CN108071007B - Method for preparing silver nanowire and graphene-based calcium alginate composite conductive fiber - Google Patents
Method for preparing silver nanowire and graphene-based calcium alginate composite conductive fiber Download PDFInfo
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Abstract
The invention discloses a method for preparing a silver nanowire and graphene-based calcium alginate composite conductive fiber, which comprises the steps of preparing a sodium alginate micron-scale fiber by using a wet spinning technology, carrying out surface modification on the fiber, carrying out positive charge, immersing the fiber into a silver nanowire alcohol solution containing surface negative charge, forming a silver nanowire conductive network structure on the surface of the fiber, and finally adsorbing a graphene layer on the surface of the conductive fiber, so that the stability of the conductive fiber is improved. The invention discloses a preparation method of composite conductive fibers, which has the advantages of simple preparation process, low cost, mass preparation and application prospect in the aspects of microelectronic device circuit preparation, flexible conductors and the like.
Description
Technical Field
The application relates to the field of conductive paste, in particular to the technical field of preparation of silver nanowire (Ag NWs) and Graphene (Graphene) based calcium alginate composite conductive fibers.
Background
At present, there is extensive research and application for various composite conductive fibers, among which the most classical one is made of conductive particles, such as: carbon black, metal particles, conductive fibers and the like are taken as basic functional units, thermoplastic resin is taken as a base material of the conductive composite fibers, and the carbon black, the metal particles, the conductive fibers and the like are combined together through a spinning technology to form the complete conductive fibers.
In order to obtain composite conductive fibers with good properties, it is necessary to continuously disperse conductive functional particles in a matrix material, however, there are problems such as: 1. the conductive particles and the matrix material with proper proportion have great difference according to different materials, which brings great obstruction to practical production; 2. how to uniformly and continuously disperse the conductive particles in the matrix material is also a great challenge, and we know that the conductive particles are uniformly dispersed with the matrix material, and how to control the ordered arrangement of the conductive particles is still a current problem; 3. when the content of the conductive particles in the matrix reaches a certain ratio, the performance of the final composite fiber is seriously degraded due to the increase of the conductive particles, such as the spinnability and the stretchability thereof are seriously degraded.
In recent years, with the continuous emergence of new materials, people have more and more researches on conductive composite materials, such as Chinese patent application 201210564807.9 discloses a carbon nanotube/polyurethane/polyacrylonitrile composite conductive fiber having a conductivity of about 10-5About S/cm, the better use effect cannot be achieved, and in addition, the preparation cost of the carbon nano tube is higher, so that the industrial application of the composite fiber is limited.
In addition, chinese patent application 201410506432.X discloses a preparation method of a graphene-doped conductive composite fiber, specifically, after graphene, a dispersing agent and a high molecular polymer are uniformly mixed, a double-screw extruder is used for melting, filtering, spinning, cooling and forming, stretching and heat setting the mixture to obtain the conductive composite fiber, and the conductivity of the conductive composite fiber can reach 10-4About S/cm, and the elongation at break is more than 10%.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: because the process of the existing prepared conductive composite fiber is relatively complex, and the performance, especially the conductivity and the processability, of the obtained conductive composite fiber are low, the invention provides a brand-new conductive composite fiber system, and the composite conductive fiber of the silver nanowires and the graphene-based calcium alginate is prepared by continuously perfecting and optimizing the process.
In order to achieve the purpose, the invention adopts the following experimental technical scheme:
a method for preparing silver nanowires and graphene-based calcium alginate composite conductive fibers is characterized by comprising the following steps: the method comprises the following steps:
(1) silver nanowires and graphene are prepared by a common polyol method and a modified Hummers method, respectively, and are dispersed in an alcohol solution, and graphene is dispersed in an aqueous solution.
