TW201804478A - Preparation method of silver-carbon composite aqueous solution, silver-carbon composite aqueous solution, silver-carbon composite unit, conductor, and preparation method of conductor capable of forming a better dispersed and long-term storage solution without precipitation - Google Patents

Abstract

A method for preparing an aqueous solution of a silver-carbon composite comprises the steps of: mixing a plurality of unmodified carbon materials, water and a sulfonate anionic surfactant and subjecting them to an ultrasonic wave treatment so that the unmodified carbon materials are dispersed in water to form a dispersed aqueous solution, then a plurality of atomized droplets formed from a silver salt aqueous solution containing silver salt and water are added into said dispersed water solution by means of spraying, followed by an ultrasonic wave treatment to form a silver carbon composite aqueous solution, wherein, the size of the unmodified carbon material is of nanometer or micrometer, the silver carbon composite aqueous solution comprises the water and a plurality of silver carbon composite materials that are dispersed in the water, and each of the silver carbon composite materials includes a plurality of silver metal nanoparticles and individual unmodified carbon materials provided for bonding the silver nanoparticles.

Description

Preparation method of silver-carbon composite material aqueous solution, silver-carbon composite material aqueous solution, silver-carbon composite unit, conductor, and preparation method of conductor

The invention relates to a method for preparing a composite material, in particular to a method for preparing an aqueous solution of a silver-carbon composite material.

An electrochemical capacitor (also known as a supercapacitor) is an element that stores energy using an electroactive material or a conductor of a porous substance. The conductive body of the electroactive material or the porous material is mainly a metal-supported carbon material, and among them, a silver-carbon composite material is widely used as the conductive body. In terms of the technology for preparing the silver-carbon composite material, the general method is to first reduce the silver ions in the silver salt compound with alcohols to obtain silver metal particles, and then mix them with a carbon material in an aqueous solution by machine stirring or ultrasonic method. Made by. This practice can be found in Materials Transactions, Vol. 51, No. 10 (2010) pp. 1769.

Chinese Patent Publication No. 100434167C discloses a method for preparing a noble metal-supported carbon nano material, which includes the following steps: dispersing the carbon nano material in water to form a mixed solution, and then, dropping an aqueous solution containing a noble metal compound to The mixed solution is stirred at 20 ° C. to 25 ° C. for 5 minutes to 120 hours to form a noble metal-supported carbon nanomaterial aqueous solution. The noble metal-supported carbon nanomaterial aqueous solution includes water and noble metal-supported carbon. Nano materials. The noble metal-supported carbon nanomaterial material aqueous solution is subjected to centrifugal separation treatment and drying treatment to obtain the noble metal-supported carbon nanomaterial material. The noble metal particles in the noble metal-supported carbon nanomaterial have a particle size ranging from 3 nm to 5 μm.

Although the method for preparing the noble metal-supported carbon nanomaterial does not require a reducing agent, the obtained noble metal-supported carbon nanomaterial aqueous solution has poor dispersibility, and during the preparation or storage process, the noble metal-supported carbon Nanomaterials will precipitate from the noble metal-supported carbon nanomaterial aqueous solution, so that when using the noble metal-supported carbon nanomaterial aqueous solution, a further procedure is required to disperse the noble metal-supported carbon nanomaterial in water. There are problems with inconvenience.

Therefore, a first object of the present invention is to provide a method for preparing an aqueous solution of a silver-carbon composite material with good dispersibility and long shelf life.

Therefore, the preparation method of the silver-carbon composite material aqueous solution of the present invention includes the following steps: mixing water, a sulfonate-based anionic surfactant, and a plurality of unmodified carbon materials and performing an ultrasonic vibration treatment to make the The modified carbon material is dispersed in water to form a dispersed aqueous solution. Then, a plurality of atomized liquid droplets formed by the silver salt aqueous solution containing silver salt and water are added to the dispersed aqueous solution in a spraying manner, and the ultrasonic vibration treatment is continued. To form a silver-carbon composite material aqueous solution, wherein the size of the unmodified carbon material is nanometers or micrometers, the silver-carbon composite material aqueous solution includes the water and a plurality of silver-carbon composite materials dispersed in the water, and each silver The carbon composite material includes a plurality of silver metal nano particles and respective unmodified carbon materials for combining the silver metal nano particles.

