TWI602199B - Preparation method of silver-carbon composite aqueous solution, silver-carbon composite aqueous solution, silver-carbon composite unit, electric conductor, and preparation method of electric conductor - Google Patents
Preparation method of silver-carbon composite aqueous solution, silver-carbon composite aqueous solution, silver-carbon composite unit, electric conductor, and preparation method of electric conductor Download PDFInfo
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本發明是有關於一種複合材料的製備方法，特別是指一種銀碳複合材料水溶液的製備方法。The invention relates to a preparation method of a composite material, in particular to a preparation method of an aqueous solution of a silver carbon composite material.
電化學電容(electrochemical Capacitor，又稱超級電容)是一種以電活性材料或多孔性物質的導電體來儲存能量的元件。該電活性材料或多孔性物質的導電體，以負載金屬的碳材料為主，其中，以銀碳複合材料廣泛被使用來作為導電體。在製備該銀碳複合材料的技術方面，一般的做法是先將銀鹽化合物中的銀離子以醇類還原取得銀金屬粒子後，再與一碳材在水溶液中用機器攪拌或超音波法混合所製得。該作法可參閱materials Transactions, Vol. 51, No. 10 (2010) pp. 1769。An electrochemical capacitor (also known as a supercapacitor) is an element that stores energy by means of an electroactive material or an electrical conductor of a porous substance. The conductor of the electroactive material or the porous material is mainly a metal-supporting carbon material, and a silver-carbon composite material is widely used as a conductor. In the technical aspect of preparing the silver-carbon composite material, the silver ion of the silver salt compound is first reduced with an alcohol to obtain silver metal particles, and then mixed 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.
中國大陸公告第100434167C號專利案揭示一種負載貴金屬的碳奈米材料的製備方法，包含以下步驟：將碳奈米材料分散於水中，形成一混合液，接著，將含有貴金屬化合物的水溶液滴加至該混合液中，並於20℃至25℃下攪拌5分鐘至120小時後，形成一負載貴金屬的碳奈米材料水溶液，其中，該負載貴金屬的碳奈米材料水溶液包含水及負載貴金屬的碳奈米材料。該負載貴金屬的碳奈米材料水溶液經離心分離處理及乾燥處理，得到該負載貴金屬的碳奈米材料。該負載貴金屬的碳奈米材料中的貴金屬粒子的粒子尺寸範圍為3nm至5μm。The Chinese Patent Publication No. 100434167C discloses a method for preparing a noble metal-loaded carbon nanomaterial, comprising the steps of dispersing a carbon nanomaterial in water to form a mixed solution, and then adding an aqueous solution containing a precious metal compound to the aqueous solution. After the mixture is stirred at 20 ° C to 25 ° C for 5 minutes to 120 hours, an aqueous solution of a noble metal-loaded carbon nanomaterial is formed, wherein the noble metal-loaded carbon nanomaterial aqueous solution contains water and a noble metal-loaded carbon. Nano material. The noble metal-loaded carbon nanomaterial aqueous solution is subjected to centrifugal separation treatment and drying treatment to obtain the noble metal-loaded carbon nanomaterial. The noble metal particles in the noble metal-loaded carbon nanomaterial have a particle size ranging from 3 nm to 5 μm.
雖然該負載貴金屬的碳奈米材料的製備方法不需還原劑，但所獲得的該負載貴金屬的碳奈米材料水溶液存在有分散性不佳，且於製備或儲存過程中，該負載貴金屬的碳奈米材料會自該負載貴金屬的碳奈米材料水溶液中沉澱下來，使得利用該負載貴金屬的碳奈米材料水溶液時，需再一道程序將該負載貴金屬的碳奈米材料分散於水中，而存在有使用不便的問題。Although the method for preparing the noble metal-loaded carbon nanomaterial does not require a reducing agent, the obtained noble metal-loaded carbon nanomaterial aqueous solution has poor dispersibility, and the noble metal-loaded carbon is prepared or stored. The nano material is precipitated from the noble metal-loaded carbon nanomaterial aqueous solution, so that when the noble metal-loaded carbon nanomaterial aqueous solution is used, the noble metal-loaded carbon nanomaterial is dispersed in water and exists in a procedure. There is a problem with inconvenience.
因此，本發明的第一目的，即在提供一種分散性佳且儲存期限長的銀碳複合材料水溶液的製備方法。Accordingly, a first object of the present invention is to provide a method for preparing an aqueous solution of a silver-carbon composite material having good dispersibility and long shelf life.
於是，本發明銀碳複合材料水溶液的製備方法，包含以下步驟：將水、磺酸鹽系陰離子型界面活性劑及複數未修飾的碳材混合並進行一超音波震盪處理，以使該等未修飾的碳材分散於水中，形成一分散水溶液，接著，將複數由包含銀鹽及水的銀鹽水溶液所形成的霧化液滴以噴灑方式加入該分散水溶液，並持續進行該超音波震盪處理，以形成銀碳複合材料水溶液，其中，該未修飾的碳材的尺寸為奈米或微米，該銀碳複合材料水溶液包含該水及複數分散在該水中的銀碳複合材料，且每一個銀碳複合材料包括複數個銀金屬奈米粒子及供該等銀金屬奈米粒子結合的各別的未修飾的碳材。Therefore, the method for preparing an aqueous solution of the silver-carbon composite material of the present invention comprises the steps of 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, and then a plurality of atomized droplets formed from an aqueous solution of a silver salt containing silver salt and water are sprayed into the dispersed aqueous solution, and the ultrasonic oscillation is continuously performed. To form an aqueous solution of a silver-carbon composite material, wherein the unmodified carbon material has a size of nanometer or micrometer, and the aqueous solution of the silver-carbon composite material comprises 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 nanoparticles and respective unmodified carbon materials for bonding the silver metal nanoparticles.
