技术领域technical field
本发明涉及导电油墨领域，特别是一种石墨烯有机银导电油墨及其制备方法。The invention relates to the field of conductive ink, in particular to a graphene organic silver conductive ink and a preparation method thereof.
背景技术Background technique
随着科技的高速发展，集成电路的大规模使用，微电子器件越来越小型化，印刷电路、智能标签、柔性显示器件、传感器等的电子线路也向微小、精细化、多样性发展，其对应的印刷方式和基材种类越来越多。印刷方法包括丝网印刷方法、凹版印刷方法、蚀刻方法、旋转涂布方法、电镀方法、化学气相沉积方法、喷墨打印方法、直接笔写方法等；作为打印的基材，可分为硬性基材，如玻璃、金属、半导体、硅片、陶瓷、环氧树脂等；以及柔性基材，如PET膜、聚酰亚胺膜等。With the rapid development of science and technology and the large-scale use of integrated circuits, microelectronic devices are becoming more and more miniaturized, and electronic circuits such as printed circuits, smart labels, flexible display devices, and sensors are also developing towards miniaturization, refinement, and diversity. There are more and more types of corresponding printing methods and substrates. Printing methods include screen printing methods, gravure printing methods, etching methods, spin coating methods, electroplating methods, chemical vapor deposition methods, inkjet printing methods, direct pen writing methods, etc.; as printed substrates, they can be divided into rigid substrates Materials, such as glass, metal, semiconductor, silicon wafer, ceramics, epoxy resin, etc.; and flexible substrates, such as PET film, polyimide film, etc.
导电油墨通常由导电功能单元、溶剂、粘结剂、分散剂、改性添加剂等组成，可以分为金属或金属氧化物系、碳系、复合物系三大类；金属或金属氧化物系导电油墨的导电功能单元主要有金粉、银粉、铜粉等，其性能好，但金粉价格昂贵，而铜粉易因氧化降低导电性；因此目前主要使用银粉系导电油墨，但银粉易迁移、烧结过程易开裂，抗弯曲性能差，故而主要用于低电阻硬性基材导电电路中。碳系导电油墨的导电功能单元主要有石墨、碳黑、乙炔黑等，其性能稳定，不易氧化，固化后耐腐蚀，但电阻率较低，主要应用于薄膜开关中。上述材质的油墨材料都存在着自身的优缺点，为提高印刷制件性能，扩大导电油墨的使用范围，导电功能单元的改进及探索应用新导电单元是国内外导电油墨研发的趋势。Conductive inks are usually composed of conductive functional units, solvents, binders, dispersants, modifying additives, etc., and can be divided into three categories: metal or metal oxide systems, carbon systems, and composite systems; metal or metal oxide systems are conductive The conductive functional units of the ink mainly include gold powder, silver powder, copper powder, etc., which have good performance, but gold powder is expensive, and copper powder is easy to reduce conductivity due to oxidation; therefore, silver powder-based conductive ink is mainly used at present, but silver powder is easy to migrate and sintering process It is easy to crack and has poor bending resistance, so it is mainly used in low-resistance rigid substrate conductive circuits. The conductive functional units of carbon-based conductive ink mainly include graphite, carbon black, acetylene black, etc. It has stable performance, is not easy to oxidize, and is corrosion-resistant after curing, but its resistivity is low. It is mainly used in membrane switches. The ink materials of the above materials have their own advantages and disadvantages. In order to improve the performance of printed parts and expand the use range of conductive inks, the improvement of conductive functional units and the exploration and application of new conductive units are the trends in the research and development of conductive inks at home and abroad.
