix for the first time, and the conductivity of the conductive polymer composite material reaches 1S/cm. However, it also has a problem of low conductivity. In order to improve the conductivity of BC-PPy, an article congratulate on the basis of the traditional Chinese medicine, Xujie, is used for preparing a polypyrrole composite fabric electrode material of a super capacitor and researching the performance of the polypyrrole composite fabric electrode material, a bacterial cellulose membrane is used as a base material, the polypyrrole/bacterial cellulose composite electrode material is prepared through an in-situ oxidation polymerization method, the polypyrrole is uniformly attached to a BC membrane, and the composite electrode material has high conductivity (3.9S/cm). The paper WANG Fan, KIM H, PARK S, et al, Bendable and flexible superconductor substrate coated on polypyrole-coated bacterial cellulose-shell composite network [ J ] in Composites Science and Technology, Wang et al, applied pyrrole nanoparticles uniformly on the surface of a TOBC (TEMPO-oxidized bacterial cellulose) by means of in situ oxidative polymerization, to obtain a core-shell structured PPy-TOBC composite exhibiting high porosity and high electrical conductivity.
As the demand for energy increases, energy storage devices with higher energy densities are required to be manufactured, which require electrode materials with higher conductivity and capacitance values. However, the BC-PPy film still has problems of low conductivity and small capacitance value. Researchers have begun investigating BC-PPy in combination with another material to make conductive materials. In the article Li S, Huang D, Yang J, et al, free analysing bacterial cell-polypyrrole nanofibers sheets for advanced energy storage devices, Li et al prepared BC-PPy fibers by in situ oxidative polymerization followed by simple processThe single vacuum filtration method prepares the BC-PPy nano-fiber and the MWCNTs into a high-conductivity independent BC/PPy/MWCNTs conductive film. In the article Ma L, Liu R, Niu H, et al.free connecting reduced film based on polypyrole/basic cell/graphene paper for flexible superparameter, Ma and the like prepare BC/PPY/RGO (reduced graphene oxide) composite film by simple in-situ polymerization and filtration method, and obtain 13.5mg cm-2A high loading of 1mA · cm-23.66 F.cm-2And at 50mA · cm-22.59 F.cm-2High area capacitance. In the article Liu Y, Zhou J, Tang J, et al, three-Dimensional, chemical bound Polypyrrole/Bacterial cell/Graphene compositions for High-Performance supercapacitors, Liu et al reported that the highest conductivity (1320S/m) and the largest volume capacitance (278F/cm) of intercalated Graphene sheets and BC nanofibers have been reported3). PPy is coated on a chemically bonded BC/GO hybrid material, a definite 3D conductance path is constructed, and the negative influence of oxygen-containing groups on the surface of GO is eliminated. This PPy/BC/GO composite also exhibits high specific capacitance and significant recyclability (95.2% capacity retention for asymmetry after 5000 cycles), which was first reported on chemically bonded hybrid composites such as supercapacitor working electrodes. Article Peng S, Fan L, Wei C, et al.Flexible polypyrrole/chip refractory/bacterial cellulose composite membranes as supercapacitor electrodes; peng S, Fan L, Wei C, et al. polypyrole/nitrile resin/bacterial cellulose composite membranes for flexible superparameter electrodes and]peng et al prepared BC/PPy/CuS, BC/PPy/NiS and BC/PPy/CoS flexible supercapacitor electrode materials, and the addition of CuS, NiS and CoS increased the specific capacitance of BC-based electrode to 580 F.g.g.-1、713F·g-1、614F·g-1。
In order to solve the problems of low conductivity and small capacitance of the BC-PPy film and meet the requirements of flexible electronic equipment on elastic stretching and bending of materials, the electrode material with the advantages of simple and feasible preparation method, stable material structure, high conductivity and large capacitance is provided, and the electrode material is bound to become the best choice for meeting the requirements of current consumer markets on the electrode material.
Disclosure of Invention
The invention can improve the conductivity and electrochemical performance of the electrode material by utilizing the synergistic effect of the two materials, takes polypyrrole (PPy) and Bacterial Cellulose (BC) as main base materials, and prepares the electrode material with flexibility and high conductivity by cooperating with single-walled carbon nanotubes (SWCNTs), thereby not only meeting the requirements of flexible electronic equipment on elastic stretching and bending of the material, but also having stable material structure, high conductivity and large capacitance value, and the preparation method is simple and easy to implement.