本發明的功效在於：透過該磺酸鹽系陰離子型界面活性劑及該超音波震盪處理，使該等未修飾的碳材均勻地分散於水中，而不會沉澱。且該銀鹽水溶液以霧化液滴搭配噴灑方式接觸該分散水溶液，並採超音波震盪處理使該銀鹽水溶液與該分散水溶液混合，使該銀鹽水溶液中的至少大部分銀鹽可均勻地分散並結合於該分散水溶液中的未修飾的碳材上，並使該銀鹽還原成銀金屬奈米粒子。透過本發明銀碳複合材料水溶液的製備方法，可快速且簡單的形成該銀碳複合材料水溶液，且在不需要還原劑的參與下，獲得該等銀碳複合材料，同時，所形成的該銀碳複合材料水溶液具有分散性佳，且長時間儲存下該等銀碳複合材料不會自該銀碳複合材料水溶液中沉澱下來。The effect of the present invention is that the unmodified carbon material is uniformly dispersed in water through the sulfonate anionic surfactant and the ultrasonic vibration treatment without precipitation. And the silver salt aqueous solution contacts the dispersed aqueous solution by atomizing droplets in a sprayed manner, and ultrasonically oscillates to mix the silver salt aqueous solution with the dispersed aqueous solution, so that at least a majority of the silver salt in the silver salt aqueous solution can be uniformly Dispersing and binding to the unmodified carbon material in the dispersed aqueous solution, and reducing the silver salt to silver metal nanoparticles. Through the preparation method of the silver carbon composite aqueous solution of the invention, the silver carbon composite aqueous solution can be formed quickly and simply, and the silver carbon composite material is obtained without the participation of a reducing agent, and at the same time, the silver is formed. The aqueous solution of the carbon composite material has good dispersibility, and the silver-carbon composite material does not precipitate from the aqueous solution of the silver-carbon composite material under long-term storage.
本發明的第二目的，即在提供一種分散性佳且儲存期限長的銀碳複合材料水溶液。A second object of the present invention is to provide an aqueous solution of a silver-carbon composite material which is excellent in dispersibility and has a long shelf life.
本發明銀碳複合材料水溶液，包含水及複數分散於該水中的銀碳複合材料，其中，每一銀碳複合材料包括一未修飾的碳材及複數分散在該未修飾的碳材上的銀金屬奈米粒子，該未修飾的碳材的尺寸為奈米或微米，該等銀金屬奈米粒子的粒徑範圍為1nm至25nm，以該等銀碳複合材料的總量為100wt%計，該等銀金屬奈米粒子的總重量和範圍為35wt%以上。The silver carbon composite 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 comprises an unmodified carbon material and a plurality of silver dispersed on the unmodified carbon material. a metal nanoparticle having a size of nanometer or micrometer, wherein the silver metal nanoparticle has a particle diameter ranging from 1 nm to 25 nm, and the total amount of the silver carbon composite is 100% by weight. The total weight and range of the silver metal nanoparticles are 35 wt% or more.
本發明的第三目的，即在提供一種銀碳複合單元。A third object of the present invention is to provide a silver carbon composite unit.
本發明銀碳複合單元，包含複數銀碳複合材料，其中，每一銀碳複合材料包括一未修飾的碳材及複數分散在該未修飾的碳材上的銀金屬奈米粒子，該未修飾的碳材的尺寸為奈米或微米，該等銀金屬奈米粒子的粒徑範圍為1nm至25nm，以該等銀碳複合材料的總量為100wt%計，該等銀金屬奈米粒子的總重量和範圍為35wt%以上。The silver-carbon composite unit of the present invention comprises a plurality of silver-carbon composite materials, wherein each of the silver-carbon composite materials comprises an unmodified carbon material and a plurality of silver metal nanoparticles dispersed on the unmodified carbon material, the unmodified The carbon material has a size of nanometer or micrometer, and the silver metal nanoparticle has a particle diameter ranging from 1 nm to 25 nm, and the total amount of the silver-carbon composite material is 100% by weight, and the silver metal nanoparticle is The total weight and range are 35 wt% or more.
本發明的第四目的，即在提供一種導電體。A fourth object of the present invention is to provide an electrical conductor.
本發明導電體，包含一基材及複數分散在該基材上的銀碳複合材料，其中，每一銀碳複合材料包括一未修飾的碳材及複數分散在該未修飾的碳材上的銀金屬奈米粒子，該未修飾的碳材的尺寸為奈米或微米，該等銀金屬奈米粒子的粒徑範圍為1nm至25nm，以該等銀碳複合材料的總量為100wt%計，該等銀金屬奈米粒子的總重量和範圍為35wt%以上。The electrical conductor of the present invention comprises a substrate and a plurality of silver-carbon composite materials dispersed on the substrate, wherein each of the silver-carbon composite materials comprises an unmodified carbon material and a plurality of particles dispersed on the unmodified carbon material. a silver metal nanoparticle having a size of nanometer or micrometer, wherein the silver metal nanoparticle has a particle diameter ranging from 1 nm to 25 nm, and the total amount of the silver carbon composite is 100 wt% The total weight and range of the silver metal nanoparticles are 35 wt% or more.
本發明的第五目的，即在提供一種導電體的製備方法，包含以下步驟：將一基材與一銀碳複合材料水溶液接觸，並將與該銀碳複合材料水溶液接觸的基材進行一處理，其中，該銀碳複合材料水溶液包含水及複數分散於該水中的銀碳複合材料，每一銀碳複合材料包括一未修飾的碳材及複數分散在該未修飾的碳材上的銀金屬奈米粒子，該未修飾的碳材的尺寸為奈米或微米，該等銀金屬奈米粒子的粒徑範圍為1nm至25nm，以該等銀碳複合材料的總量為100wt%計，該等銀金屬奈米粒子的總重量和範圍為35wt%以上，該處理包含一乾燥步驟。A fifth object of the present invention is to provide a method for preparing an electrical conductor comprising the steps of: contacting a substrate with an aqueous solution of a silver-carbon composite material, and subjecting the substrate in contact with the aqueous solution of the silver-carbon composite material to a treatment. The silver carbon composite aqueous solution comprises water and a plurality of silver-carbon composite materials dispersed in the water, and each of the silver-carbon composite materials comprises an unmodified carbon material and a plurality of silver metals dispersed on the unmodified carbon material. a nanoparticle having a size of nanometer or micrometer, wherein the silver metal nanoparticle has a particle size ranging from 1 nm to 25 nm, and the total amount of the silver carbon composite is 100 wt%, The total weight and range of the silver metal nanoparticles are more than 35 wt%, and the treatment comprises a drying step.
以下將就本發明內容進行詳細說明。The contents of the present invention will be described in detail below.
該未修飾的碳材是選自於活性碳、纖維素(cellulose)、碳球、多孔性碳材、網狀性碳材、碳棒、碳纖維、石墨烯、石墨、氧化石墨烯(graphene oxide)、奈米碳管、富勒烯(fullerene)，或上述任意組合。該奈米碳管例如但不限於單壁奈米碳管或多壁奈米碳管。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, graphene oxide. , carbon nanotubes, fullerene, or any combination of the above. The carbon nanotubes are, for example but not limited to, single-walled carbon nanotubes or multi-walled carbon nanotubes.