石墨烯是2004年Geim小组报道的新一代纳米碳材料，具有极高的电子迁移率、优异的导热性、室温反常量子霍尔效应、双极化电场效应和高杨氏模量等特点，在复合材料、储能器件、透明电极等领域具有极大的应用前景。石墨烯导电性高，密度远小于铜、银，抗弯曲性能好，本身稳定；随着石墨烯制备工艺的成熟，价格越来越便宜，因此石墨烯代替铜、银作为印刷电路的导线不但符合微电子产业集成化、轻量化的发展方向，还可以减少贵金属的耗损。Graphene is a new generation of nano-carbon materials reported by the Geim group in 2004. It has the characteristics of extremely high electron mobility, excellent thermal conductivity, anomalous quantum Hall effect at room temperature, dual polarization electric field effect and high Young's modulus. Composite materials, energy storage devices, transparent electrodes and other fields have great application prospects. Graphene has high electrical conductivity, its density is much lower than that of copper and silver, and it has good bending resistance and is stable in itself; with the maturity of graphene preparation technology, the price is getting cheaper and cheaper, so graphene replaces copper and silver as the wire of printed circuit not only meets the requirements The integration and lightweight development direction of the microelectronics industry can also reduce the consumption of precious metals.
然而，利用石墨烯制备导电材料时存在片层界面电阻，所制备的导电油墨易团聚，分散性差，实际导电性与石墨烯理论导电性差距很大。目前采用在石墨烯中添加纳米银的方式保证其导性能，该方法纳米银的添加量一般大于50 wt%；纳米银的制备也繁琐复杂，这无疑增加了生产成本；另外，这种状态的导电油墨中石墨烯与金属银均为固态，给油墨配置中颗粒的分散和某些印刷方式（如喷墨、直写）应用带来困难，因此，提供一种可调制成液态的银前驱体方法制备石墨烯和银复合类型的导电油墨具有重大的现实意义。However, when graphene is used to prepare conductive materials, there is a layer interface resistance, and the prepared conductive ink is easy to agglomerate and has poor dispersion. The actual conductivity is far from the theoretical conductivity of graphene. At present, the method of adding nano-silver to graphene is used to ensure its conductivity. The amount of nano-silver added in this method is generally greater than 50 wt%. The preparation of nano-silver is also cumbersome and complicated, which undoubtedly increases the production cost; Both graphene and metallic silver in conductive ink are solid, which brings difficulties to the dispersion of particles in the ink configuration and the application of certain printing methods (such as inkjet, direct writing). Therefore, a silver precursor that can be adjusted into a liquid state is provided Methods The preparation of graphene and silver composite conductive ink has great practical significance.
有机银为银的有机化合物，可通过络合将其调制成液态，但有机银不稳定，外加的组分极易引起其快速分解还原，因此有机银中复合其它导电单元构建新型导电油墨并未有报道。我们的研究证实石墨烯不具还原性或还原性较弱，借助合理的配置工艺，石墨烯与有机银能稳定共存。Organic silver is an organic compound of silver, which can be prepared into a liquid state through complexation, but organic silver is unstable, and the added components can easily cause its rapid decomposition and reduction. There are reports. Our research has confirmed that graphene has no reducibility or weak reducibility, and with the help of a reasonable configuration process, graphene and organic silver can coexist stably.
发明内容Contents of the invention
本发明提供一种稳定的石墨烯有机银导电油墨及其制备方法，与导电单元全部为石墨烯或纳米银的导电油墨相比，该导电油墨固含量低，油墨的稳定性好，印刷性能好，应用广泛，本发明是这样实现的： 一种石墨烯有机银导电油墨，其特征在于，原料与组分如下，以质量百分比计，包括：The invention provides a stable graphene organic silver conductive ink and a preparation method thereof. Compared with the conductive ink whose conductive units are all graphene or nano-silver, the conductive ink has low solid content, good ink stability and good printing performance , is widely used, and the present invention is achieved in this way: A graphene organic silver conductive ink is characterized in that the raw materials and components are as follows, in mass percent, including:
导电功能单元前驱体 23-40%，Conductive functional unit precursor 23-40%,
有机银络合剂 25-57%，Organic silver complexing agent 25-57%,
粘结剂 3-10%Binder 3-10%
溶剂 0.5-20%，Solvent 0.5-20%,
助剂 2.5-6%；Auxiliary 2.5-6%;
所述导电功能单元前驱体由石墨烯和有机银组成，石墨烯与有机银中单质银的质量比为4-92:96-8。The conductive functional unit precursor is composed of graphene and organic silver, and the mass ratio of graphene to elemental silver in the organic silver is 4-92:96-8.