The invention provides a flexible conductive composite film, which is formed by compounding bacterial cellulose BC, polypyrrole PPy and single-walled carbon nanotube SWCNTs materials, and the preparation of the conductive composite film comprises the following steps: the preparation method comprises the steps of preparing BC membrane into BC nanofiber suspension, mixing the BC nanofiber suspension with an oxidant and a dopant to obtain mixed liquor, adding a Py monomer into the mixed liquor, performing mixing reaction and dialysis to obtain a BC/PPy composite product, mixing a surfactant and a single-walled carbon nanotube, performing ultrasonic treatment to obtain single-walled carbon nanotube dispersion, adding the single-walled carbon nanotube dispersion into the BC/PPy composite product, and performing mixing and suction filtration to obtain the BC/PPy/SWCNTs composite membrane.
Preferably, the oxidant is one of hydrochloric acid or ammonium persulfate, and the dopant is one of Sodium Dodecyl Benzene Sulfonate (SDBS) or ferric chloride.
More preferably, the oxidizing agent is hydrochloric acid and the dopant is ferric chloride.
Another object of the present invention is to provide a method for preparing the conductive composite film, which specifically comprises:
(1) pulping and dispersing the BC membrane to prepare BC nano-fiber suspension;
(2) adding the BC nanofiber suspension into a mixed solution A mixed with hydrochloric acid and ferric chloride, carrying out ultrasonic treatment for 15-20min, stirring, and cooling to obtain a mixed solution B; the volume ratio of the BC nano-fiber suspension to the mixed liquor A is 1: 1-4;
(3) py monomer is mixed according to the volume ratio of 0.3-0.5: 100, adding the mixture into the mixed solution B, reacting for 30-300min at low temperature to obtain BC/PPy composite pulp, dialyzing the composite pulp by a dialysis bag to remove free Py monomers, and centrifuging to obtain a BC/PPy composite product;
(4) preparing a mixed solution C, wherein the mixed solution C comprises the following components: 0.04-0.07mg/mL of single-walled carbon nanotube, 2-5mg/mL of cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) and the balance of water, and respectively carrying out common ultrasonic treatment and cell crushing ultrasonic treatment on the mixed solution C to obtain a single-walled carbon nanotube dispersion solution; and adding the BC/PPy composite product into the single-walled carbon nanotube dispersion liquid according to the volume ratio of 2-4:5, stirring, carrying out suction filtration to form a membrane, and carrying out freeze drying to obtain the BC/PPy/SWCNTs composite membrane.
Preferably, in the step (1), the BC membrane is beaten for 5-10min, and then dispersed by a high-speed disperser at 7000-10000rpm for 10-15 min.
Preferably, in the step (1), the concentration of the BC nano fiber suspension is 1-3 mg/mL.
More preferably, in the step (1), the concentration of the BC nanofiber suspension is 1.5 mg/mL.
Preferably, in the step (2), the concentration of hydrochloric acid in the mixed solution is 1.0-3.0mol/L, and the concentration of ferric chloride is 8-12 mmol/L.
Preferably, in the step (2), the concentration of hydrochloric acid in the mixed solution is 2.0mol/L, and the concentration of ferric chloride in the mixed solution is 10 mmol/L.
Preferably, in the step (2), after stirring for 15-20min, cooling to 1-4 ℃.
Preferably, in the step (3), the low temperature condition is 1-10 ℃.
Preferably, in the step (3), the centrifugation treatment is 7000-10000rpm centrifugation for 15-20 min.
Preferably, in the step (3), the cut-off molecular weight of the dialysis bag is 8000-14000Da, the dialysis treatment time is 40-50h, and the water is changed every 6-12h to remove the unbound pyrrole.
Preferably, in the step (3), after centrifugation, the lower layer slurry is taken, wherein the volume ratio of the lower layer slurry to the supernatant liquid taken is controlled to be 2.5-3.5: 6.5-7.5.
Preferably, in the step (4), common ultrasound is performed by using an ultrasonic cleaning machine, and the ultrasound time is 20-40 min.
Preferably, in the step (4), cell crushing ultrasound is performed by using an ultrasonic cell crusher, and the ultrasound time is 20-40 min.