The effect of the present invention is that through the sulfonate anionic surfactant and the ultrasonic vibration treatment, the unmodified carbon materials are uniformly dispersed in water without precipitation. In addition, the silver salt aqueous solution is contacted with the dispersed aqueous solution by atomizing droplets and spraying, and ultrasonic vibration processing is performed to mix the silver salt aqueous solution with the dispersed aqueous solution, so that at least most of the silver salts in the silver salt aqueous solution can be uniformly Disperse and bind to the unmodified carbon material in the dispersed aqueous solution, and reduce the silver salt to silver metal nano particles. Through the preparation method of the silver-carbon composite material aqueous solution of the present invention, the silver-carbon composite material aqueous solution can be quickly and simply formed, and the silver-carbon composite materials can be obtained without the participation of a reducing agent. At the same time, the formed silver The carbon composite material aqueous solution has good dispersibility, and the silver-carbon composite material does not precipitate from the silver-carbon composite material aqueous solution after long-term storage.

A second object of the present invention is to provide an aqueous silver-carbon composite material solution with good dispersibility and long storage life.

The silver-carbon composite material aqueous solution of the present invention comprises water and a plurality of silver-carbon composite materials dispersed in the water, wherein each silver-carbon composite material includes an unmodified carbon material and a plurality of silver dispersed on the unmodified carbon material. Metal nano particles, the size of the unmodified carbon material is nano or micron, the particle size of the silver metal nano particles ranges from 1nm to 25nm, based on the total amount of the silver-carbon composite materials, 100wt%, The total weight and range of the silver metal nano particles is 35 wt% or more.

A third object of the present invention is to provide a silver-carbon composite unit.

The silver-carbon composite unit of the present invention includes a plurality of silver-carbon composite materials, wherein each silver-carbon composite material includes an unmodified carbon material and a plurality of silver metal nano particles dispersed on the unmodified carbon material. The size of the carbon material is nanometers or micrometers, and the particle size of the silver metal nanoparticle ranges from 1nm to 25nm. Based on the total weight of the silver-carbon composite material, 100% by weight of the silver metal nanoparticle. The total weight and range are above 35 wt%.

A fourth object of the present invention is to provide a conductive body.

The electrical conductor of the present invention comprises a substrate and a plurality of silver-carbon composite materials dispersed on the substrate, wherein each silver-carbon composite material includes an unmodified carbon material and a plurality of silver-carbon composite materials dispersed on the unmodified carbon material. Silver metal nano particles, the size of the unmodified carbon material is nano or micron, the particle size range of the silver metal nano particles is from 1nm to 25nm, based on the total amount of the silver-carbon composite materials as 100wt% The total weight and range of the silver metal nano particles is above 35 wt%.

A fifth object of the present invention is to provide a method for preparing a conductor, comprising the steps of: contacting a substrate with an aqueous solution of a silver-carbon composite material, and subjecting the substrate contacted with the aqueous solution of the silver-carbon composite material to a treatment Wherein, the silver-carbon composite material aqueous solution includes water and a plurality of silver-carbon composite materials dispersed in the water, and each silver-carbon composite material includes an unmodified carbon material and a plurality of silver metals dispersed on the unmodified carbon material. Nano particles, the size of the unmodified carbon material is nano or micron, the particle size of the silver metal nano particles ranges from 1nm to 25nm, based on the total amount of the silver-carbon composite material being 100wt%, the The total weight and range of the iso-silver metal nano particles is more than 35 wt%, and the treatment includes a drying step.

The content of the present invention will be described in detail below.

The unmodified carbon material is selected from the group consisting of activated carbon, cellulose, carbon spheres, porous carbon materials, reticulated carbon materials, carbon rods, carbon fibers, graphene, graphite, and graphene oxide. Carbon nanotubes, fullerenes, or any combination thereof. The nano carbon tube is, for example, but not limited to, a single-walled carbon nanotube or a multi-walled carbon tube.

