CN115182192A - Silver-based conductive paper and preparation method and application thereof - Google Patents

Silver-based conductive paper and preparation method and application thereof Download PDF

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Publication number
CN115182192A
CN115182192A CN202210825954.0A CN202210825954A CN115182192A CN 115182192 A CN115182192 A CN 115182192A CN 202210825954 A CN202210825954 A CN 202210825954A CN 115182192 A CN115182192 A CN 115182192A
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silver
filter paper
paper
based conductive
conductive paper
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CN115182192B (en
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张素风
刘亚丽
李楠
李磊
朱新月
邓婷婷
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/02—Chemical or biochemical treatment
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/04—Physical treatment, e.g. heating, irradiating
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/08—Filter paper

Abstract

The invention discloses silver-based conductive paper and a preparation method and application thereof, wherein the preparation method comprises the following steps: placing the filter paper in acid NaIO 4 In the solution, after the constant-temperature light-resistant reaction is finished, drying to obtain aldehyde-based filter paper; placing the aldehyde-group filter paper in a PEI solution, and drying after the constant-temperature reaction is finished to obtain aminated filter paper; placing the aminated filter paper in AgNO 3 In the solution, after the room temperature reaction is finished, drying to obtain filter paper loaded with silver ions; and adding a reducing agent to the filter paper loaded with silver ions, controlling the adding rate and the adding time of the reducing agent, and obtaining the silver-based conductive paper loaded with the fractal structure silver particles after the reaction is finished. Silver obtained by the methodThe base conductive paper has good conductivity, mechanical property and thermal stability.

Description

Silver-based conductive paper and preparation method and application thereof
Technical Field
The invention belongs to the field of biological high polymer materials, and relates to silver-based conductive paper, and a preparation method and application thereof.
Background
With the rapid development of science and technology, the conventional electronic products gradually fail to meet the needs of people in daily life. Flexible electronic products are currently receiving attention due to their excellent flexibility, conductivity and portability, and have been widely used in the fields of flexible sensors, supercapacitors, solar cells, flexible electrodes, and the like. However, the environment-friendly flexible electronic device is prepared by the petrochemical-based polymer plastic, and the plastic substrate has the defects of high price, large thermal expansion coefficient, no high temperature resistance, no regeneration, difficult biodegradation and the like.
The Filter Paper (FP) has the reproducibility and mechanical flexibility of the cellulose component, and the unique three-dimensional network structure of the filter paper enables the filter paper to have excellent self-supporting performance and larger specific surface area. On the basis, a series of bionic composite materials are constructed by taking the filter paper and derivative materials thereof as structural templates, wherein the filter paper carrier-silver nanoparticle composite material is mainly applied to the fields of antibacterial medical materials, catalysis and the like. In the technology, the filter paper is dissolved and broken up, and silver nanoparticles are mixed to obtain the antibacterial material or catalytic material with good silver loading capacity, but the mechanical property of the whole material is reduced due to the structure.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the silver-based conductive paper, and the preparation method and the application thereof, so that the conductive paper with good conductivity, mechanical property and thermal stability is obtained.
The invention is realized by the following technical scheme:
a preparation method of silver-based conductive paper comprises the following steps:
s1: placing the filter paper in acid NaIO 4 Drying the solution after the constant-temperature light-resistant reaction is finished to obtain the aldehyde-based filter paper;
s2: placing the aldehyde-group-treated filter paper in a PEI solution, and drying after the constant-temperature reaction is finished to obtain aminated filter paper;
s3: placing the aminated filter paper in AgNO 3 In the solution, after the room temperature reaction is finished, drying to obtain filter paper loaded with silver ions;
s4: and adding a reducing agent to the filter paper loaded with the silver ions, controlling the adding rate and the adding time of the reducing agent, and obtaining the silver-based conductive paper loaded with the fractal structure silver particles after the reaction is finished.
Preferably, the porosity of the filter paper is 70-90%, and the specific surface area is more than 150m 2 /g。
Preferably, the acidic NaIO 4 The pH of (A) is 3 to 4.
Preferably, the addition rate of the reducing agent in the step S4 is 1.5 to 5 mL/min -1 。
Preferably, the adding time of the reducing agent in the step S4 is 10-50 min.
Silver-based conductive paper is prepared by the method.
Preferably, the sheet resistance of the conductive paper is 1.5 Ω · sq -1 ～6.5Ω·sq -1 The conductivity was 6.8 S.cm -1 ～34.5S·cm -1
Preferably, the weight loss rate of the conductive paper after being heated is 40-60%.