該磺酸鹽系陰離子型界面活性劑的選擇以能協助該未修飾的碳材分散於水中的界面活性劑皆可。較佳地，該磺酸鹽系陰離子型界面活性劑選自於十二烷基磺酸鈉(sodium dodecyl sulfate，簡稱SDS )。用以形成該分散水溶液的該超音波震盪處理是利用一超音波震盪器來進行。因為該超音波震盪器的細部構造並非本發明主要的技術特徵，且該超音波震盪器為本領域技術人員所公知的，為了精簡的因素，故細節在此不多作說明。較佳地，該超音波震盪處理的震盪頻率範圍為1kHZ 至20kHZ。較佳地，該超音波震盪處理的額定功率範圍為1W至750W。較佳地，該超音波震盪處理的震盪時間範圍為1分鐘至30分鐘。The sulfonate anionic surfactant is selected to be a surfactant which can assist the unmodified carbon material to be dispersed in water. Preferably, the sulfonate anionic surfactant is selected from the group consisting of sodium dodecyl sulfate (SDS). The ultrasonic oscillation process for forming the dispersed aqueous solution is performed using an ultrasonic oscillator. Since the detailed construction of the ultrasonic oscillator is not a primary technical feature of the present invention, and the ultrasonic oscillator is well known to those skilled in the art, the details are not described here for the sake of streamlining. Preferably, the ultrasonic oscillation process has an oscillation frequency ranging from 1 kHZ to 20 kHz. Preferably, the ultrasonic oscillation process has a power rating ranging from 1W to 750W. Preferably, the ultrasonic oscillation process has an oscillation time ranging from 1 minute to 30 minutes.
該等霧化液滴的形成是利用一霧化器使該銀鹽水溶液分散且微小化而形成。因為該霧化器的細部構造並非本發明主要的技術特徵，且該霧化器為本領域技術人員所公知的，為了精簡的因素，故細節在此不多作說明。The formation of the atomized droplets is formed by dispersing and miniaturizing the aqueous silver salt solution using an atomizer. Since the detailed construction of the atomizer is not a primary technical feature of the present invention, and the atomizer is well known to those skilled in the art, the details are not described herein for the sake of streamlining.
該銀鹽選自於硝酸銀(silver nitrate)、亞硝酸銀(silver nitrite)、氯化銀(silver chloride)、碘化銀(silver iodide)、硫酸銀(silver sulphate)、乳酸銀(silver lactate)、溴化銀(silver bromide)、醋酸銀(silver acetate)、硫氰酸銀(silver thiocyanate)、檸檬酸鹽(silver citrate)、碳酸鹽(silver carbonate)，或上述任意組合。The silver salt is selected from the group consisting of silver nitrate, silver nitrite, silver chloride, silver iodide, silver sulphate, silver lactate, and bromination. Silver bromide, silver acetate, silver thiocyanate, silver citrate, silver carbonate, or any combination thereof.
較佳地，在加入由該銀鹽水溶液所形成的該等霧化液滴的期間，該分散水溶液的溫度範圍為40℃至80℃。為使該銀碳複合材料中的銀金屬奈米粒子的尺寸範圍為1nm至25nm，更佳地，在加入由該銀鹽水溶液所形成的該等霧化液滴的期間，該分散水溶液的溫度範圍為40℃至60℃。該分散水溶液的溫度的調控是用冰浴或水浴來進行。較佳地，以該等銀碳複合材料的總量為100wt%計，該等銀金屬奈米粒子的總重量和範圍為48wt%以上。Preferably, the temperature of the dispersed aqueous solution ranges from 40 ° C to 80 ° C during the addition of the atomized droplets formed from the aqueous silver salt solution. In order to make the size of the silver metal nanoparticles in the silver-carbon composite material ranging from 1 nm to 25 nm, more preferably, the temperature of the dispersed aqueous solution during the addition of the atomized droplets formed by the aqueous solution of the silver salt The range is from 40 ° C to 60 ° C. The temperature of the dispersed aqueous solution is controlled by an ice bath or a water bath. Preferably, the total weight and range of the silver metal nanoparticles are 48% by weight or more based on 100% by weight of the total of the silver-carbon composite materials.
較佳地，用以形成該銀碳複合材料水溶液的超音波震盪處理的震盪頻率範圍為1kHZ 至20kHZ。較佳地，該超音波震盪處理的額定功率範圍為1W至750W。較佳地，該超音波震盪處理的震盪時間範圍為1分鐘至25分鐘。Preferably, the ultrasonic oscillation process for forming the aqueous solution of the silver-carbon composite material has an oscillation frequency ranging from 1 kHZ to 20 kHZ. Preferably, the ultrasonic oscillation process has a power rating ranging from 1W to 750W. Preferably, the ultrasonic oscillation process has an oscillation time ranging from 1 minute to 25 minutes.
因磺酸鹽系陰離子型界面活性劑與水會反應，產生氫氧根離子，因該未修飾的碳材本身具有SP 2混成，而具有較高活性，使得氫氧根離子鍵結於該未修飾的碳材上，而使該未修飾的碳材帶有氫氧基，當硝酸銀水溶液加入後，透過超音波震盪處理產生的熱以及氫氧基，可使硝酸銀水溶液的硝酸銀中的銀離子被還原並促使結晶作用產生，而形成銀金屬奈米粒子。 The sulfonate anionic surfactant reacts with water to produce hydroxide ions, since the unmodified carbon material itself has SP 2 mixing and has higher activity, so that the hydroxide ions are bonded to the undoped On the modified carbon material, the unmodified carbon material is provided with a hydroxyl group. When the silver nitrate aqueous solution is added, the silver ions in the silver nitrate solution can be silver ions in the silver nitrate aqueous solution by the heat generated by the ultrasonic vibration treatment and the hydroxyl group. Reduction and crystallization are caused to form silver metal nanoparticles.
本發明該銀碳複合材料水溶液可應用至電化學電池中作為一導電體(例如電極)的一部分或全部、可應用至導電材料(例如導電墨水、導電紡織等)，或可應用至醫療材料(例如抗菌材料、消炎材料，或藥物傳遞介質)等上。The silver carbon composite aqueous solution of the present invention can be applied to an electrochemical cell as a part or all of an electric conductor (for example, an electrode), can be applied to a conductive material (for example, conductive ink, conductive textile, etc.), or can be applied to medical materials ( For example, antibacterial materials, anti-inflammatory materials, or drug delivery media).