The sulfonate anionic surfactant can be selected as the surfactant that can help the unmodified carbon material to be dispersed in water. Preferably, the sulfonate anionic surfactant is selected from sodium dodecyl sulfate (abbreviated as SDS). The ultrasonic vibration treatment to form the dispersed aqueous solution is performed using an ultrasonic oscillator. Because the detailed structure of the ultrasonic oscillator is not the main technical feature of the present invention, and the ultrasonic oscillator is well known to those skilled in the art, for the sake of simplicity, the details are not described here. Preferably, the oscillating frequency of the ultrasonic oscillating process ranges from 1 kHZ to 20 kHZ. Preferably, the rated power range of the ultrasonic vibration processing is 1W to 750W. Preferably, the oscillating time of the ultrasonic oscillating process ranges from 1 minute to 30 minutes.

The atomized droplets are formed by dispersing and miniaturizing the silver salt aqueous solution using an atomizer. Because the detailed structure of the atomizer is not the main technical feature of the present invention, and the atomizer is well known to those skilled in the art, for the sake of simplicity, details are not described here.

The silver salt is selected from the group consisting of silver nitrate, silver nitrite, silver chloride, silver iodide, silver sulphate, silver lactate, and bromide. Silver bromide, silver acetate, silver thiocyanate, silver citrate, silver carbonate, or any combination thereof.

Preferably, during the addition of the atomized droplets formed by the silver salt aqueous solution, the temperature of the dispersed aqueous solution ranges from 40 ° C to 80 ° C. In order to make the size of the silver metal nano particles in the silver-carbon composite material range from 1 nm to 25 nm, more preferably, the temperature of the dispersed aqueous solution is added during the addition of the atomized droplets formed by the silver salt aqueous solution. The range is 40 ° C to 60 ° C. The temperature of the dispersed aqueous solution is adjusted by using an ice bath or a water bath. Preferably, based on the total amount of the silver-carbon composite materials being 100 wt%, the total weight and range of the silver metal nano particles is 48 wt% or more.

Preferably, the oscillating frequency of the ultrasonic oscillating process used to form the silver-carbon composite material aqueous solution ranges from 1 kHZ to 20 kHZ. Preferably, the rated power range of the ultrasonic vibration processing is 1W to 750W. Preferably, the oscillating time of the ultrasonic oscillating process ranges from 1 minute to 25 minutes.

The sulfonate-based anionic surfactant reacts with water to generate hydroxide ions. Because the unmodified carbon material has a SP ² blend and has a high activity, the hydroxide ions are bonded to the On the modified carbon material, the unmodified carbon material is provided with hydroxyl groups. After the silver nitrate aqueous solution is added, the heat and hydroxyl groups generated by the ultrasonic vibration treatment can cause the silver ions in the silver nitrate aqueous solution to be removed. It reduces and promotes crystallization to form silver metal nano particles.

The silver-carbon composite material aqueous solution of the present invention can be applied to an electrochemical cell as a part or all of a conductor (such as an electrode), can be applied to a conductive material (such as conductive ink, conductive textile, etc.), or can be applied to a medical material ( Such as antibacterial materials, anti-inflammatory materials, or drug delivery media).

By contacting the silver-carbon composite material aqueous solution of the present invention with a substrate and performing a treatment, a conductor for an electrochemical cell can be formed. The contacting is performed, for example, but not limited to, by coating or diping. The coating is, for example, but not limited to, spray coating or ink jet printing. The substrate is made of a material selected from the group consisting of a polysaccharide, a modified polysaccharide, a polyvinylpyrrolidone, a polyvinyl alcohol, and a polyvinyl ether ( polyvinyl ether, polyurethane, polyacrylate, polyacrylamide, collagen, gelatin, polyethylene terephthalate, polyester Fibers, or any combination thereof. The process includes a drying step.

The average surface resistance of the conductor of the present invention ranges from 10 ohm / cm ² to 150 ohm / cm ² .

The present invention will be further described with reference to the following examples, but it should be understood that this example is for illustrative purposes only and should not be construed as a limitation on the implementation of the present invention.