优选的，本发明中，所述导电功能单元前驱体中，石墨烯与有机银中单质银的质量比为4-20：96-80或80-92:20-8。Preferably, in the present invention, in the conductive functional unit precursor, the mass ratio of graphene to elemental silver in organic silver is 4-20:96-80 or 80-92:20-8.
优选的，本发明中，所述导电功能单元前驱体中，石墨烯与有机银中单质银的质量比为4:96-82:18。Preferably, in the present invention, in the conductive functional unit precursor, the mass ratio of graphene to elemental silver in organic silver is 4:96-82:18.
优选的，本发明中，所述石墨烯为单层或多层的层片状结构。Preferably, in the present invention, the graphene is a single-layer or multi-layer lamellar structure.
优选的，本发明中，所述有机银为辛癸酸银、β-酮酸银、2-[2-(2-甲氧乙氧基)乙氧基]醋酸银、丁酸银、柠檬酸银、丁二酸银、苹果酸银、酒石酸银、醋酸银、草酸银中的一种。Preferably, in the present invention, the organic silver is silver octadecanoate, silver β-ketoate, 2-[2-(2-methoxyethoxy) ethoxy] silver acetate, silver butyrate, citric acid One of silver, silver succinate, silver malate, silver tartrate, silver acetate, and silver oxalate.
优选的，本发明中，所述粘结剂为乙基纤维素、羟乙基纤维素、聚乙烯醇、酚醛树脂、聚酯树脂、聚酰亚胺树脂、环氧树脂、有机硅树脂、氟碳树脂、聚酯树脂、乙烯基树脂、丙烯酸树脂、丙烯酸酯类低聚物和活性单体、醇酸树脂、合成纤维素、聚酰胺树脂、氯醋树脂、聚氨酯树脂、聚偏氟乙烯树脂、热塑性树脂、合成橡胶、有机硅改性环氧、聚氨酯改性环氧、环氧改性丙烯酸树脂、有机硅改性丙烯酸环氧树脂、改性丙烯酸树脂、改性酚醛、改性醇酸树脂中的一种。Preferably, in the present invention, the binder is ethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, phenolic resin, polyester resin, polyimide resin, epoxy resin, silicone resin, fluorine Carbon resins, polyester resins, vinyl resins, acrylic resins, acrylate oligomers and reactive monomers, alkyd resins, synthetic cellulose, polyamide resins, vinyl resins, polyurethane resins, polyvinylidene fluoride resins, Thermoplastic resin, synthetic rubber, silicone modified epoxy, polyurethane modified epoxy, epoxy modified acrylic resin, silicone modified acrylic epoxy resin, modified acrylic resin, modified phenolic resin, modified alkyd resin kind of.
优选的，本发明中，所述的有机银络合剂为胺类化合物或胺基类化合物；其中，所述胺类化合物是指氨水、正丙胺、正丁胺、异丁胺、正己胺、正辛胺、1，2-丙二胺、1，3-丙二胺、二异丙胺、二正丁胺、二乙醇胺、三乙胺、三丙胺或仲丁胺；所述胺基类化合物是指2-（甲氨基）乙醇、3-氨丙基乙氧基硅烷或二乙氨基乙醇。Preferably, in the present invention, the organic silver complexing agent is an amine compound or an amine-based compound; wherein, the amine compound refers to ammonia water, n-propylamine, n-butylamine, isobutylamine, n-hexylamine, N-octylamine, 1,2-propylenediamine, 1,3-propylenediamine, diisopropylamine, di-n-butylamine, diethanolamine, triethylamine, tripropylamine or sec-butylamine; the amino compounds are Refers to 2-(methylamino)ethanol, 3-aminopropylethoxysilane or diethylaminoethanol.