Preferably, the stress of the conductive paper is greater than 6Mpa.
The silver-based conductive paper is applied to flexible electronic devices.
Compared with the prior art, the invention has the following beneficial technical effects:
a process for preparing the silver-base electrically conducting paper includes such steps as preparing the filter paper as substrate by acidic NaIO 4 The preparation method comprises the steps of realizing the dialdehyde oxidation of cellulose, then realizing the amination of the aldehydic filter paper by PEI, wherein PEI has a multi-branched flexible chain structure, the mechanical property of the filter paper can be effectively ensured, PEI has rich amino groups, the subsequent chelation of more silver ions is ensured, and then the reduction of the silver ions is realized by a reducing agent, so that the conductive paper loaded with the fractal structure silver particles is obtained. The filter paper has the characteristics ofThree-dimensional network structure, excellent self-supporting performance and great specific surface area have, the realization that can be fine is to the support of fractal structure silver particle, combine its three-dimensional space structure to ensure the good electric conductivity of conductive paper simultaneously, be chemical bonding between each layer of modification simultaneously, have stronger effort, combine the interactive force between basement filter paper fibre simultaneously, the mechanical properties of final conductive paper has wholly been ensured, in addition through chemical bonding's silver particle, cover on the surface of filter paper basement, the heat stability of material has effectively been ensured.
Furthermore, the porosity of the filter paper is 70-90%, and the specific surface area is more than 150m 2 The conductive paper can effectively support fractal structure silver particles in a product, and the good conductivity of the conductive paper is enhanced.
Further, control of acidic NaIO 4 The pH value of the solution is 3-4, so that NaIO can be effectively improved 4 Oxidation of (2).
Further, the addition rate of the reducing agent in the step S4 is 1.5-5 mL/min -1 And good fractal structure silver particles can be formed.
Further, the adding time of the reducing agent in the step S4 is 10-50 min, and the thickness of the fractal structure silver particles on the surface of the filter paper can be effectively controlled.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic view of a process for preparing silver-based conductive paper according to the present invention;
FIG. 2 shows FP-NaIO of the present invention 4 FT-IR spectra of FP-PEI and FP;
FIG. 3 is an XRD spectrum of FP-PEI/FSSPs prepared in the present invention with simple FP and FSSPs;
FIG. 4 is EDS spectrogram and element content analysis after FP surface deposition of FSSPs in the present invention;
FIG. 5 shows SEM spectra of FP-PEI/FSSPs prepared in examples 1-3 of the present invention and the thickness of the final material: (a) SEM image of unmodified FP surface; SEM images of FP surfaces at different times of reductant addition: (b) 10min; (c) 20min; (d) 30min; (e) 50min; (f) The thickness of the material changes when the reducing agent is added for different time;
FIG. 6 is a thermal analysis chart of FP-PEI, FP-PEI/FSSPs and unmodified FP obtained in examples 1-3 of the present invention: (a) a TGA profile; (b) a DTG curve;
FIG. 7 shows the conductivity tests of FP-PEI/FSSPs obtained in examples 1 to 3 of the present invention: testing the sheet resistance; (b) conductivity testing;
FIG. 8 is a topography of the FP-PEI/FSSPs conductive paper surface prepared in example 2 of the present invention under different magnifications.
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as values, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
In this document, unless otherwise specified, "comprising," including, "" containing, "" having, "or similar language, shall mean" consisting of … … "and" consisting essentially of … …, "e.g.," A comprises a "shall mean" A comprises a and the other "and" A comprises a only.
In the present context, for the sake of brevity, all possible combinations of various features in various embodiments or examples are not described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
As shown in fig. 1, the invention provides a preparation method of silver-based conductive paper, which specifically comprises the following steps:
s1: the porosity is 70 to 90 percent, and the specific surface area is more than 150m 2 Putting filter paper per gram in acid NaIO with pH value of 3-4 4 In the solution, after the constant-temperature and light-resistant reaction at 50 ℃, drying to obtain aldehyde-group filter paper; wherein, the filter paper and the acidic NaIO 4 The mass ratio of (1) to (3). Control of acidic NaIO 4 The pH value of the reaction kettle is 3-4, the oxidability of an oxidant can be effectively improved, and the constant temperature reaction temperature is 50 ℃ to ensure that the Schiff base reaction is smoothly carried out.