Example 1 Aqueous solution of silver-carbon composite material

An unmodified multi-walled carbon nanotube and sodium dodecyl sulfonate were arranged at a weight ratio of 1: 2, and added to 80 ml of deionized water and stirred for 5 minutes. Then, an ultrasonic oscillator (factory Brand: Sonics & Materials, Inc; Model: SONICS VCX750). The operating conditions of the ultrasonic vibration processing: the vibration time is 30 minutes, the vibration frequency is 20KHz, and the rated power is 750W. 20 ml of a 0.1 M silver nitrate aqueous solution is atomized into a plurality of atomized droplets through an atomizing bottle (including a bottle body for containing the silver nitrate aqueous solution and an atomizing nozzle installed at a bottle mouth of the bottle body). And sprayed into the dispersed aqueous solution four times, and continued the ultrasonic vibration treatment, and the dispersed aqueous solution was controlled to a temperature of 45 ° C through an ice bath to form a silver-carbon composite material aqueous solution. The silver-carbon composite material aqueous solution includes water, a plurality of silver-carbon composite materials dispersed in the water, and a plurality of silver metal nano particles dispersed in the water. The operating conditions of this ultrasonic vibration processing: the vibration time is 20 minutes, the vibration frequency is 20KHz, and the rated power is 750W. The silver metal nano-particles in the silver-carbon composite material have a particle diameter of 1 nm to 25 nm. Based on the total amount of the silver-carbon composite materials being 100 wt%, the total weight of the silver metal nano particles is 48 wt. %.

Example 2

An unmodified multi-walled carbon nanotube and sodium dodecyl sulfonate were arranged at a weight ratio of 1: 2, and added to 80 ml of deionized water and stirred for 5 minutes. Then, an ultrasonic oscillator (factory Brand: Sonics & Materials, Inc; Model: SONICS VCX750). The operating conditions of the ultrasonic vibration processing: the vibration time is 30 minutes, the vibration frequency is 20KHz, and the rated power is 750W. 20 ml of a 0.1 M silver nitrate aqueous solution was atomized into a plurality of atomized droplets through an atomizing bottle, and sprayed into the dispersed aqueous solution in four times, and the ultrasonic vibration treatment was continued to form an aqueous silver-carbon composite material solution, wherein: During the addition of the atomized droplets, the temperature of the dispersed aqueous solution was 70 ° C to 80 ° C. The silver-carbon composite material aqueous solution includes water, a plurality of silver-carbon composite materials dispersed in the water, and a plurality of silver metal nano particles dispersed in the water. The operating conditions of the ultrasonic vibration processing: the vibration time is 25 minutes, the vibration frequency is 20KHz, and the rated power is 750W. The silver metal nano-particles in the silver-carbon composite material have a particle diameter of about 50 nm to 100 nm. Based on the total amount of the silver-carbon composite materials being 100 wt%, the total weight of the silver metal nano-particles and It is 35 wt%.

Application Example 1 Electrode

Step (a): Cut the cotton cloth [consisting of cotton and polyester fiber] into 1x2 cm ² , remove impurities with 95% absolute alcohol, wash with deionized water, and perform a 20-minute Dry treatment to form a treated cotton cloth. Step (b): The treated cotton cloth was immersed in the silver-carbon composite material aqueous solution of Example 10 for 10 seconds, and after being taken out, it was dried in a vacuum environment for 45 minutes. Step (c): Wash with deionized water for 30 seconds to remove surface salts, silver metal nanoparticles and impurities that are not bound to the unmodified multi-walled carbon nanotubes, and dry in a vacuum environment for 20 minutes deal with. Step (d): Repeat steps (b) and (c) five times to form a cotton cloth containing silver-carbon composite material as an electrode.

Comparative Example 1

An unmodified multi-walled carbon nanotube and sodium dodecyl sulfonate were arranged at a weight ratio of 1: 2, and added to 80 ml of deionized water and stirred for 5 minutes. Then, an ultrasonic oscillator (factory Brand: Sonics & Materials, Inc; Model: SONICS VCX750). The operating conditions of the ultrasonic vibration processing: the vibration time is 30 minutes, the vibration frequency is 20KHz, and the rated power is 750W. 20 ml of a 0.1M silver nitrate aqueous solution was dropped into the dispersed aqueous solution through a dropper, and the ultrasonic vibration treatment was continued, and the dispersed aqueous solution was controlled to a temperature between 50 ° C and 60 ° C through an ice bath to form a silver-carbon composite Material aqueous solution. The silver-carbon composite material aqueous solution includes water, a plurality of silver-carbon composite materials, and a plurality of silver metal particles. The operating conditions of the ultrasonic vibration processing: the vibration time is 25 minutes, the vibration frequency is 20KHz, and the rated power is 750W. The silver metal particles in the silver-carbon composite material have a particle diameter of 200 nm to 1 μm. Based on the total amount of the silver-carbon composite materials being 100 wt%, the total weight of the silver metal particles is about 20 wt%.