Preferably, in the step (4), the stirring time is 30-60min, and the membrane is formed by suction filtration through a vacuum filter.
Preferably, in the step (4), the freeze-drying time is 12-24 h.
Has the advantages that:
the single-walled carbon nanotube is formed by single-layer graphene curling, has a unique tubular structure and a perfect carbon-carbon covalent bond, and has good chemical stability and special optical performance. In addition, the single-walled carbon nanotube has good mechanical properties, can enhance the comprehensive properties of the composite material, the composite material doped with the carbon nanotube has good light stability and high strength, and the electrical conductivity of the composite material can be greatly improved by doping a small amount of carbon nanotubes.
The carbon nano tube is a seamless nano tube formed by winding single-layer or multi-layer graphite around a central shaft according to a certain helical angle, and each layer of the nano tube is a cylindrical surface consisting of hexagonal planes formed by passing through one carbon atom and hybridizing with the surrounding carbon atoms in a complete bonding way. The single-walled carbon nanotube is composed of a single-layer cylindrical graphite layer, has small diameter distribution range, few defects and higher uniformity. The diameter of the SWCNTs is generally 1-6 nm, the length can reach hundreds of nanometers to tens of micrometers, and the SWCNTs have extremely high length-diameter ratio. The invention utilizes the excellent conductivity of polypyrrole and single-walled carbon nanotubes to endow the bacterial cellulose membrane with conductivity. Wherein, the pyrrole monomer takes BC fiber as a substrate, and is oxidized on the surface of the BC fiber in a mixed solution of ferric chloride serving as an oxidant and hydrochloric acid serving as a dopantAnd (3) carrying out polymerization reaction to form BC/PPy fiber with a core-shell structure, wherein BC and PPy are combined in a hydrogen bond mode. However, the conductivity of the BC/PPy conductive film is low, the single-walled carbon nanotube is added to be embedded in the BC/PPy composite film or attached to the surface of the film to be combined with the BC/PPy film by Van der Waals force, and the conductivity of the BC/PPy conductive film is changed from 3.55 multiplied by 10 by the addition of the single-walled carbon nanotube-3The S/cm is increased to 6.42S/cm, 3 orders of magnitude are improved, the types of conductive materials are widened, and the thought is widened in the fields of electrode material application of energy storage equipment such as super capacitors and the like, development of functional textiles and the like.
The invention does not modify the single-walled carbon nanotube, does not damage the large pi bond of the single wall, and preserves the electrical property of the single-walled carbon nanotube. In the BC/PPy/SWCNTs composite membrane added with the single-walled carbon nano tube, the content of the single-walled carbon nano tube is 0.06mg/mL, and the mass load of the electrode material is 1-2mg cm-2(total weight of membrane electrode divided by geometric area of electrode) the conductivity can be made to 6.42S/cm. In the literature, the content of the single-walled carbon nanotube is 10-20mg in the BC/PPy/MWCNTs membrane added into the multi-walled carbon nanotube, and the mass load of the electrode needs to be 7-12mg cm-2The corresponding conductivity can only be reached. Therefore, the invention can achieve the same effect with a small amount of single-walled carbon nanotubes and electrode material loading.
Drawings
FIG. 1 is a photograph of the appearance of a film, wherein (a) is a photograph of a pure BC film, (b) is a photograph of a BC/PPy/SWCNTs film, and (c) is a photograph of a BC/PPy/SWCNTs film in a bent state;
FIG. 2 is a scanning electron microscope (hereinafter abbreviated as SEM) photograph of the membrane, wherein (a) is a SEM photograph of a pure BC membrane, (b) a BC/PPy membrane SEM photograph (arrow indicates polypyrrole), (c) a BC/PPy/SWCNTs membrane SEM photograph (arrow indicates single-walled carbon nanotube) at 9000 times, (d) a BC/PPy/SWCNTs membrane SEM photograph (arrow indicates single-walled carbon nanotube) at 2500 times;
FIG. 3 is a graph of the FTIR spectrum (hereinafter referred to as FTIR), wherein (1) is the FTIR spectrum of BC film, (2) is the FTIR spectrum of BC/PPy film, and (3) is the FTIR spectrum of BC/PPy/SWCNTs film.