S2: placing the aldehydized filter paper in a PEI solution, wherein the mass ratio of the aldehydized filter paper to PEI is 1 (1-3), and drying after the constant temperature reaction at 50 ℃ is finished to obtain the aminated filter paper;
s3: placing the aminated filter paper in AgNO 3 In the solution, after the room temperature reaction is finished, drying to obtain filter paper loaded with silver ions;
s4: reducing agent is added in the amount of 1.5-5 mL/min -1 Adding the silver-based conductive paper onto the filter paper loaded with silver ions at the speed of (1), controlling the addition time of the reducing agent to be 10-50 min, and obtaining the silver-based conductive paper after the reaction is finished; the silver on the silver-based conductive paper is fractal structure silver particles. Wherein the reducing agent may be NH 2 Any one of OH, citric acid, ascorbic acid, glucose and sodium borohydride. The addition speed of the reducing agent is controlled, and AgNO can be controlled 3 The molar ratio of the solution to the reducing agent and the reduction process of the silver ions are controlled, so that good fractal structure silver particles can be formed.
The invention also discloses silver-based conductive paper which is prepared by the method. The sheet resistance of the conductive paper is 1.5 omega sq -1 ～6.5Ω·sq -1 The electrical conductivity was 6.8 S.cm -1 ～34.5S·cm -1 The stress is greater than 6MPa.
The stress test method of the silver-based conductive paper comprises the following steps: and (3) adopting a servo material multifunctional high-low temperature control testing machine to test the tensile mechanical strength of the paper. And (3) testing conditions: the sample was cut into a 10X 30mm rectangle at a test speed of 2 mm. Min-1 and a jig distance of 10mm.
The natural porous, reticulated and rough structure of the FP acts as a template, providing structural support and a conductive network for the deposition of conductive materials. In addition, pores beneficial to electron transfer are formed by abundant pore structures in the filter paper, conductivity is improved, and the nano or micron rough surface structure naturally formed on the surface can ensure firm adhesion between the cellulose substrate filter paper and the conductive layer, which is very important for the conductive stability of the conductive device. In addition, compared with silver nanoparticles and nanowires, fractal-structured silver particles (FSSPs) having micro-scale dendrites and nano-scale tips on the surface form a perfect conductive network through mutual contact between the dendrites, which can better improve the conductivity of the conductive paper.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The following examples use instrumentation conventional in the art. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. The various starting materials used in the examples which follow, unless otherwise indicated, are conventional commercial products having specifications which are conventional in the art. In the description of the present invention and the following examples, "%" represents weight percent, "parts" represents parts by weight, and proportions represent weight ratios, unless otherwise specified.
Example 1
A preparation method of silver-based conductive paper specifically comprises the following steps:
step 1, filter paper (FP-NaIO) formylated 4 ) And (4) preparing. First, using NaIO 4 And performing aldehyde group functionalization on the FP surface. 1.3g of NaIO was taken 4 Dissolving the powder in a beaker filled with 100mL of deionized water, and accelerating NaIO by adopting ultrasonic treatment 4 Dissolution in water. The pH of the solution was then adjusted to about 3.5 by 0.1% HCl solution. 3cm FP is cut and put into the prepared solution, and the beaker is placed in a constant temperature water bath kettle at 50 ℃ to react for 5 hours in a dark place. After the reaction is finished, the FP is taken out, washed three times by 100mL of deionized water and absolute ethyl alcohol respectively, and dried in a vacuum oven at 60 ℃ for 4 hours to obtain the aldehyde-based filter paper (FP-NaIO) 4 )。
And 2, preparing aminated filter paper (FP-PEI). Aldehyde filter paper (FP-NaIO) 4 ) Amino functionalization (FP-PEI) is achieved by Schiff base reaction. Specifically, 3g of PEI is dissolved in a beaker filled with 50mL of absolute ethyl alcohol solution, and FP-NaIO is added 4 And placing the beaker in a constant-temperature water bath kettle at 50 ℃ again for reaction for 5 hours. After the reaction is finished, the FP is taken out and washed three times by 100mL of deionized water and absolute ethyl alcohol respectively. And (4) drying in a vacuum oven at 60 ℃ for 4h to obtain the FP-PEI.