Comparative Example 2

An unmodified multi-walled carbon nanotube and sodium dodecyl sulfonate were arranged at a weight ratio of 1: 2, and added to 80 ml of deionized water and stirred for 5 minutes. Then, an ultrasonic oscillator (factory Brand: Sonics & Materials, Inc; Model: SONICS VCX750). The operating conditions of the ultrasonic vibration processing: the vibration time is 30 minutes, the vibration frequency is 20KHz, and the rated power is 750W. 20 ml of a 0.1 M silver nitrate aqueous solution was atomized into a plurality of atomized droplets via an atomizing bottle, and sprayed into the dispersed aqueous solution in four times, and the magnet was stirred for 25 minutes, and the rotation speed was 1200 rpm to make the silver nitrate aqueous solution It is mixed with the dispersed aqueous solution to form a mixed solution, and the mixed solution includes water, a plurality of silver metal particles, and a plurality of unmodified multi-walled carbon nanotubes. The silver metal particles in the mixed solution had a particle diameter of more than 1 μm, and no silver-carbon composite material was formed.

Application Example 2, Comparative Application Example 1 and Comparative Application Example 2

Application Example 2, Comparative Application Examples 1 and 2 The electrodes were prepared in the same steps as in Application Example 1, except that three treated cotton cloths were immersed in the silver-carbon composite material aqueous solution of Example 2, respectively, and compared. The silver-carbon composite material aqueous solution of Example 1 and the mixed solution of Comparative Example 2.

Evaluation item

Crystal form analysis of silver-carbon composite material: The silver-carbon composite material aqueous solution of Example 1 was dried to remove water to obtain a silver-carbon composite material. The silver-carbon composite material was analyzed with an X-ray diffractometer (brand: BRUKER; model: D8 SSS), and the analysis conditions were: the target was copper; the scanning range was 10 degrees to 80 degrees. See Figure 1.

Structural analysis of silver-carbon composite materials: The electrodes of application example 1, application example 2, comparative application example 1, and comparative application example 2 were analyzed by a scanning electron microscope (brand: Zeiss; model: UltraPlus), and the analysis was performed. Conditions: The acceleration voltage is 3.5kv; the ambient pressure is 10 ^-5 torr. Please refer to FIG. 2, FIG. 4, FIG. 8 and FIG. 9, respectively.

Structural analysis of silver-carbon composite material: The silver-carbon composite material aqueous solution of Example 1 was filtered using a 0.2 μm syringe filter to obtain a filter cake. The filter cake was dried and analyzed by TEM (Transmission Electron Microscopy, brand: JEOL; model: JEM-2010), and the analysis conditions: the acceleration voltage was 200 kv. See Figure 3. The silver-carbon composite material aqueous solution of Example 2 was analyzed according to the above method, and refer to FIG. 5.

Identification and analysis of silver-carbon composite material: The electrode in Application Example 1 was washed with deionized water for 30 seconds, and dried in a vacuum environment for 15 minutes to form a test object. The D-band and G-band measurements were performed on the test object using a Raman spectrometer (brand: Tokyo Instruments .; model: Nanofinder 30; excitation light source: He-Ne Laser, 633 nm). The control group was a cotton cloth containing carbon nanotubes. The cotton cloth containing carbon nanotubes is formed by the following steps: Step (a): cut the cotton cloth into 1x2 cm ² , remove impurities with 95% absolute alcohol, wash with deionized water, and carry out under vacuum environment for 20 Minute drying treatment to form a treated cotton cloth. Step (b): The treated cotton cloth was immersed in the dispersed aqueous solution of Example 1 for 10 seconds, and after being taken out, it was dried in a vacuum environment for 45 minutes to form a cotton cloth containing carbon nanotubes.

Silver metal particle size analysis: The electrodes of application example 1, application example 2, comparative application example 1, and comparative application example 2 were analyzed by SigmaScan image measurement and analysis software.