Detailed Description
The invention is described below by means of specific embodiments. Unless otherwise specified, the technical means used in the present invention are well known to those skilled in the art. In addition, the embodiments should be considered illustrative, and not restrictive, of the scope of the invention, which is defined solely by the claims. It will be apparent to those skilled in the art that various changes or modifications in the components and amounts of the materials used in these embodiments can be made without departing from the spirit and scope of the invention.
Example 1 preparation of BC/PPy/SWCNTs composite Membrane
(1) Firstly, cutting a BC membrane into small cubes, pulping for 5min by using a soybean milk machine, and dispersing for 10min at 7000rpm by using a high-speed disperser to prepare a BC nano-fiber suspension with the concentration of 1 mg/mL;
(2) adding the BC nanofiber suspension into a mixed solution A mixed with hydrochloric acid and ferric chloride, carrying out ultrasonic treatment for 15min, stirring for 15min, and cooling to 1 ℃ to obtain a mixed solution B; the volume ratio of the BC nano-fiber suspension to the mixed liquor A is 1: 1;
wherein, in the mixed liquid A, the concentration of hydrochloric acid is 1.0mol/L, and the concentration of ferric chloride is 8 mmol/L.
(3) Mixing Py monomer according to a volume ratio of 0.3: 100, adding the mixture into the mixed solution B, reacting for 30min at the low temperature of 1-10 ℃ to obtain BC/PPy composite pulp, dialyzing the composite pulp by a dialysis bag with the molecular weight cutoff of 8000Da to remove free Py monomers, centrifuging at 7000rpm for 15min, and taking down the lower layer pulp to obtain a BC/PPy composite product;
wherein the dialysis treatment time is 40h, and the water is changed every 6h to remove unbound pyrrole.
After centrifugation, taking the lower-layer slurry, wherein the volume ratio of the taken lower-layer slurry to the taken supernatant is controlled to be 2.5: 6.5.
(4) preparing a mixed solution C, wherein the mixed solution C comprises the following components: 0.04mg/mL of single-walled carbon nanotube, 2mg/mL of cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) and the balance of water, and respectively carrying out common ultrasonic treatment on the mixed solution C for 20min and carrying out cell crushing ultrasonic treatment for 20min to obtain a single-walled carbon nanotube dispersion solution; mixing the BC/PPy composite product according to a volume ratio of 3:5, adding the mixture into the single-walled carbon nanotube dispersion liquid, stirring for 30-60min, performing suction filtration through a vacuum filter to form a membrane, and freeze-drying for 12h to obtain the BC/PPy/SWCNTs composite membrane.
Example 2 preparation of BC/PPy/SWCNTs composite Membrane
(1) Firstly, cutting a BC membrane into small cubes, pulping for 10min by using a soybean milk machine, and dispersing for 15min at 10000rpm by using a high-speed disperser to prepare a BC nano-fiber suspension with the concentration of 3 mg/mL;
(2) adding the BC nanofiber suspension into a mixed solution A mixed with hydrochloric acid and ferric chloride, carrying out ultrasonic treatment for 20min, stirring for 20min, and cooling to 4 ℃ to obtain a mixed solution B; the volume ratio of the BC nano-fiber suspension to the mixed liquor A is 1: 4;
wherein, in the mixed liquid A, the concentration of hydrochloric acid is 3.0mol/L, and the concentration of ferric chloride is 12 mmol/L.
(3) Mixing Py monomer according to a volume ratio of 0.5: 100, adding the mixture into the mixed solution B, reacting for 300min at the low temperature of 1-10 ℃ to obtain BC/PPy composite pulp, dialyzing the composite pulp by a dialysis bag with the molecular weight cutoff of 14000Da to remove free Py monomers, centrifuging at 10000rpm for 20min, and taking down the lower layer of pulp to obtain a BC/PPy composite product;
wherein the dialysis treatment time is 50h, and the water is changed every 12h to remove unbound pyrrole.
After centrifugation, taking the lower-layer slurry, wherein the volume ratio of the taken lower-layer slurry to the taken supernatant is controlled to be 3.5: 7.5.