优选的，本发明中，所述溶剂为水、芳香烃类溶剂、脂肪烃类溶剂、醚类溶剂、醇类溶剂、醇醚类溶剂、酰胺类溶剂、酮类溶剂、酯类溶剂中的一种或几种。Preferably, in the present invention, the solvent is one of water, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, ether solvents, alcohol solvents, alcohol ether solvents, amide solvents, ketone solvents, and ester solvents species or several.
优选的，本发明中，所述助剂为分散剂、稳定剂、保护剂、成膜剂、偶联剂、增塑剂、消泡剂、增稠剂、润湿剂、流平剂、触变剂、交联剂、紫外吸收剂中的一种或几种。Preferably, in the present invention, the auxiliary agent is a dispersant, a stabilizer, a protective agent, a film-forming agent, a coupling agent, a plasticizer, a defoamer, a thickener, a wetting agent, a leveling agent, a contact agent One or more of variable agents, crosslinking agents, and UV absorbers.
一种本发明所述石墨烯有机银导电油墨的制备方法，其具体步骤如下：A kind of preparation method of graphene organic silver conductive ink of the present invention, its concrete steps are as follows:
A)按比例将有机银、溶剂以及有机银络合剂在避光条件下搅拌 0.5-12 h，超声分散1-12 h，获得有机银络合溶液；A) Stir the organic silver, solvent, and organic silver complexing agent in proportion to 0.5-12 h under dark conditions, and ultrasonically disperse for 1-12 h to obtain an organic silver complex solution;
B)按比例将石墨烯、粘结剂、助剂以及步骤A获得的有机银络合溶液于避光、温度低于10 °C的环境中搅拌反应0.5-12 h或超声分散0.5-12 h或球磨0.5-1 h混合均匀，所得产物即为石墨烯有机银导电油墨。B) Graphene, binder, auxiliary agent and the organic silver complex solution obtained in step A are stirred and reacted for 0.5-12 h or ultrasonically dispersed for 0.5-12 h in an environment protected from light and at a temperature lower than 10 °C in proportion Or ball mill for 0.5-1 h to mix evenly, and the resulting product is graphene organic silver conductive ink.
优选的，本发明中，所述有机银是这样获得的：将银盐或氧化银溶液缓慢滴入相应有机物溶液中，避光条件下搅拌0.5-2 h，将获得的沉淀洗涤、过滤，室温避光阴干，所得产物即为有机银。Preferably, in the present invention, the organic silver is obtained as follows: slowly drop the silver salt or silver oxide solution into the corresponding organic solution, stir for 0.5-2 h under dark conditions, wash and filter the obtained precipitate, and store it at room temperature Avoid light and dry in the shade, and the resulting product is organic silver.
本发明的有益效果在于：The beneficial effects of the present invention are:
1、本发明所提供的导电油墨导电单元配料比、固含量、表面张力以及粘度等物理性质可以根据实际需要印刷的制件导电性要求来调节，该导电油墨烧结温度最低可至150°C，因此其承印基材的选择范围较宽，如玻璃、陶瓷、金属、半导体、硅片、陶瓷、环氧树脂等硬性基材；因导电油墨中含有石墨烯，极大地改善了纯银油墨抗弯曲性能，满足柔性器件的印刷要求，其也适用聚酰亚胺膜等柔性基材。1. Physical properties such as the proportioning ratio, solid content, surface tension and viscosity of the conductive ink provided by the present invention can be adjusted according to the conductivity requirements of the parts to be printed, and the sintering temperature of the conductive ink can be as low as 150°C. Therefore, the selection range of its printing substrate is wide, such as glass, ceramics, metals, semiconductors, silicon wafers, ceramics, epoxy resin and other hard substrates; because the conductive ink contains graphene, it greatly improves the bending resistance of pure silver ink Performance, to meet the printing requirements of flexible devices, it is also suitable for flexible substrates such as polyimide film.