Analysis of silver metal particle content: The electrodes of Application Example 1, Application Example 2 and Comparative Application Example 1 were analyzed with a thermogravimetric analyzer, and the heat loss weight when heated to 500 ° C (for cotton and unmodified) was calculated. The weight of the multi-walled carbon nanotubes), and then the weight of the electrode is used to deduct the weight of heat loss, which is the content of silver metal particles.

Storage period measurement: The silver-carbon composite material aqueous solution of Example 1 and the mixed solution of Comparative Example 2 were left to stand at 27 ° C. for 14 days, and the presence of precipitates was observed with the naked eye.

Referring to Figure 1, there are signal peaks at 2θ of 25 °, 38.31 °, 44.49 °, 64.61 °, and 77.53 °. According to JCPDS cards No. 04–0783, it can be seen that the carbon material is at 2 ° of 25 ° in Figure 1 Signal peaks, and 2θ at 38.31 degrees, 44.49 degrees, 64.61 degrees, and 77.53 degrees are face-centered cubic structure silver metal signal peaks. Therefore, it can be known that the silver-carbon composite material can be obtained by the method for preparing the silver-carbon composite material aqueous solution of the present invention.

Referring to FIG. 2, the strips are cotton fibers, and the spheres are silver metal nano particles. In FIG. 2, the silver-carbon composite material aqueous solution is coated on the cotton cloth, showing that the silver metal nano particles are dispersed on the cotton cloth without being agglomerated, indicating that the method of Example 1 would make the silver metal Nano particles are uniformly dispersed on the unmodified carbon materials, and the silver-carbon composite materials are uniformly dispersed in the water, so that the silver-carbon composite material aqueous solution can be uniformly dispersed and coated on the cotton cloth.

Referring to FIG. 4, the strips are cotton fibers, and the balls are silver metal nano particles. In FIG. 4, the silver-carbon composite material aqueous solution is coated on the cotton cloth, showing that the silver metal nano particles are dispersed on the cotton cloth without being agglomerated, indicating that the method of Example 2 would make the silver metal Nano particles are uniformly dispersed on the unmodified carbon materials, and the silver-carbon composite materials are uniformly dispersed in the water, so that the silver-carbon composite material aqueous solution can be uniformly dispersed and coated on the cotton cloth.

Referring to FIG. 3 and FIG. 5, the black dots indicate silver metal nano-particles bound to the multi-walled carbon carbon tube and silver metal nano-particles not bound to the multi-walled carbon carbon tube, and the strip is multi-walled Nano carbon tubes. In the silver salt aqueous solution of the present invention, the dispersed aqueous solution is contacted by atomized droplets and spraying, and the ultrasonic vibration treatment is used to mix the silver salt aqueous solution with the dispersed aqueous solution so that the silver metal nano particles can be uniformly dispersed and combined. On these unmodified carbon materials.

In FIG. 6, the two curves are the signal peaks of the unmodified multi-walled carbon nanotube and the signal peak of the silver-carbon composite material in the silver-carbon composite material aqueous solution of Example 1. D-band 1330 cm ^-1 represents sp ³ and G-band 1580 cm ^-1 represents sp ² . The ratio of the D-band signal strength to the G-band signal strength of the unmodified multi-walled carbon nanotube is 1.71, and the ratio of the D-band signal strength to the G-band signal strength of the silver-carbon composite material is 1.18. From this data, it can be seen that in the silver-carbon composite material, the structure of the unmodified multi-walled carbon nanotubes is disordered because silver metal nano-particles are bound to the unmodified multi-walled carbon tubes (sp ³ , sp ² ) rises, resulting in a plasmonic effect, which reduces the ratio of the D-band signal strength to the G-band signal strength.

Referring to FIG. 3, FIG. 7 and FIG. 10, the silver salt aqueous solution of the present invention contacts the dispersed aqueous solution by atomizing droplets and spraying, and performs ultrasonic vibration treatment to mix the silver salt aqueous solution with the dispersed aqueous solution to make the silver Metal nano particles can be uniformly dispersed and bound on the unmodified carbon materials (see FIG. 3). In addition, when the atomized droplets are added, no precipitate is formed in the formed aqueous solution of the silver-carbon composite material, which has good dispersibility (see Figure 7), and the silver-carbon composite is stored for a long time. The material does not precipitate from the silver-carbon composite aqueous solution (see Figure 10).