將本發明該銀碳複合材料水溶液接觸一基材並進行一處理，即可形成電化學電池用的導電體。該接觸例如但不限於利用塗佈(coating)或含浸(diping)來進行。該塗佈例如但不限於噴塗塗佈(spray coating)或噴墨印刷(ink jet printing)等。該基材是由一材料所製得，且該材料選自於多醣(polysaccharide)、經修飾的多醣(modified polysaccharide)、聚乙烯吡咯烷酮(polyvinylpyrrolidone)、聚乙烯醇(polyvinyl alcohol)、聚乙烯醚(polyvinyl ether)、聚胺酯(polyurethane)、聚丙烯酸酯(polyacrylate)、聚丙烯醯胺(polyacrylamide)、膠原蛋白(collagen)、明膠(gelatin)、聚對苯二甲酸乙二酯(polyethylene terephthalate)、聚酯纖維(polyester)，或上述任意組合。該處理包含一乾燥步驟。The aqueous solution of the silver-carbon composite material of the present invention is contacted with a substrate and subjected to a treatment to form an electrical conductor for an electrochemical cell. This contact is 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 Polyester, or any combination of the above. This treatment involves a drying step.
本發明導電體的平均表面電阻範圍為10ohm/cm 2至 150ohm/cm 2。 The electrical conductors of the present invention have an average surface resistance ranging from 10 ohm/cm 2 to 150 ohm/cm 2 .
本發明將就以下實施例來作進一步說明，但應瞭解的是，該實施例僅為例示說明之用，而不應被解釋為本發明實施之限制。The present invention will be further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting.
實施例1 銀碳複合材料水溶液Example 1 Silver carbon composite aqueous solution
將未修飾的多壁奈米碳管與十二烷基磺酸鈉以重量比1:2配置，並加入至80毫升的去離子水中攪拌5分鐘，接著，置入一超音波震盪器(廠牌: Sonics & Materials, Inc；型號：SONICS VCX750)中進行超音波震盪處理，形成一分散水溶液。該超音波震盪處理的操作條件：震盪時間為30分鐘、震盪頻率為20KHz、額定功率為750W。將20毫升的0.1M硝酸銀水溶液經由一霧化瓶(包含一用來容置該硝酸銀水溶液的瓶身及一安裝在該瓶身的一瓶口處的霧化噴嘴)霧化成複數霧化液滴，並分四次噴灑至該分散水溶液中，並持續進行該超音波震盪處理，且該分散水溶液透過冰浴將溫度控制在45℃間，形成銀碳複合材料水溶液。該銀碳複合材料水溶液包含水、複數分散在該水中的銀碳複合材料及複數分散於該水中的銀金屬奈米粒子。該超音波震盪處理的操作條件：震盪時間為20分鐘、震盪頻率為20KHz、額定功率為750W。該銀碳複合材料中的該等銀金屬奈米粒子的粒徑為1nm至25nm，以該等銀碳複合材料的總量為100wt%計，該等銀金屬奈米粒子的總重量和為48wt%。The unmodified multi-walled carbon nanotubes and sodium dodecyl sulfate were disposed at a weight ratio of 1:2, and added to 80 ml of deionized water for 5 minutes, and then placed in an ultrasonic oscillator (factory) Card: Sonics & Materials, Inc; Model: SONICS VCX750) Ultrasonic vibration treatment to form a dispersed aqueous solution. The operating conditions of the ultrasonic oscillation processing are: the oscillation time is 30 minutes, the oscillation frequency is 20 KHz, and the rated power is 750 W. 20 ml of a 0.1 M aqueous solution of silver nitrate was atomized into a plurality of atomized droplets via an atomizing flask (containing a bottle for containing the aqueous solution of silver nitrate and an atomizing nozzle installed at a mouth of the bottle) And spraying into the dispersed aqueous solution in four times, and the ultrasonic vibration treatment was continued, and the dispersed aqueous solution was controlled to a temperature of 45 ° C through an ice bath to form an aqueous solution of a silver-carbon composite material. The silver carbon composite aqueous solution contains water, a plurality of silver-carbon composite materials dispersed in the water, and a plurality of silver metal nanoparticles dispersed in the water. The operating conditions of the ultrasonic oscillation processing are: an oscillating time of 20 minutes, an oscillating frequency of 20 kHz, and a rated power of 750 watts. The silver metal nano particles in the silver carbon composite material have a particle diameter of 1 nm to 25 nm, and the total weight of the silver metal nano particles is 48 wt% based on the total amount of the silver carbon composite materials. %.
實施例2Example 2
將未修飾的多壁奈米碳管與十二烷基磺酸鈉以重量比1:2配置，並加入至80毫升的去離子水中攪拌5分鐘，接著，置入一超音波震盪器(廠牌: Sonics & Materials, Inc；型號：SONICS VCX750)中進行超音波震盪處理，形成一分散水溶液。該超音波震盪處理的操作條件：震盪時間為30分鐘、震盪頻率為20KHz、額定功率為750W。將20毫升的0.1M硝酸銀水溶液經由一霧化瓶霧化成複數霧化液滴，並分四次噴灑至該分散水溶液中，並持續進行該超音波震盪處理，形成銀碳複合材料水溶液，其中，在加入該等霧化液滴的期間，該分散水溶液的溫度為70℃至80℃。該銀碳複合材料水溶液包含水、複數分散在該水中的銀碳複合材料及複數分散於該水中的銀金屬奈米粒子。該超音波震盪處理的操作條件：震盪時間為25分鐘、震盪頻率為20KHz、額定功率為750W。該銀碳複合材料中的該等銀金屬奈米粒子的粒徑為約50nm至100nm，以該等銀碳複合材料的總量為100wt%計，該等銀金屬奈米粒子的總重量和約為35wt%。The unmodified multi-walled carbon nanotubes and sodium dodecyl sulfate were disposed at a weight ratio of 1:2, and added to 80 ml of deionized water for 5 minutes, and then placed in an ultrasonic oscillator (factory) Card: Sonics & Materials, Inc; Model: SONICS VCX750) Ultrasonic vibration treatment to form a dispersed aqueous solution. The operating conditions of the ultrasonic oscillation processing are: the oscillation time is 30 minutes, the oscillation frequency is 20 KHz, and the rated power is 750 W. 20 ml of 0.1 M aqueous silver nitrate solution is atomized into a plurality of atomized droplets through an atomization bottle, and sprayed into the dispersed aqueous solution in four times, and the ultrasonic vibration treatment is continued to form an aqueous solution of silver carbon composite material, wherein The temperature of the dispersed aqueous solution is from 70 ° C to 80 ° C during the addition of the atomized droplets. The silver carbon composite aqueous solution contains water, a plurality of silver-carbon composite materials dispersed in the water, and a plurality of silver metal nanoparticles dispersed in the water. The operating conditions of the ultrasonic oscillation processing are: an oscillation time of 25 minutes, an oscillation frequency of 20 KHz, and a rated power of 750 W. The silver metal nano particles in the silver-carbon composite material have a particle diameter of about 50 nm to 100 nm, and the total weight of the silver metal nano particles is about 100% by weight based on the total amount of the silver-carbon composite materials. It is 35 wt%.