And 3, chelating silver ions. Amino-functionalized filter paper surface chelated silver ion (FP-PEI-Ag) + ). First, 0.509g of AgNO was weighed 3 Dispersing the particles in a beaker containing 50mL of deionized water solution, and carrying out ultrasonic treatment to enable AgNO to be dispersed 3 The particles were completely dissolved. In AgNO 3 Putting FP-PEI into the solution, and reacting for 30min at room temperature to obtain Ag + Adsorbing on the FP surface by the chelation of amino to obtain FP-PEI-Ag + 。
Step 4, loading conductive paper (FP-PEI/FSSPs) of fractal structure silver particles, FP-PEI-Ag + And (3) preparing the conductive paper of the Fractal Structure Silver Particles (FSSPs) by in-situ reduction. Take 0.735mL NH 2 The OH solution was dissolved in a beaker containing 50mL of deionized water and the solution was mixed well by sonication.Mixing FP-PEI-Ag + Putting into a clean beaker, adding NH 2 OH is dripped into a beaker, and NH is controlled by a peristaltic pump 2 The dropping rate of the OH solution is 2.5 mL/min -1 The reaction time was controlled to 10min, and the filter paper was removed after the reaction was completed. The mixture is dried in a vacuum oven at 60 ℃ for 4 hours to obtain FP-PEI/FSSPs.
The sheet resistance of the FP-PEI/FSSPs conductive paper is 6.41 omega sq -1 The stress reaches 6.19MPa, the residual mass is respectively 38.66 percent after thermal stability test, and the prepared FP-PEI/FSSPs conductive paper has good conductivity, excellent mechanical property and thermal stability.
Example 2
The invention relates to a method for preparing silver-based conductive paper on a filter paper template, which specifically comprises the following steps:
step 1, aldehyde group functionalization (FP-NaIO) on the surface of filter paper 4 ). First, using NaIO 4 And performing aldehyde group functionalization on the FP surface. 1.3g of NaIO was taken 4 Dissolving the powder in a beaker filled with 100mL of deionized water, and accelerating NaIO by adopting ultrasonic treatment 4 Dissolution in aqueous solution. The pH of the solution was then adjusted to about 3.5 by 0.1% HCl solution. 3cm FP is cut and put into the prepared solution, and the beaker is placed in a constant temperature water bath kettle at 50 ℃ to react for 5 hours in a dark place. After the reaction is finished, the FP is taken out, washed by 100mL of deionized water and absolute ethyl alcohol for three times respectively, and dried in a vacuum oven at 60 ℃ for 4 hours to obtain the FP-NaIO 4 。
Step 2, aldehyde filter paper (FP-NaIO) 4 ) Amino functionalization (FP-PEI) is achieved by Schiff base reaction. Dissolving 3g PEI in a beaker filled with 50mL absolute ethyl alcohol solution, and putting FP-NaIO 4 And placing the beaker in a constant-temperature water bath kettle at 50 ℃ again for reaction for 5 hours. After the reaction is finished, the FP is taken out and washed three times by 100mL of deionized water and absolute ethyl alcohol respectively. And (4) drying in a vacuum oven at 60 ℃ for 4h to obtain the FP-PEI.
Step 3, chelating silver ions (FP-PEI-Ag) on the surface of the amino functionalized filter paper + ). First, 0.509g of AgNO was weighed 3 Dispersing the particles in a beaker containing 50mL of deionized water solution, and carrying out ultrasonic treatment to enable AgNO to be dispersed 3 The granules are completely dissolvedAnd (5) solving. In AgNO 3 Putting FP-PEI into the solution, and reacting for 30min at room temperature to obtain Ag + Adsorbing on the FP surface by the chelation of amino to obtain FP-PEI-Ag + 。
Step 4, FP-PEI-Ag + And (3) preparing FSSPs conductive paper (FP-PEI/FSSPs) by in-situ reduction. Take 0.735mL NH 2 The OH solution was dissolved in a beaker containing 50mL of deionized water and sonicated to allow the solution to mix well. Mixing FP-PEI-Ag + Putting into a clean beaker, adding NH 2 OH is dripped into a beaker, and NH is controlled by a peristaltic pump 2 The dropping rate of the OH solution is 2.5 mL/min -1 The reaction time was controlled to 30min, and the filter paper was removed after the reaction was completed. The mixture is dried in a vacuum oven at 60 ℃ for 4 hours to obtain FP-PEI/FSSPs.
The FP-PEI/FSSPs conductive paper has good conductivity (the sheet resistance is 1.47 omega. Sq) -1 ) And excellent mechanical properties (stress up to 6.19 MPa). Meanwhile, the conductive paper has excellent thermal stability (the residual mass is 49.39% respectively).