Referring to FIG. 8, the strips are cotton fibers, and the agglomerates are silver metal nano particles. In FIG. 8, the silver-carbon composite material aqueous solution is coated on cotton cloth, showing that the silver metal particles are unevenly dispersed and agglomerated. This shows that the silver salt aqueous solution in Comparative Example 1 was in contact with the dispersed aqueous solution in a dripping manner. , The silver metal particles cannot be uniformly dispersed and agglomerated on the unmodified carbon materials, and the silver-carbon composite materials cannot be uniformly dispersed in the water, so that the silver-carbon composite material aqueous solution cannot be uniform. The cotton cloth was dispersedly coated.

Referring to FIG. 9, the strips are cotton fibers, and the agglomerates are silver metal nano particles. In FIG. 9, the mixed solution was applied to cotton cloth, and the silver metal particles were unevenly dispersed and agglomerated. Referring again to FIG. 11, in FIG. 11, there are many fine particles on the bottle wall, indicating that the mixed solution of Comparative Example 2 is stored for a long time, and the silver metal particles and unmodified carbon materials will precipitate from the mixed solution. Come down.

The RTS-3 four-probe tester was used to measure the surface resistance of the electrodes of Application Example 1, Comparative Application Example 1 and Comparative Application Example 1 with a size of 1x1 cm ² and the cotton cloth containing carbon nanotubes described in paragraph [0044]. Surface resistance of cotton containing silver carbon composite material to the application example 1 of 100ohm / cm ^2, and Comparative Application Example 1 and the surface resistance of the electrode of Comparative Application Example 2 were 250 ohm / cm ² and greater than 300ohm / cm ^2, The surface resistance of the cotton cloth containing the carbon nanotube was 300 ohm / cm ² .

In summary, through the preparation method of the silver-carbon composite material aqueous solution of the present invention, the silver-carbon composite material aqueous solution can be formed quickly and simply, and the silver-carbon composite materials can be obtained without the participation of a reducing agent. The formed silver-carbon composite material aqueous solution has good dispersibility, and the silver-carbon composite material does not precipitate from the silver-carbon composite material aqueous solution after long-term storage, so it can indeed achieve the purpose of the present invention.

However, the above are only examples of the present invention. When the scope of implementation of the present invention cannot be limited by this, any simple equivalent changes and modifications made according to the scope of the patent application and the contents of the patent specification of the present invention are still Within the scope of the invention patent.

Other features and effects of the present invention will be clearly presented in the embodiments with reference to the drawings, in which: FIG. 1 is an X-ray diffraction spectrum diagram illustrating an embodiment 1 of a method for preparing an aqueous silver-carbon composite material solution according to the present invention; The silver-carbon composite material in the obtained silver-carbon composite material aqueous solution and the crystal form of the silver-carbon composite material are illustrated. FIG. 2 is a SEM image illustrating the silver-carbon composite material of the silver-carbon composite material aqueous solution obtained in Example 1. The silver metal nano particles will not be agglomerated; FIG. 3 is a TEM image illustrating that the silver metal nano particles in the silver-carbon composite material of the silver-carbon composite aqueous solution obtained in Example 1 are uniformly dispersed on the unmodified carbon material, and No agglomeration; FIG. 4 is a SEM image illustrating that the silver metal nanoparticle of the silver-carbon composite material of the silver-carbon composite material aqueous solution obtained in Example 6 does not agglomerate; FIG. 5 is a TEM image illustrating the obtained in Example 6 The silver metal nano particles in the silver-carbon composite material of the aqueous solution of the silver-carbon composite material are dispersed on the unmodified carbon material; Figure 6 is a Raman spectrum diagram illustrating the silver-carbon composite material of Example 1; Figure 7 is a photograph illustrating the Dispersibility of the aqueous solution of the silver-carbon composite material obtained in Example 1; FIG. 8 is a SEM image illustrating the aggregation of the silver metal particles of the silver-carbon composite material of the silver-carbon composite material aqueous solution obtained in Comparative Example 1; FIG. 9 is a SEM image The silver metal particles in the mixed liquid obtained in Comparative Example 2 will be agglomerated; FIG. 10 is a photograph illustrating the state of the silver-carbon composite material aqueous solution obtained in Example 1 after being left for two weeks; and FIG. 11 is a photograph, The state of the mixed liquid obtained in Comparative Example 2 after standing for two weeks will be described.