應用例1 電極Application Example 1 Electrode
步驟(a)：將棉布[由棉(cotton)及聚酯纖維所構成]裁成1x2 cm 2，用95%無水酒精清除雜質，再用去離子水清洗，並於真空環境下進行20 分鐘的乾燥處理，形成一經處理的棉布。步驟(b)：將該經處理的棉布浸泡於實施例1的銀碳複合材料水溶液中10秒，取出後，於真空環境下進行45分鐘的乾燥處理。步驟(c)：使用去離子水清洗30秒，以去除表面的鹽類、未結合在未修飾的多壁奈米碳管的銀金屬奈米粒子和雜質，於真空環境下進行20分鐘的乾燥處理。步驟(d)；重複步驟(b)及(c)共五次，形成一作為電極的含有銀碳複合材料的棉布。 Step (a): Cut cotton cloth [consisting of cotton and polyester fiber] into 1x2 cm 2 , remove impurities with 95% absolute alcohol, wash with deionized water, and carry out in vacuum for 20 minutes. Drying treatment forms a treated cotton cloth. Step (b): The treated cotton cloth was immersed in the silver carbon composite aqueous solution of Example 1 for 10 seconds, taken out, and dried in a vacuum atmosphere for 45 minutes. Step (c): washing with deionized water for 30 seconds to remove surface salts, silver metal nanoparticles and impurities not bound to unmodified multi-walled carbon nanotubes, and dried in a vacuum for 20 minutes. deal with. Step (d); repeating steps (b) and (c) a total of five times to form a cotton cloth containing a silver-carbon composite material as an electrode.
比較例1Comparative example 1
將未修飾的多壁奈米碳管與十二烷基磺酸鈉以重量比1:2配置，並加入至80毫升的去離子水中攪拌5分鐘，接著，置入一超音波震盪器(廠牌: Sonics & Materials, Inc；型號：SONICS VCX750)中進行超音波震盪處理，形成一分散水溶液。該超音波震盪處理的操作條件：震盪時間為30分鐘、震盪頻率為20KHz、額定功率為750W。將20毫升的0.1M硝酸銀水溶液透過一滴管滴入至該分散水溶液中，並持續進行該超音波震盪處理，且該分散水溶液透過冰浴將溫度控制在50℃至60℃間，形成銀碳複合材料水溶液。該銀碳複合材料水溶液包括水、複數銀碳複合材料及複數銀金屬粒子。該超音波震盪處理的操作條件：震盪時間為25分鐘、震盪頻率為20KHz、額定功率為750W。該銀碳複合材料中的該等銀金屬粒子的粒徑為200nm至1μm，以該等銀碳複合材料的總量為100wt%計，該等銀金屬粒子的總重量和約為20wt%。The unmodified multi-walled carbon nanotubes and sodium dodecyl sulfate were disposed at a weight ratio of 1:2, and added to 80 ml of deionized water for 5 minutes, and then placed in an ultrasonic oscillator (factory) Card: Sonics & Materials, Inc; Model: SONICS VCX750) Ultrasonic vibration treatment to form a dispersed aqueous solution. The operating conditions of the ultrasonic oscillation processing are: the oscillation time is 30 minutes, the oscillation frequency is 20 KHz, and the rated power is 750 W. 20 ml of a 0.1 M aqueous solution of silver nitrate 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. Aqueous material solution. The silver carbon composite aqueous solution includes water, a plurality of silver carbon composite materials, and a plurality of silver metal particles. The operating conditions of the ultrasonic oscillation processing are: an oscillation time of 25 minutes, an oscillation frequency of 20 KHz, and a rated power of 750 W. The silver metal particles in the silver-carbon composite material have a particle diameter of 200 nm to 1 μm, and the total weight of the silver metal particles is about 20% by weight based on 100% by weight of the total of the silver-carbon composite materials.
比較例2Comparative example 2
將未修飾的多壁奈米碳管與十二烷基磺酸鈉以重量比1:2配置，並加入至80毫升的去離子水中攪拌5分鐘，接著，置入一超音波震盪器(廠牌: Sonics & Materials, Inc；型號：SONICS VCX750)中進行超音波震盪處理，形成一分散水溶液。該超音波震盪處理的操作條件：震盪時間為30分鐘、震盪頻率為20KHz、額定功率為750W。將20毫升的0.1M硝酸銀水溶液經由一霧化瓶霧化成複數霧化液滴，並分四次噴灑至該分散水溶液中，利用磁石進行25分鐘的攪拌，且轉速為1200rpm，以使該硝酸銀水溶液與該分散水溶液混合，形成一混合液，且該混合液包含水、複數銀金屬粒子及複數未修飾的多壁奈米碳管。該混合液中的該等銀金屬粒子的粒徑為大於1μm，且未形成有銀碳複合材料。The unmodified multi-walled carbon nanotubes and sodium dodecyl sulfate were disposed at a weight ratio of 1:2, and added to 80 ml of deionized water for 5 minutes, and then placed in an ultrasonic oscillator (factory) Card: Sonics & Materials, Inc; Model: SONICS VCX750) Ultrasonic vibration treatment to form a dispersed aqueous solution. The operating conditions of the ultrasonic oscillation processing are: the oscillation time is 30 minutes, the oscillation frequency is 20 KHz, and the rated power is 750 W. 20 ml of 0.1 M aqueous silver nitrate solution was atomized into a plurality of atomized droplets through an atomization bottle, and sprayed into the dispersed aqueous solution four times, and stirred by a magnet for 25 minutes at a rotation speed of 1200 rpm to make the silver nitrate aqueous solution. The mixed aqueous solution is mixed to form a mixed liquid, and the mixed liquid contains water, a plurality of silver metal particles, and a plurality of unmodified multi-walled carbon nanotubes. The silver metal particles in the mixed solution have a particle diameter of more than 1 μm and no silver-carbon composite material is formed.
應用例2、比較應用例1及比較應用例2Application Example 2, Comparative Application Example 1 and Comparative Application Example 2
應用例2、比較應用例1及2是以與應用例1相同的步驟來製備電極，不同的地方在於：是將三個經處理的棉布分別浸泡於實施例2的銀碳複合材料水溶液、比較例1的銀碳複合材料水溶液及及比較例2的混合液中。Application Example 2, Comparative Application Examples 1 and 2 were prepared by the same procedure as in Application Example 1, except that three treated cotton fabrics were respectively immersed in the silver carbon composite aqueous solution of Example 2, and compared. The silver carbon composite aqueous solution of Example 1 and the mixed liquid of Comparative Example 2.