Example 3
The invention relates to a method for preparing silver-based conductive paper on a filter paper template, which specifically comprises the following steps:
step 1, aldehyde group functionalization (FP-NaIO) on the surface of filter paper 4 ). First, using NaIO 4 And performing aldehyde group functionalization on the FP surface. 1.3g of NaIO was taken 4 Dissolving the powder in a beaker filled with 100mL of deionized water, and accelerating NaIO by adopting ultrasonic treatment 4 Dissolution in aqueous solution. The pH of the solution was then adjusted to about 3.5 by 0.1% HCl solution. 3cm FP is cut and put into the prepared solution, and the beaker is placed in a constant temperature water bath kettle at 50 ℃ to react for 5 hours in a dark place. After the reaction is finished, the FP is taken out, washed three times by 100mL of deionized water and absolute ethyl alcohol respectively, and dried in a vacuum oven at 60 ℃ for 4 hours to obtain FP-NaIO 4 。
Step 2, aldehyde filter paper (FP-NaIO) 4 ) Amino functionalization (FP-PEI) is achieved through Schiff base reaction. Dissolving 3g PEI in a beaker filled with 50mL absolute ethyl alcohol solution, and putting FP-NaIO 4 And placing the beaker in a constant-temperature water bath kettle at 50 ℃ again for reaction for 5 hours. After the reaction is finished, taking out FP, and dividingWashed three times with 100mL of deionized water and absolute ethyl alcohol, respectively. And (4) drying in a vacuum oven at 60 ℃ for 4h to obtain the FP-PEI.
Step 3, chelating silver ions (FP-PEI-Ag) on the surface of the amino functionalized filter paper + ). First, 0.509g of AgNO was weighed 3 Dispersing the particles in a beaker containing 50mL of deionized water solution, and carrying out ultrasonic treatment to enable AgNO to be dispersed 3 The particles were completely dissolved. In AgNO 3 Putting FP-PEI into the solution, and reacting for 30min at room temperature to obtain Ag + Adsorbing on the FP surface by the chelation of amino to obtain FP-PEI-Ag + 。
Step 4, FP-PEI-Ag + And (3) preparing FSSPs conductive paper (FP-PEI/FSSPs) by in-situ reduction. Take 0.735mL NH 2 The OH solution was dissolved in a beaker containing 50mL of deionized water and the solution was mixed well by sonication. Mixing FP-PEI-Ag + Putting into a clean beaker, adding NH 2 OH is dripped into a beaker, and NH is controlled by a peristaltic pump 2 The dropping rate of the OH solution is 2.5 mL/min -1 The reaction time was controlled to 50min, and the filter paper was removed after the reaction was complete. The mixture is dried in a vacuum oven at 60 ℃ for 4 hours to obtain FP-PEI/FSSPs.
The FP-PEI/FSSPs conductive paper has good conductivity (the sheet resistance is 1.56 omega. Sq) -1 ) And excellent mechanical properties (stress up to 6.19 MPa). Meanwhile, the conductive paper has excellent thermal stability (residual mass of 51.67%, respectively).
FP and FP-NaIO were analyzed by FT-IR as shown in FIG. 2 4 Change in the surface chemical structure of FP-PEI. As can be seen from the figure, the unmodified FP surface exhibited the characteristic absorption peak of cellulose. NaIO 4 After oxidation, the surface chemistry of the filter paper is changed. At 1726cm -1 The absorption peak is corresponding to the characteristic peak of tensile vibration of C = O on the surface of the paper after aldehyde group modification, and is 890cm -1 The absorption peak at (A) then corresponds to the absorption peak of the hemiacetal bond between-CHO and the adjacent-OH. The appearance of these absorption peaks indicates NaIO 4 In the oxidation process, the C of glucose units on the cellulose molecular chain is destroyed 2 -C 3 Chemical bonds, successfully introduced-CHO functional groups on the FP surface. After modification with PEI 1726cm -1 The intensity of the absorption peak is obviously weakened and even disappears. And 1577cm -1 The characteristic absorption peak of C = N bond appears at 1469cm -1 The absorption peak at (a) corresponds to the C-N stretching vibration. The appearance of the new peaks indicates that the amino group on the PEI and the aldehyde group on the FP surface have Schiff base reaction, and the amino group is successfully grafted on the FP surface.