Claims (10)

A method for preparing a silver-carbon composite material aqueous solution includes the following steps: mixing water, a sulfonate-based anionic surfactant, and a plurality of unmodified carbon materials and performing an ultrasonic vibration treatment to make the unmodified carbons The material is dispersed in water to form a dispersed aqueous solution. Next, a plurality of atomized droplets formed by the silver salt aqueous solution containing silver salt and water are added to the dispersed aqueous solution in a spraying manner, and the ultrasonic vibration treatment is continued to form Silver-carbon composite material aqueous solution, wherein the size of the unmodified carbon material is nanometer or micron, the silver-carbon composite material aqueous solution includes the water and a plurality of silver-carbon composite materials dispersed in the water, and each silver-carbon composite material The method includes a plurality of silver metal nano particles and respective unmodified carbon materials for combining the silver metal nano particles. The method for preparing an aqueous solution of a silver-carbon composite material according to claim 1, wherein during the addition of the atomized droplets, the temperature of the dispersed aqueous solution is controlled at 40 ° C to 80 ° C. The method for preparing an aqueous solution of a silver-carbon composite material according to claim 2, wherein during the addition of the atomized droplets, the temperature of the dispersed aqueous solution is controlled to 40 ° C to 60 ° C. The method for preparing an aqueous solution of a silver-carbon composite material according to claim 1, wherein the unmodified carbon material is selected from the group consisting of activated carbon, cellulose, carbon spheres, porous carbon materials, reticulated carbon properties, and carbon rods. , Carbon fiber, graphene, graphite, graphene oxide, carbon nanotube, fullerene, or any combination thereof. The method for preparing an aqueous solution of a silver-carbon composite material according to claim 1, wherein the silver salt is selected from the group consisting of silver nitrate, silver nitrite, silver chloride, silver iodide, silver sulfate, silver lactate, silver bromide, silver acetate, and sulfur. Silver cyanate, citrate, carbonate, or any combination thereof. The method for preparing a silver-carbon composite material aqueous solution according to claim 1, wherein the sulfonate-based anionic surfactant is selected from sodium dodecylsulfonate. An aqueous silver-carbon composite material solution includes water and a plurality of silver-carbon composite materials dispersed in the water, wherein each silver-carbon composite material includes an unmodified carbon material and a plurality of silver dispersed on the unmodified carbon material. Metal nano particles, the size of the unmodified carbon material is nano or micron, the particle size of the silver metal nano particles ranges from 1nm to 25nm, based on the total amount of the silver-carbon composite materials, 100wt%, The total weight and range of the silver metal nano particles is 35 wt% or more. A silver-carbon composite unit includes a plurality of silver-carbon composite materials, wherein each silver-carbon composite material includes an unmodified carbon material and a plurality of silver metal nano particles dispersed on the unmodified carbon material. The size of the carbon material is nanometers or micrometers, and the particle size of the silver metal nanoparticle ranges from 1nm to 25nm. Based on the total amount of the silver-carbon composite material, the total weight of the silver metal nanoparticle is 100wt%. The weight and range are above 35 wt%. A conductor includes a substrate and a plurality of silver-carbon composite materials dispersed on the substrate, wherein each silver-carbon composite material includes an unmodified carbon material and a plurality of silver dispersed on the unmodified carbon material. Metal nano particles, the size of the unmodified carbon material is nano or micron, the particle size of the silver metal nano particles ranges from 1nm to 25nm, based on the total amount of the silver-carbon composite materials, 100wt%, The total weight and range of the silver metal nano particles is 35 wt% or more. A method for preparing a conductor includes the following steps: a substrate is contacted with an aqueous solution of silver-carbon composite material, and the substrate contacted with the aqueous solution of silver-carbon composite material is treated, wherein the aqueous solution of silver-carbon composite material includes Water and a plurality of silver-carbon composite materials dispersed in the water, each silver-carbon composite material includes an unmodified carbon material and a plurality of silver metal nano particles dispersed on the unmodified carbon material, the unmodified carbon material The size is nanometers or micrometers. The particle size of the silver metal nanoparticle ranges from 1nm to 25nm. Based on the total weight of the silver-carbon composite material, the total weight of the silver metal nanoparticle is The range is above 35 wt%, and the treatment includes a drying step.