評價項目Evaluation project
銀碳複合材料晶型分析：將實施例1的銀碳複合材料水溶液乾燥以移除水，得到銀碳複合材料。將銀碳複合材料以X-ray繞射儀(廠牌：BRUKER；型號： D8 SSS)進行分析，且該分析條件：靶材為銅；掃瞄範圍為10度至80度。參閱圖1。Crystalline Analysis of Silver Carbon Composite: The aqueous solution of the silver-carbon composite of Example 1 was dried to remove water to obtain a silver-carbon composite. The silver-carbon composite material was analyzed by an X-ray diffractometer (label: BRUKER; model: D8 SSS), and the analysis conditions were as follows: the target was copper; the scanning range was 10 to 80 degrees. See Figure 1.
銀碳複合材料結構分析：分別將應用例1、應用例2、比較應用例1及比較應用例2的電極以SEM(Scanning electron microscope，廠牌：Zeiss；型號：UltraPlus)進行分析，且該分析條件：加速電壓為3.5kv；環境壓力為 10 -5torr。分別參閱圖2、圖4、圖8及圖9。 Structural analysis of silver carbon composites: The electrodes of Application Example 1, Application Example 2, Comparative Application Example 1 and Comparative Application Example 2 were respectively analyzed by SEM (Scanning electron microscope, brand: Zeiss; model: UltraPlus), and the analysis was performed. Conditions: Acceleration voltage is 3.5kv; ambient pressure is 10 -5 torr. See Figures 2, 4, 8, and 9, respectively.
銀碳複合材料結構分析：將實施例1的銀碳複合材料水溶液使用0.2μm的針筒過濾器進行過濾，得到濾餅。將該濾餅進行乾燥，並以TEM(Transmission Electron Microscopy，廠牌：JEOL；型號：JEM-2010)進行分析，且該分析條件：加速電壓為200kv。參閱圖3。將實施例2的銀碳複合材料水溶液依據上述方法進行分析，參閱圖5。Structural Analysis of Silver Carbon Composite Material: The silver carbon composite 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 were as follows: the acceleration voltage was 200 kV. See Figure 3. The silver carbon composite aqueous solution of Example 2 was analyzed in accordance with the above method, see Fig. 5.
銀碳複合材料鑑定分析：將應用例1中的電極以去離子水清洗30秒，於真空環境下進行15分鐘的乾燥處理，形成一待測物。將該待測物以拉曼光譜儀(廠牌：Tokyo Instruments.；型號：Nanofinder 30；激發光源：He-Ne Laser，633nm)進行D-band及G-band量測。對照組為含有奈米碳管的棉布。該含有奈米碳管的棉布是由以下步驟所形成：步驟(a)：將棉布裁成1x2 cm 2，用95%無水酒精清除雜質，再用去離子水清洗，並於真空環境下進行20 分鐘的乾燥處理，形成一經處理的棉布。步驟(b)：將該經處理的棉布浸泡於實施例1的分散水溶液中10秒，取出後，於真空環境下進行45分鐘的乾燥處理，形成一含有奈米碳管的棉布。 Silver carbon composite material identification analysis: The electrode in Application Example 1 was washed with deionized water for 30 seconds, and dried in a vacuum atmosphere for 15 minutes to form a test object. The analyte was subjected to D-band and G-band measurement by a Raman spectrometer (label: Tokyo Instruments.; model: Nanofinder 30; excitation light source: He-Ne Laser, 633 nm). The control group was a cotton cloth containing a carbon nanotube. The cotton cloth containing the carbon nanotubes is formed by the following steps: Step (a): Cut the cotton cloth into 1x2 cm 2 , remove the impurities with 95% absolute alcohol, wash with deionized water, and carry out in a vacuum environment. A minute of drying treatment to form a treated cotton cloth. Step (b): The treated cotton cloth was immersed in the dispersion aqueous solution of Example 1 for 10 seconds, taken out, and dried in a vacuum atmosphere for 45 minutes to form a cotton cloth containing a carbon nanotube.
銀金屬粒子尺寸分析：將應用例1、應用例2、比較應用例1及比較應用例2的電極以SigmaScan影像量測分析軟體進行銀金屬粒子粒徑分析。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 analysis software for silver metal particle size analysis.
銀金屬粒子含量分析：將應用例1、應用例2及比較應用例1的電極以熱重量分析儀(thermogravimetric Analyzer)進行分析，計算加熱至500℃時的熱損失重量(為棉布及未修飾的多壁奈米碳管的重量)，然後，以電極全重扣掉熱損失重量，即為銀金屬粒子含量。Silver metal particle content analysis: The electrodes of Application Example 1, Application Example 2, and Comparative Application Example 1 were analyzed by a thermogravimetric analyzer, and the heat loss weight (for cotton cloth and unmodified) heated to 500 ° C was calculated. The weight of the multi-walled carbon nanotubes), and then the weight loss of the electrode is the total weight of the electrode, which is the content of silver metal particles.
儲存期限量測：將實施例1的銀碳複合材料水溶液及比較例2的混合液靜置於27℃下14天，以肉眼觀測是否有沉澱物出現。Storage period measurement: The silver carbon composite aqueous solution of Example 1 and the mixed solution of Comparative Example 2 were allowed to stand at 27 ° C for 14 days, and it was visually observed whether or not a precipitate appeared.
參閱圖1，在2θ 為25度、38.31度、44.49度、 64.61度，及77.53度有訊號峰出現，依據JCPDS cards No. 04–0783可知，在圖1中的2θ 為25度處為碳材訊號峰，而2θ 為38.31度、44.49度、 64.61度，及77.53度處為面心立方結構的銀金屬訊號峰。由此可知，透過本發明銀碳複合材料水溶液的製備方法，確實可獲得銀碳複合材料。Referring to Fig. 1, there are signal peaks at 25 degrees, 38.31 degrees, 44.49 degrees, 64.61 degrees, and 77.53 degrees at 2θ. According to JCPDS cards No. 04-0783, the carbon of 2θ is 25 degrees in Fig. 1. The signal peak, while 2θ is 38.31 degrees, 44.49 degrees, 64.61 degrees, and 77.53 degrees is the silver metal signal peak of the face-centered cubic structure. From this, it is understood that the silver-carbon composite material can be obtained by the method for preparing the aqueous solution of the silver-carbon composite material of the present invention.