As shown in FIG. 3, the change of the crystal form of the material after FSSPs are deposited on the surface of the FP obtained by the invention is analyzed by XRD. It can be seen from the figure that peaks of pure FSSPs at 2 θ =38.14 °, 44.34 °, 64.46 °, 77.43 ° and 81.58 ° correspond to the (111), (200), (220), (331) and (222) diffraction crystal planes of face-centered cubic silver (JCPDS document No. 04-0783). FP modified with PEI showed characteristic absorption peaks at 2 θ =14.9 °, 16.3 °, 22.7 °, and 34.5 °, corresponding to diffraction crystal planes of (101), (200), and (004) of cellulose, respectively. Showing that the crystalline structure of the cellulose part is retained after depositing FSSPs on the surface of the PEI-modified FP.
As shown in FIG. 4, the element change of the cellulose surface after FSSPs are deposited on the FP surface obtained by the invention is analyzed by EDS, and as can be seen from the figure, the FP-PEI/FSSPs conductive paper surface element is mainly C, O, N, ag. Wherein, the content of C element is 30.53 percent, the content of O element is 38.14 percent, the content of N element is 2.28 percent, and the content of Ag element is 29.05 percent, which indicates that FSSPs are successfully deposited on the FP surface.
As shown in fig. 5, the effect of conductive paper on FP surface morphology before and after FSSPs deposition and deposition time was characterized by SEM. Fig. 5 (a) is a SEM image of the surface of unmodified FP, which consists of interconnected cellulose and a small portion of filler as shown in fig. 5 (a). The purpose of the filler is mainly to improve the smoothness and whiteness of the paper. FIG. 5 (b) shows NH control 2 The OH solution was added for 10min, and NH was controlled in FIG. 5 (c) 2 The OH solution was added for 20min, and NH control in FIG. 5 (d) 2 The OH solution was added for 30min, and NH control in FIG. 5 (e) 2 The adding time of the OH solution is 50min, namely, the figure 5 (b-e) shows the topography of the FP-PEI/FSSPs conductive paper under different reducing times. As can be seen from the figure, FSSPs are uniformly distributed over the FP surface,the grain diameter is 2-3 μm. When the reaction time is 10min (as shown in fig. 5 (b)), the FSSPs are less distributed on the FP surface and are more loosely distributed due to the shorter reaction time, and no uniform conductive network is formed on the FP surface. As the reaction time increases, FSSPs deposit on the FP surface in increasing amounts. When the reaction time is 30min, as can be seen from the graph in fig. 5 (d), a layer of dense FSSPs is uniformly deposited on the FP surface, and is uniformly distributed, so that a perfect conductive network is formed on the FP surface. FIG. 5 (f) shows the change in filter paper thickness with increasing deposition time of FSSPs. As can be seen in FIG. 5 (f), the thickness of a simple filter paper is 0.15mm, and the FP thickness increases with the deposition time of FSSPs. When the deposition time is 30min, the FP thickness is increased to 0.20mm; the FP thickness was 0.208mm at a deposition time of 50min. When the deposition time is 10min to 30min, the FP thickness is obviously increased, and the increase amplitude of the FP thickness tends to be smooth when the deposition time is 30min to 50min. This is because the FP surface has not yet formed a uniform FSSPs layer at deposition times less than 30 min. As the deposition time increases, the FSSPs on the FP surface are distributed more uniformly and reach a saturated state. So that its thickness does not increase substantially.
As shown in fig. 6, the thermal stability of the sample was investigated by heat treatment. As can be seen from FIG. 6 (a), the weight loss of the unmodified FP is relatively serious, the weight loss rate is about 80%, and the weight loss rate of the FP-PEI/FSSPs conductive paper is obviously reduced. The thermal stability of the PEI/FSSPs modified FP is obviously improved. Meanwhile, as can be seen from FIG. 6 (b), the thermal decomposition temperature of the unmodified FP was 349.3 ℃. After modification by PEI, the thermal decomposition temperature is reduced, probably because the crystal structure of the cellulose is damaged in the modification process, thereby reducing the thermal decomposition temperature. The thermal decomposition temperature of the FP-PEI/FSSPs conductive paper is slightly increased to 357.8 ℃. This is because the thermal stability of silver is higher than that of cellulose, and during the reaction, the fiber surface is uniformly coated with FSSPs, so that the thermal stability of the paper is improved.