(4) preparing a mixed solution C, wherein the mixed solution C comprises the following components: 0.07mg/mL of single-walled carbon nanotube, 5mg/mL of cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) and the balance of water, and respectively carrying out common ultrasonic treatment on the mixed solution C for 40min and carrying out cell crushing ultrasonic treatment for 40min to obtain a single-walled carbon nanotube dispersion solution; mixing the BC/PPy composite product according to a volume ratio of 4: and 5, adding the mixture into the single-walled carbon nanotube dispersion liquid, stirring for 60min, performing suction filtration through a vacuum filter to form a membrane, and performing freeze drying for 24h to obtain the BC/PPy/SWCNTs composite membrane.
Example 3 preparation of BC/PPy/SWCNTs composite Membrane
(1) Firstly, cutting a BC membrane into blocks, mechanically pulping for 7min, and dispersing for 12min at 8500rpm by a high-speed disperser to prepare a BC nanofiber suspension with the concentration of 2 mg/mL;
(2) adding the BC nanofiber suspension into a mixed solution A mixed with hydrochloric acid and ferric chloride, carrying out ultrasonic treatment for 16min, stirring for 16min, and cooling to 2.5 ℃ to obtain a mixed solution B; the volume ratio of the BC nano-fiber suspension to the mixed liquor A is 1: 1.5;
wherein, in the mixed liquid A, the concentration of hydrochloric acid is 2.0mol/L, and the concentration of ferric chloride is 10 mmol/L.
(3) Mixing Py monomer according to a volume ratio of 0.4: 100, adding the mixture into the mixed solution B, reacting for 180min at the low temperature of 4 ℃ to obtain BC/PPy composite slurry, dialyzing the composite slurry by a dialysis bag with the molecular weight cutoff of 10000Da to remove free Py monomers, carrying out centrifugal treatment, centrifuging for 15-20min at 7000-10000rpm, and taking down the slurry to obtain a BC/PPy composite product;
wherein the dialysis treatment time is 45h, and the water is changed every 8h to remove unbound pyrrole.
After centrifugation, taking the lower-layer slurry, wherein the volume ratio of the taken lower-layer slurry to the taken supernatant is controlled to be 3.0: 7.0.
(4) preparing a mixed solution C, wherein the mixed solution C comprises the following components: 0.055mg/mL of single-walled carbon nanotube, 4mg/mL of cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) and the balance of water, respectively carrying out common ultrasonic treatment on the mixed solution C for 25min, and carrying out cell crushing ultrasonic treatment for 25min to obtain a single-walled carbon nanotube dispersion solution; and adding the BC/PPy composite product into the single-walled carbon nanotube dispersion liquid according to the volume ratio of 3.5:5, stirring for 30min, carrying out suction filtration through a vacuum filter to form a membrane, and freeze-drying for 18h to obtain the BC/PPy/SWCNTs composite membrane.
Example 4 preparation of BC/PPy/SWCNTs composite Membrane
(1) Firstly, cutting the BC membrane into small cubes, pulping for 5min by using a soybean milk machine, and then dispersing for 10min at 10000r/min by using a high-speed dispersion machine to prepare 1.5mg/mL BC nano-fiber suspension.
(2) Subsequently, 50mLBC nanofiber suspension was weighed and added to 50mL of a mixed solution of hydrochloric acid (2.0M) and ferric chloride (10mM), sonicated for 15min, stirred for 15min and cooled to 4 ℃.
(3) Then 0.35mL of pyrrole monomer was added to the mixture and the reaction time was 30, 60, 120, 180, 300min at 4 ℃ to obtain BC/PPy composite slurry. The reacted slurry was centrifuged at 8000rpm for 20min, followed by dialysis treatment in 8000-. And carrying out suction filtration on the dialyzed BC/PPy pulp to obtain the BC/PPy composite membrane.
(4) Weighing 3mg of single-walled carbon nanotubes (SWCNTs) and 0.15g of cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB), adding into 50ml of water, performing common ultrasound for 30min by using an ultrasonic cleaner, and performing ultrasound for 30min by using an ultrasonic cell crusher to obtain the single-walled carbon nanotube dispersion liquid. And adding the BC/PPy slurry into the single-walled carbon nanotube dispersion liquid, stirring for 30min, and performing suction filtration to form a membrane by using a vacuum filter to obtain the BC/PPy/SWCNTs composite membrane.