參閱圖2，條狀物為綿布的纖維，而一顆顆球狀物為銀金屬奈米粒子。在圖2中，該銀碳複合材料水溶液塗佈在該棉布上，顯示出該等銀金屬奈米粒子分散在該棉布上，而未團聚，表示實施例1的方法，會使該等銀金屬奈米粒子均勻地分散於該等未修飾的碳材上，且該等銀碳複合材料均勻地分散於該水中，繼而使得該銀碳複合材料水溶液可均勻分散塗佈在該棉布上。Referring to Figure 2, the strips are fibers of cotton and the individual spheres are silver metal nanoparticles. In FIG. 2, the silver carbon composite aqueous solution is coated on the cotton cloth, and the silver metal nanoparticles are dispersed on the cotton cloth without agglomeration, indicating that the method of Embodiment 1 causes the silver metal to be The nanoparticles are uniformly dispersed on the unmodified carbon materials, and the silver carbon composite materials are uniformly dispersed in the water, and then the aqueous solution of the silver carbon composite material is uniformly dispersed and coated on the cotton cloth.
參閱圖4，條狀物為綿布的纖維，而一顆顆球狀物為銀金屬奈米粒子。在圖4中，該銀碳複合材料水溶液塗佈在該棉布上，顯示出該等銀金屬奈米粒子分散在該棉布上，而未團聚，表示實施例2的方法，會使該等銀金屬奈米粒子均勻地分散於該等未修飾的碳材上，且該等銀碳複合材料均勻地分散於該水中，繼而使得該銀碳複合材料水溶液可均勻分散塗佈在該棉布上。Referring to Figure 4, the strips are fibers of cotton and the individual spheres are silver metal nanoparticles. In FIG. 4, the silver carbon composite aqueous solution is coated on the cotton cloth, and the silver metal nanoparticles are dispersed on the cotton cloth without agglomeration, indicating that the method of Embodiment 2 causes the silver metal to be The nanoparticles are uniformly dispersed on the unmodified carbon materials, and the silver carbon composite materials are uniformly dispersed in the water, and then the aqueous solution of the silver carbon composite material is uniformly dispersed and coated on the cotton cloth.
參閱圖3及圖5，黑點表示結合在多壁奈米碳管上的銀金屬奈米粒子及未結合在多壁奈米碳管上的銀金屬奈米粒子，而長條物為多壁奈米碳管。本發明該銀鹽水溶液以霧化液滴搭配噴灑方式接觸該分散水溶液，並採超音波震盪處理使該銀鹽水溶液與該分散水溶液混合，使該等銀金屬奈米粒子可均勻地分散並結合於該等未修飾的碳材上。Referring to Figures 3 and 5, black dots indicate silver metal nanoparticles bonded to a multi-walled carbon nanotube and silver metal nanoparticles not bonded to a multi-walled carbon nanotube, and the long strip is multi-walled. Carbon nanotubes. The silver salt aqueous solution of the present invention contacts the dispersed aqueous solution by atomizing droplets in a sprayed manner, and ultrasonic wave oscillating 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 the unmodified carbon materials.
在圖6中，兩條曲線分別為未修飾的多壁奈米碳管的訊號峰及實施例1銀碳複合材料水溶液中的銀碳複合材料的訊號峰。D-band 1330cm -1代表 sp 3，而G-band 1580 cm -1代表 sp 2。該未修飾的多壁奈米碳管的D-band訊號強度與G-band的訊號強度比值為1.71，而該銀碳複合材料的D-band訊號強度與G-band的訊號強度比值為1.18。由該數據可知，在該銀碳複合材料中，因銀金屬奈米粒子結合在該未修飾的多壁奈米碳管上，使該未修飾的多壁奈米碳管的結構亂度(sp 3、 sp 2)上升，產生電漿子效應(plasmonic effect)，而使得D-band訊號強度與G-band的訊號強度比值下降。 In Fig. 6, the two curves are the signal peaks of the unmodified multi-walled carbon nanotubes and the signal peaks of the silver-carbon composite materials in the aqueous solution of the silver-carbon composite 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 intensity of the unmodified multi-walled carbon nanotubes to the signal intensity of the G-band is 1.71, and the ratio of the D-band signal intensity of the silver-carbon composite to the signal intensity of the G-band is 1.18. It can be seen from the data that in the silver-carbon composite material, the structural irregularity of the unmodified multi-walled carbon nanotubes is caused by the binding of silver metal nanoparticles to the unmodified multi-walled carbon nanotubes (sp 3 , sp 2 ) rises, producing a plasmonic effect, which causes the ratio of the signal intensity of the D-band signal to the G-band to decrease.
參閱圖3、圖7及圖10，本發明該銀鹽水溶液以霧化液滴搭配噴灑方式接觸該分散水溶液，並採超音波震盪處理使該銀鹽水溶液與該分散水溶液混合，使該等銀金屬奈米粒子可均勻地分散並結合於該等未修飾的碳材上(參閱圖3)。再者，在該等霧化液滴加入完畢時，所形成的銀碳複合材料水溶液未有沉澱物出現，具有分散性佳的特性(參閱圖7)，且長時間儲存下該等銀碳複合材料不會自該銀碳複合材料水溶液中沉澱下來(參閱圖10)。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 in a sprayed manner, and ultrasonically oscillates to mix the silver salt aqueous solution with the dispersed aqueous solution to make the silver The metal nanoparticles can be uniformly dispersed and bonded to the unmodified carbon materials (see Fig. 3). Furthermore, when the atomized droplets are added, the formed silver carbon composite material solution has no precipitates, has good dispersibility (see FIG. 7), and is stored for a long time under the silver-carbon composite. The material does not precipitate from the aqueous solution of the silver carbon composite (see Figure 10).
參閱圖8，條狀物為綿布的纖維，而塊狀團聚物為銀金屬奈米粒子。在圖8中，該銀碳複合材料水溶液塗佈在棉布上，顯示出該等銀金屬粒子分散不均且團聚的現象，表示比較例1中的該銀鹽水溶液以滴入方式接觸該分散水溶液，應會使該等銀金屬粒子無法均勻地分散並團聚於該等未修飾的碳材上，且該等銀碳複合材料無法均勻地分散於該水中，繼而使得該銀碳複合材料水溶液無法均勻分散塗佈在該棉布上。Referring to Figure 8, the strips are fibers of cotton and the bulk agglomerates are silver metal nanoparticles. In FIG. 8, the silver carbon composite aqueous solution is coated on a cotton cloth, and shows that the silver metal particles are unevenly dispersed and agglomerated, and the aqueous silver salt solution of Comparative Example 1 is contacted with the dispersed aqueous solution by dropping. The silver metal particles should not be uniformly dispersed and agglomerated on the unmodified carbon materials, and the silver carbon composite materials cannot be uniformly dispersed in the water, which in turn makes the silver carbon composite aqueous solution not uniform. Disperse coated on the cotton cloth.