(2) Preparing 0.5-5% sodium alginate and 30-80% calcium chloride alcoholic solution as calcium alginate precursor, and injecting sodium alginate into calcium chloride alcoholic solution at an injection rate of 2-20m L/min by using a double injection pump to obtain calcium alginate microfiber;
(3) immersing the calcium alginate micron fibers prepared in the step (2) into a modifier solution with the mass concentration of 3-10% for 2-10 hours to enable the surfaces of the fibers to be positively charged;
(4) dropwise adding the fiber prepared in the step (3) into the silver nanowire alcohol solution prepared in the step (1) under the stirring condition, and continuously stirring for 0.2-1 hour after the dropwise adding of the silver nanowire alcohol solution is finished; then dropwise adding the aqueous solution of graphene under the stirring condition, and continuously stirring for 0.2-1 hour; obtaining silver nanowires and graphene-based calcium alginate one-dimensional composite conductive fibers;
(5) and (4) sequentially centrifuging and washing the composite conductive fiber prepared in the step (4) to obtain the silver nanowire and graphene-based calcium alginate one-dimensional composite conductive fiber.
To further illustrate this embodiment, a more preferred embodiment is:
in the step (1), the concentration of the silver nanowires and the graphene solution is 0.1-1mg/m L, and the molar ratio of the addition amount of the silver nanowires to the graphene solution is 1 (0.1-2).
Further preferably, the modifier in the step (3) is one or more of Sodium Dodecyl Benzene Sulfonate (SDBS), hexadecyl trimethyl quaternary ammonium bromide or octadecyl dimethyl benzyl ammonium chloride.
The composite conductive fiber prepared by the method has the conductivity of 5 x 10-3More than S/cm and can be quickly and conveniently prepared on a large scale.
The principle of the invention is as follows: firstly, the wet spinning technology is used to prepare the calcium alginate fiber, the sodium alginate is a linear polysaccharide extracted from natural seaweed, and comprises M unit and G unit, the content and arrangement mode of the M unit and the G unit in the macromolecule vary with the type and the producing area of the seaweed, and the G unit in the sodium alginate can be mixed with Ca2+Forming a special 'eg-box' structure, and obtaining a fiber with uniform longitudinal thickness, grooves on the surface, irregular sawtooth-shaped cross section and no skin core layer structure by utilizing the property of sodium alginate; secondly, the surface electrical property of the calcium alginate fiber is changed through the action of the modifier, so that the surface of the calcium alginate fiber is positively charged, and the silver nanowires with negative charges and graphene can be uniformly coated under the stirring conditionCoated on the calcium alginate fiber, thereby obtaining the composite conductive fiber with excellent conductivity and processability.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the invention uses wet spinning technology to prepare high-performance calcium alginate fiber, which is a simple and low-cost fiber preparation method;
2. the silver nanowire and graphene-based calcium alginate composite conductive fiber is prepared by modifying the surface of the calcium alginate fiber, and has good conductivity and processability.
3. The composite conductive fiber prepared by the method has better universality, and not only can use the silver nanowires and the graphene as conductive elements, but also other conductive materials can be used as the conductive elements.
Drawings
FIG. 1 is a scanning electron micrograph of calcium alginate fibers;
FIG. 2 is a scanning electron micrograph of a calcium alginate fiber coated with silver nanowires;
fig. 3 is a scanning electron micrograph of the silver nanowires and the graphene-based calcium alginate composite conductive fibers.
Detailed Description
Example 1
Firstly, respectively preparing 0.5mg/m L silver nanowire alcohol solution and graphene water solution, secondly, using 1.5% sodium alginate and 30% calcium chloride alcohol solution as calcium alginate precursors, injecting the sodium alginate into the calcium chloride alcohol solution by using a double-injection pump at an injection speed of 5m L/min to obtain calcium alginate micro-fibers, immersing the prepared calcium alginate micro-fibers into a sodium dodecyl benzene sulfonate solution with a mass concentration of 3% for 2 hours to enable the surfaces of the fibers to be positively charged, thirdly, dropwise adding the prepared fibers into the prepared silver nanowire alcohol solution under the stirring condition, continuously stirring for 0.2 hour after the completion of dropwise adding the silver nanowire alcohol solution, then dropwise adding the graphene water solution under the stirring condition, continuously stirring for 0.2 hour, and finally, sequentially centrifuging and washing the products to obtain the silver nanowire and graphene-based calcium alginate one-dimensional composite conductive fibers.