Example 5 preparation of BC/PPy/SWCNTs composite Membrane
(1) Firstly, cutting a BC film into small cubes, pulping for 5min by using a beater, and dispersing for 10min at 8000rpm by using a high-speed disperser to prepare a BC nano-fiber suspension with the concentration of 1.5 mg/mL;
(2) adding the BC nano-fiber suspension into a mixed solution A mixed with ammonium persulfate and Sodium Dodecyl Benzene Sulfonate (SDBS), carrying out ultrasonic treatment for 15min, stirring for 15min, and cooling to 2 ℃ to obtain a mixed solution B; the volume ratio of the BC nano-fiber suspension to the mixed liquor A is 1: 2;
in the mixed solution A, the concentration of ammonium persulfate is 10mmol/L, and the concentration of sodium dodecyl benzene sulfonate is 2.0 mol/L.
(3) Mixing Py monomer according to a volume ratio of 0.3: 100, adding the mixture into the mixed solution B, reacting for 180min at the low temperature of 4 ℃ to obtain BC/PPy composite pulp, dialyzing the composite pulp by a dialysis bag with the molecular weight cutoff of 11000Da to remove free Py monomers, centrifuging at 8000rpm for 15min, and taking down the pulp to obtain a BC/PPy composite product;
wherein the dialysis treatment time is 40h, and the water is changed every 12h to remove unbound pyrrole.
After centrifugation, taking the lower-layer slurry, wherein the volume ratio of the taken lower-layer slurry to the taken supernatant is controlled to be 3.0: 7.0.
(4) preparing a mixed solution C, wherein the mixed solution C comprises the following components: respectively carrying out common ultrasonic treatment on the mixed solution C for 20min by an ultrasonic cleaner and then carrying out ultrasonic treatment for 25min by an ultrasonic cell crusher to obtain a single-walled carbon nanotube dispersion liquid, wherein the single-walled carbon nanotube dispersion liquid is 0.04mg/mL, the cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) is 3mg/mL, and the balance is water; and adding the BC/PPy composite product into the single-walled carbon nanotube dispersion liquid according to the volume ratio of 3:5, stirring for 30min, carrying out suction filtration through a vacuum filter to form a membrane, and freeze-drying for 12h to obtain the BC/PPy/SWCNTs composite membrane.
EXAMPLE 6 Performance testing of conductive films
The structure and the performance of the conductive film can be represented through appearance observation, a scanning electron microscope test, an external spectrum test and a conductivity test.
1. Photograph of conductive film
The experiment was divided into two groups, group 1 being pure BC membranes and group 2 being BC/PPy/SWCNTs membranes prepared from example 3.
Description of the parameters fig. 1, (a) group 1, (b) group 2, (c) group 2 in a bent state, illustrates: the pure BC membrane is white, after the polypyrrole and the single-walled carbon nanotube are compounded, the composite membrane is black, and the BC/PPy/SWCNTs membrane has certain flexibility.
2. Scanning electron microscope test
The experiment was divided into three groups, group 1 being pure BC membranes, group 2 being BC/PPy membranes prepared from steps 1-3 of example 3, and group 3 being BC/PPy/SWCNTs membranes prepared from example 3.
FIG. 2 shows (a) SEM pictures of group 1, (b) SEM pictures of group 2, (c) SEM pictures of group 3 at 9000 magnification, and (d) SEM pictures of group 3 at 2500 magnification.
(a) Description of the drawings: the pure BC membrane has smooth surface and a porous network structure. (b) The BC/PPy film is rough in surface, and a layer of PPy polymer is attached to the BC surface to form a core-shell structure. (c) The BC/PPy/SWCNTs membrane contains a small amount of single-walled carbon nanotubes which are attached or embedded in the BC/PPy membrane, so that a stable BC/PPy/SWCNTs composite membrane structure is formed.
3. Fourier Infrared Spectroscopy testing
The experiment was divided into three groups, group 1 being pure BC membranes, group 2 being BC/PPy membranes prepared from steps 1-3 of example 3, and group 3 being BC/PPy/SWCNTs membranes prepared from example 3.
FIG. 3 (1) set 1FTIR spectra, (2) set 2FTIR spectra, (3) set 3FTIR spectra.