As shown in FIG. 7, the conducting performance of FP-PEI/FSSPs conducting paper is studied, and from FIG. 7 (a), the sheet resistance value of FP-PEI/FSSPs conducting paper is reduced and then basically kept unchanged along with the increase of the reduction reaction timeTrend is shown. When the reduction time of silver ions is 10min, the sheet resistance of the FP-PEI/FSSPs conductive paper is 6.41 omega sq -1 (ii) a When the reaction time is 30min, the sheet resistance is reduced to 1.47 omega sq -1 . The reason is that the FSSPs deposition amount on the FP surface gradually increases along with the increase of the reaction time, so that good fractal-structure silver conductive particles are gradually formed, and a perfect conductive network is formed. When the reaction time is 50min, the FP surface sheet resistance is 1.50 omega sq -1 There was no significant change from reaction for 30 min. This is because the amount of FSSPs deposited is sufficient to form a perfect conductive network at a reaction time of 30 min. FIG. 7 (b) shows the change of conductivity of FP-PEI/FSSPs conductive paper with the increase of reduction reaction time. As can be seen from fig. 7 (b), the conductivity shows a tendency to increase first and then to remain substantially constant. When the reaction time is 10min, the conductivity is 679 S.m -1 (ii) a When the reaction time is 30min, the conductivity is increased to 3401 S.m -1 (ii) a The conductivity is 3340 S.m when the reaction time is 50min -1 . The reason for presenting such a tendency is the same as the reason for explaining the variation tendency of the sheet resistance. In conclusion, when the reaction time is 30min, a perfect conductive network system is formed on the FP surface.
As shown in fig. 8, a topography of the surface of FP-PEI/FSSPs conductive paper prepared in embodiment 2 of the present invention under different magnifications is shown, and it can be seen from the figure that the present invention effectively controls the reduction rate of silver ions by controlling the addition rate of the reducing agent, so that the obtained silver is not in a complete accumulation form, but in a split three-dimensional structure, which makes it easy to form a conductive network on the surface of the filter paper and in the pore structure through mutual contact between dendrites, thereby providing excellent conductivity for the conductive paper.
Example 4
A preparation method of silver-based conductive paper specifically comprises the following steps:
s1: the porosity was 70%, the specific surface area was 150m 2 Filter paper/g placed in acidic NaIO with pH 3 4 In the solution, after the constant-temperature and light-resistant reaction at 50 ℃, drying to obtain aldehyde-group filter paper; wherein the filter paper is mixed with acidic NaIO 4 Is 1:1.
S2: placing the aldehyde-group filter paper in a PEI solution, wherein the mass ratio of the aldehyde-group filter paper to the PEI is 1:1, and after the constant-temperature reaction at 50 ℃, drying to obtain the aminated filter paper;
s3: placing the aminated filter paper in AgNO 3 In the solution, after the room temperature reaction is finished, drying to obtain filter paper loaded with silver ions;
s4: citric acid at 1.5 mL/min -1 Adding the solution to the filter paper loaded with silver ions at the speed of (2), controlling the adding time of the citric acid to be 30min, and obtaining the silver-based conductive paper after the reaction is finished; the silver on the silver-based conductive paper is fractal structure silver particles. The sheet resistance of the silver-based conductive paper is 1.5 omega sq -1 The electrical conductivity was 6.79 S.cm -1 The stress was 6.1MPa.
Example 5
A preparation method of silver-based conductive paper specifically comprises the following steps:
s1: the porosity is 75 percent, and the specific surface area is 160m 2 Putting filter paper per gram in acid NaIO with pH value of 4 4 In the solution, after the constant-temperature and light-resistant reaction at 50 ℃, drying to obtain aldehyde-group filter paper; wherein, the filter paper and the acidic NaIO 4 Is 1:2.
S2: placing the aldehydized filter paper in a PEI solution, wherein the mass ratio of the aldehydized filter paper to the PEI is 1:2, and drying after the constant-temperature reaction at 50 ℃ is finished to obtain the aminated filter paper;
s3: placing the aminated filter paper in AgNO 3 In the solution, after the room-temperature reaction is finished, drying to obtain filter paper loaded with silver ions;
s4: ascorbic acid was added at 2.5 mL/min -1 Adding the mixture into the filter paper loaded with silver ions at the speed of (2), controlling the adding time of the ascorbic acid to be 40min, and obtaining the silver-based conductive paper after the reaction is finished; the silver on the silver-based conductive paper is fractal structure silver particles. The sheet resistance of the silver-based conductive paper is 2.5 omega sq -1 Conductivity of 9S cm -1 The stress is 6.5MPa.