參閱圖9，條狀物為綿布的纖維，而塊狀團聚物為銀金屬奈米粒子。在圖9中，該混合液塗佈在棉布上，顯示出該等銀金屬粒子分散不均且團聚的現象。再參閱圖11，在圖11中，瓶壁上存在有許多細微顆粒，表示比較例2的混合液於長時間儲存下，該等銀金屬粒子及未修飾的碳材會自該混合液中沉澱下來。Referring to Figure 9, the strips are fibers of cotton and the bulk agglomerates are silver metal nanoparticles. In Fig. 9, the mixed solution was coated on a cotton cloth, showing a phenomenon in which the silver metal particles were unevenly dispersed and agglomerated. Referring again to Fig. 11, in Fig. 11, a plurality of fine particles are present on the wall of the bottle, indicating that the mixed liquid of Comparative Example 2 is precipitated from the mixed liquid under long-term storage. Come down.
使用RTS-3四探針測試儀分別對1x1cm 2尺寸的應用例1、比較應用例1及比較應用例2的電極以及[0044]段落所述含有奈米碳管的棉布進行表面電阻量測。該應用例1的含有銀碳複合材料的棉布的表面電阻為100ohm/cm 2，而比較應用例1及比較應用例2的電極的表面電阻分別為250 ohm/cm 2及大於300ohm/cm 2，且該含有奈米碳管的棉布的表面電阻為300ohm/cm 2。 Surface resistance measurements were performed on the 1x1 cm 2 size application example 1, the comparison application example 1 and the application example 2 electrode, and the carbon nanotube-containing cotton cloth of paragraph [0044], respectively, using an RTS-3 four-probe tester. 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, And the surface of the cotton cloth containing the carbon nanotubes had a surface resistance of 300 ohm/cm 2 .
綜上所述，透過本發明銀碳複合材料水溶液的製備方法，可快速且簡單的形成該銀碳複合材料水溶液，且在不需要還原劑的參與下，獲得該等銀碳複合材料，同時，所形成的該銀碳複合材料水溶液具有分散性佳，且長時間儲存下該等銀碳複合材料不會自該銀碳複合材料水溶液中沉澱下來，故確實能達成本發明的目的。In summary, the silver carbon composite aqueous solution can be formed quickly and simply by the preparation method of the silver carbon composite aqueous solution of the present invention, and the silver carbon composite material can be obtained without the participation of a reducing agent. The formed aqueous solution of the silver-carbon composite material has good dispersibility, and the silver-carbon composite material does not precipitate from the aqueous solution of the silver-carbon composite material under long-term storage, so the object of the present invention can be achieved.
惟以上所述者，僅為本發明的實施例而已，當不能以此限定本發明實施的範圍，凡是依本發明申請專利範圍及專利說明書內容所作的簡單的等效變化與修飾，皆仍屬本發明專利涵蓋的範圍內。However, the above is only the embodiment of the present invention, and the scope of the invention is not limited thereto, and all the simple equivalent changes and modifications according to the scope of the patent application and the patent specification of the present invention are still Within the scope of the invention patent.
本發明的其他的特徵及功效，將於參照圖式的實施方式中清楚地呈現，其中： 圖1是X-ray繞射光譜圖，說明本發明銀碳複合材料水溶液製備方法的一實施例1可獲得的銀碳複合材料水溶液中的銀碳複合材料，並說明該銀碳複合材料的晶型； 圖2是SEM圖，說明該實施例1所獲得的銀碳複合材料水溶液的銀碳複合材料的銀金屬奈米粒子不會團聚； 圖3是TEM圖，說明該實施例1所獲得的銀碳複合材料水溶液的銀碳複合材料中銀金屬奈米粒子均勻分散於未修飾的碳材上，且不團聚； 圖4是SEM圖，說明該實施例6所獲得的銀碳複合材料水溶液的銀碳複合材料的銀金屬奈米粒子不會團聚； 圖5是TEM圖，說明該實施例6所獲得的銀碳複合材料水溶液的銀碳複合材料中銀金屬奈米粒子分散於未修飾的碳材上； 圖6是拉曼光譜圖，說明實施例1的銀碳複合材料； 圖7是照片，說明該實施例1所獲得的銀碳複合材料水溶液的分散性； 圖8是SEM圖，說明比較例1所獲得的銀碳複合材料水溶液的銀碳複合材料的銀金屬粒子會團聚； 圖9是SEM圖，說明比較例2所獲得的混合液的銀金屬粒子會團聚； 圖10是照片，說明該實施例1所獲得的銀碳複合材料水溶液靜置兩個禮拜後的狀態；及 圖11是照片，說明比較例2所獲得的混合液靜置兩個禮拜後的狀態。Other features and effects of the present invention will be apparent from the following description of the drawings, wherein: FIG. 1 is an X-ray diffraction spectrum diagram illustrating an embodiment 1 of a method for preparing an aqueous solution of a silver-carbon composite material of the present invention. A silver-carbon composite material in an aqueous solution of a silver-carbon composite material is obtained, and the crystal form of the silver-carbon composite material is illustrated; FIG. 2 is an SEM image illustrating the silver-carbon composite material of the aqueous solution of the silver-carbon composite material obtained in the first embodiment. The silver metal nanoparticle is not agglomerated; FIG. 3 is a TEM image showing that the silver metal nanoparticle in the silver-carbon composite material of the silver carbon composite aqueous solution obtained in the first embodiment is uniformly dispersed on the unmodified carbon material, and FIG. 4 is an SEM image showing that the silver metal nanoparticle of the silver-carbon composite material of the aqueous solution of the silver-carbon composite obtained in the embodiment 6 is not agglomerated; FIG. 5 is a TEM image, which is obtained by the embodiment 6. The silver-carbon nanocomposite of the silver carbon composite aqueous solution is dispersed on the unmodified carbon material; FIG. 6 is a Raman spectrum, illustrating the silver-carbon composite material of Example 1; FIG. 7 is a photograph illustrating the The dispersibility of the aqueous solution of the silver-carbon composite material obtained in Example 1; FIG. 8 is an SEM image showing that the silver-metal particles of the silver-carbon composite material of the aqueous solution of the silver-carbon composite material obtained in Comparative Example 1 are agglomerated; FIG. 9 is an SEM image. The silver metal particles of the mixed solution obtained in Comparative Example 2 are agglomerated; FIG. 10 is a photograph illustrating the state in which the aqueous solution of the silver-carbon composite material obtained in Example 1 is allowed to stand for two weeks; and FIG. 11 is a photograph. The state of the mixture obtained in Comparative Example 2 after standing for two weeks was explained.
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