Can be seen from the infrared spectrogram at 3350-1And 2900cm-1The position corresponds to an O-H stretching vibration peak and a C-H asymmetric stretching vibration peak of BC. At 1541cm-1，1455cm-1，1290cm-1，1030cm-1，876cm-1And 664cm-1The peaks at the position (A) respectively correspond to C-C and C-N aromatic amine stretching peaks in BC/PPy, namely C-H bending peaks, N-H swinging peaks, polypyrrole surface ring outer C-H peaks, and C-C peaks on polypyrrole aromatic rings, which verifies the existence of PPy in the composite membrane. At 1516cm-1A special peak appears, which is an additional peak of SWCNTs, and the existence of the single-wall carbon nano tube is verified.
4. Conductivity test
The experiment was divided into 3 groups, group 1 being pure BC membranes;
group 2 was a BC/PPy membrane, which was divided into 5 groups and prepared by the preparation methods of steps 1 to 3 of example 4, and in step (3), the BC/PPy composite reaction times were set to 30, 60, 120, 180, and 300min, respectively.
TABLE 1 conductivity test
Note: PAni: polyaniline, MWCNTs: multiwalled carbon nanotube
The composite films of BC/PAni/SWCNs according to table 1 are conductive films from Jasim a preparation, and it can be seen that the conductivity is significantly lower than the composite films prepared according to the present invention. The sources of the literature are: jasim A, Ullah M W, Shi Z, et al.A.preparation of bacterial cell/polyaniline/single-walled carbon nanotubes for potential application as biosensors [ J ]. Carbohydrate Polymers,2017,163:62-69.)
Claims (10)
1. A preparation method of a conductive composite film is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) firstly, pulping and dispersing a BC membrane to prepare a BC nanofiber suspension;
(2) adding the BC nanofiber suspension into a mixed solution A mixed with hydrochloric acid and ferric chloride, performing ultrasonic treatment, stirring, and cooling to obtain a mixed solution B; the volume ratio of the BC nano-fiber suspension to the mixed liquor A is 1: 1-4;
(3) py monomer is mixed according to the volume ratio of 0.3-0.5: 100, adding the mixture into the mixed solution B, reacting at low temperature to obtain BC/PPy composite pulp, dialyzing the composite pulp by a dialysis bag to remove free Py monomers, centrifuging, and taking the lower layer pulp to obtain a BC/PPy composite product;
(4) preparing a mixed solution C, wherein the mixed solution C comprises the following components: 0.04-0.07mg/mL of single-walled carbon nanotube, 2-5mg/mL of cationic surfactant cetyl trimethyl ammonium bromide and the balance of water, and respectively carrying out common ultrasonic treatment and cell crushing ultrasonic treatment on the mixed solution C to obtain a single-walled carbon nanotube dispersion solution; and adding the BC/PPy composite product into the single-walled carbon nanotube dispersion liquid according to the volume ratio of 2-4:5, stirring, carrying out suction filtration to form a membrane, and carrying out freeze drying to obtain the BC/PPy/SWCNTs composite membrane.
2. A method of preparing a conductive composite film according to claim 1, wherein:
in the step (1), the BC membrane is pulped for 5-10min, and then is dispersed for 10-15min at 7000-10000rpm through a high-speed dispersing machine.
3. A method of preparing a conductive composite film according to claim 1, wherein: in the step (1), the concentration of the BC nano-fiber suspension is 1-3 mg/mL.
4. A method of preparing a conductive composite film according to claim 1, wherein: in the step (2), the concentration of hydrochloric acid in the mixed solution A is 1.0-3.0mol/L, and the concentration of ferric chloride in the mixed solution A is 8-12 mmol/L.
5. A method of preparing a conductive composite film according to claim 1, wherein: in the step (2), after stirring for 15-20min, cooling to 1-4 ℃; the ultrasonic treatment time is 15-20 min.
6. A method of preparing a conductive composite film according to claim 1, wherein: in the step (3), the centrifugation is 7000-10000rpm for 15-20 min.
7. A method of preparing a conductive composite film according to claim 1, wherein: in the step (3), the reaction time is 30-300 min.
8. A method of preparing a conductive composite film according to claim 1, wherein: in the step (3), the cut-off molecular weight of the dialysis bag is 8000-14000Da, the dialysis treatment time is 40-50h, and water is changed every 6-12h to remove the unbound pyrrole.
9. A method of preparing a conductive composite film according to claim 1, wherein: in the step (4), the ultrasonic time of the common ultrasonic and ultrasonic cell disruptor is 20-40 min.
10. A conductive composite film prepared by the method of any one of claims 1 to 9.
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