Example 6
A preparation method of silver-based conductive paper specifically comprises the following steps:
s1: the porosity is 80 percent, and the specific surface area is 175m 2 Filter paper/g placed in acidic NaIO with pH 4 4 In the solution, after the constant-temperature and light-resistant reaction at 50 ℃, drying to obtain aldehyde-group filter paper; wherein, the filter paper and the acidic NaIO 4 Is 1:3.
S2: placing the aldehyde-group filter paper in a PEI solution, wherein the mass ratio of the aldehyde-group filter paper to the PEI is 1:3, and after the constant-temperature reaction at 50 ℃, drying to obtain the aminated filter paper;
s3: placing the aminated filter paper in AgNO 3 In the solution, after the room temperature reaction is finished, drying to obtain filter paper loaded with silver ions;
s4: glucose was added at 3.5 mL/min -1 Adding the mixture into the filter paper loaded with silver ions at the speed of (1), controlling the adding time of glucose to be 35min, and obtaining silver-based conductive paper after the reaction is finished; the silver on the silver-based conductive paper is fractal structure silver particles. The sheet resistance of the silver-based conductive paper is 5.5 omega sq -1 The conductivity was 10.2 S.cm -1 The stress was 7MPa.
Example 7
A preparation method of silver-based conductive paper specifically comprises the following steps:
s1: the porosity is 90%, the specific surface area is 175m 2 Filter paper/g placed in acidic NaIO with pH 3 4 In the solution, after the constant-temperature and light-resistant reaction at 50 ℃, drying to obtain the aldehyde-based filter paper; wherein, the filter paper and the acidic NaIO 4 Is 1:1.
S2: placing the aldehyde-group filter paper in a PEI solution, wherein the mass ratio of the aldehyde-group filter paper to the PEI is 1:1, and after the constant-temperature reaction at 50 ℃, drying to obtain the aminated filter paper;
s3: placing the aminated filter paper in AgNO 3 In the solution, after the room-temperature reaction is finished, drying to obtain filter paper loaded with silver ions;
s4: sodium borohydride was added at 5mL min -1 Adding the mixture into the filter paper loaded with silver ions at the speed of (1), controlling the adding time of the sodium borohydride to be 50min, and finishing the reactionThen, obtaining silver-based conductive paper; the silver on the silver-based conductive paper is fractal structure silver particles. The sheet resistance of the silver-based conductive paper is 6.5 omega sq -1 The conductivity was 34.5 S.cm -1 The stress is 7MPa.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. The preparation method of the silver-based conductive paper is characterized by comprising the following steps:
s1: placing the filter paper in acid NaIO 4 In the solution, after the constant-temperature light-resistant reaction is finished, drying to obtain aldehyde-based filter paper;
s2: placing the aldehyde-group-treated filter paper in a PEI solution, and drying after the constant-temperature reaction is finished to obtain aminated filter paper;
s3: placing the aminated filter paper in AgNO 3 In the solution, after the room temperature reaction is finished, drying to obtain filter paper loaded with silver ions;
s4: and adding a reducing agent to the filter paper loaded with the silver ions, controlling the adding rate and the adding time of the reducing agent, and obtaining the silver-based conductive paper loaded with the fractal structure silver particles after the reaction is finished.
2. The method for preparing the silver-based conductive paper as claimed in claim 1, wherein the porosity of the filter paper is 70-90%, and the specific surface area is more than 150m 2 /g。
3. The method for preparing silver-based conductive paper according to claim 1, wherein the acidic NaIO is 4 The pH of (A) is 3 to 4.
4. The method for preparing silver-based conductive paper according to claim 1, wherein the addition rate of the reducing agent in the step S4 is 1.5-5 mL-min -1 。
5. The method for preparing silver-based conductive paper according to claim 1, wherein the addition time of the reducing agent in step S4 is 10-50 min.
6. A silver-based conductive paper, characterized by being produced by the method of any one of claims 1 to 5.
7. The silver-based conductive paper according to claim 6, wherein the sheet resistance of the conductive paper is 1.5 Ω · sq -1 ～6.5Ω·sq -1 The conductivity was 6.8 S.cm -1 ～34.5S·cm -1 。
8. The silver-based conductive paper according to claim 6, wherein the weight loss rate of the conductive paper after heating is 40-60%.
9. The silver-based conductive paper according to claim 6, wherein the conductive paper has a stress greater than 6Mpa.
10. Use of the silver-based conductive paper according to any one of claims 6 to 9 in flexible electronic devices.
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CN108018744A (en) * 2017-11-08 2018-05-11 天津科技大学 A kind of preparation method of multifunctional modification filter paper
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