Example 2
Firstly, respectively preparing 1.0mg/m L silver nanowire alcohol solution and 0.5mg/m L graphene water solution, secondly, using 2.5% sodium alginate and 30% calcium chloride alcohol solution as calcium alginate precursors, injecting the sodium alginate into the calcium chloride alcohol solution by using a double-injection pump at an injection speed of 5m L/min to obtain calcium alginate micro-fibers, immersing the prepared calcium alginate micro-fibers into a sodium dodecyl benzene sulfonate solution with a mass concentration of 3% for 2 hours to enable the surfaces of the fibers to be positively charged, thirdly, dropwise adding the prepared fibers into the prepared silver nanowire alcohol solution under the stirring condition, continuously stirring for 0.2 hours after the completion of dropwise adding the silver nanowire alcohol solution, then adding the graphene water solution under the stirring condition, continuously stirring for 0.2 hours, and finally, sequentially centrifuging and washing the products to obtain the silver nanowire and graphene-based calcium alginate one-dimensional composite conductive fibers.
Example 3
Firstly, respectively preparing 1.0mg/m L silver nanowire alcohol solution and 0.5mg/m L graphene water solution, secondly, using sodium alginate with the mass concentration of 2.5% and 50% calcium chloride alcohol solution as calcium alginate precursors, injecting the sodium alginate into the calcium chloride alcohol solution by using a double-injection pump at the injection speed of 10m L/min to obtain calcium alginate micro-fibers, immersing the prepared calcium alginate micro-fibers into a hexadecyl trimethyl ammonium bromide solution with the mass concentration of 3% for 3 hours to enable the surfaces of the fibers to be positively charged, thirdly, dropwise adding the prepared fibers into the prepared silver nanowire alcohol solution under the stirring condition, continuously stirring for 0.5 hour after the dropwise adding of the silver nanowire alcohol solution is finished, then adding the graphene water solution under the stirring condition, continuously stirring for 0.5 hour dropwise, and finally, sequentially centrifuging and washing the products to obtain the silver nanowire and graphene-based calcium alginate one-dimensional conductive fibers.
Comparative example 1
The other steps are the same as example 1, except that after the calcium alginate fiber is prepared, the silver nanowires and the graphene solution are added into the calcium alginate fiber at the same time, and the composite conductive fiber can also be prepared, but the conductivity of the fiber is only 2 x 10-4S/cm。
Claims (4)
1. A method for preparing silver nanowires and graphene-based calcium alginate composite conductive fibers is characterized by comprising the following steps: the method comprises the following steps:
(1) respectively preparing silver nanowires and graphene by a common polyol method and a modified Hummers method, dispersing the silver nanowires in an alcohol solution, and dispersing the graphene in an aqueous solution;
(2) preparing 0.5-5% sodium alginate and 30-80% calcium chloride alcoholic solution as calcium alginate precursor, and injecting sodium alginate into calcium chloride alcoholic solution at an injection rate of 2-20m L/min by using a double injection pump to obtain calcium alginate microfiber;
(3) immersing the calcium alginate micro-fibers prepared in the step (2) into a sodium dodecyl benzene sulfonate solution with the mass concentration of 3-10% for 2-10 hours to enable the surfaces of the fibers to be positively charged;
(4) dropwise adding the fiber prepared in the step (3) into the silver nanowire alcohol solution prepared in the step (1) under the stirring condition, and continuously stirring for 0.2-1 hour after the dropwise adding of the silver nanowire alcohol solution is finished; then dropwise adding the aqueous solution of graphene under the stirring condition, and continuously stirring for 0.2-1 hour; obtaining silver nanowires and graphene-based calcium alginate one-dimensional composite conductive fibers;
(5) and (4) sequentially centrifuging and washing the composite conductive fiber prepared in the step (4) to obtain the silver nanowire and graphene-based calcium alginate one-dimensional composite conductive fiber.
2. The method for preparing the composite conductive fiber according to claim 1, wherein the concentration of the silver nanowires and the graphene solution in the step (1) is 0.1-1mg/m L, and the molar ratio of the addition amount of the silver nanowires and the graphene solution is 1 (0.1-2).
3. The method of preparing a composite conductive fiber according to claim 1, characterized in that: the alcoholic solution is one or more of methanol, ethanol and isopropanol.
4. The composite conductive fiber method of claim 1, wherein: the diameter of the composite conductive fiber is between 100 and 200 microns.
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