2、本发明方法制备的石墨烯有机银导电油墨的粘度可以在较宽的范围内进行调整，依制备方法和具体的使用过程而变化，优选为1-1500 cP，如粘度较低的导电墨水适合喷墨印刷、直接笔写、旋转涂布方法等多种印刷方式；粘度较高的导电墨水则可以应用于凹版印刷、丝网印刷等多种印刷方式。2. The viscosity of the graphene organic silver conductive ink prepared by the method of the present invention can be adjusted in a wide range, and varies according to the preparation method and the specific use process, preferably 1-1500 cP, such as conductive ink with lower viscosity It is suitable for various printing methods such as inkjet printing, direct pen writing, and spin coating method; the conductive ink with high viscosity can be applied to various printing methods such as gravure printing and screen printing.
3、导电性能可控，本发明可以根据印刷器件对导电性能的要求不同，通过改变导电油墨中导电单元前驱体中石墨烯和有机银的配料比和固含量，在满足使用要求的同时，来改变使用石墨烯和有机银含量，降低油墨成本。3. The conductivity is controllable. According to the different requirements of the printing device on the conductivity, the present invention can meet the requirements of use by changing the proportion and solid content of graphene and organic silver in the precursor of the conductive unit in the conductive ink. Change the use of graphene and organic silver content to reduce ink costs.
4、印刷制品稳定性好，与石墨烯银导电油墨相比，本发明所提供的导电油墨中有机银直接与有机添加剂络合以溶液形式存在油墨中，不需要考虑银颗粒团聚难以有效分散对最终制品导电性能的影响。4. The printed product has good stability. Compared with the graphene silver conductive ink, the organic silver in the conductive ink provided by the present invention is directly complexed with the organic additive and exists in the ink in the form of a solution. The influence of the electrical conductivity of the final product.
5、本发明与银导电油墨、石墨烯银导电油墨相比，相同的导电性所需导电单元的添加量减少，油墨的热处理温度极低，使性能和成本得到了优化。5. Compared with silver conductive ink and graphene silver conductive ink, the present invention requires less conductive units to be added for the same conductivity, and the heat treatment temperature of ink is extremely low, which optimizes performance and cost.
6、本发明导电油墨印刷制品不易氧化、耐腐蚀，本发明导电油墨中银含量较低，导电性相对于石墨烯油墨明显提高，导电性与单纯银油墨相当，大大降低了油墨成本，易于推广应用；此外，相对于传统高固体含量的碳浆、银浆油墨，本发明所提供的导电油墨的固体颗粒含量低，分散稳定要好，易储存和使用。6. The conductive ink printed products of the present invention are not easy to oxidize and resist corrosion. The silver content in the conductive ink of the present invention is low, and the conductivity is significantly improved compared with graphene ink, and the conductivity is equivalent to that of pure silver ink, which greatly reduces the ink cost and is easy to popularize and apply In addition, compared with traditional carbon paste and silver paste inks with high solid content, the conductive ink provided by the present invention has low solid particle content, good dispersion and stability, and is easy to store and use.
具体实施方式detailed description
以下通过实施例对本发明做进一步说明，实施例并非是对本发明的限制。The present invention will be further described by the following examples, which are not intended to limit the present invention.
实施例1 制备石墨烯苹果酸银导电油墨Example 1 Preparation of graphene silver malate conductive ink
（1）苹果酸银的制备，室温下，将1.3g DL-苹果酸钠溶解在50mL去离子水中，再将2.5g硝酸银溶解在40mL去离子水中，用滴管将硝酸银水溶液缓慢滴加入苹果酸钠水溶液中（硝酸银与苹果酸钠的摩尔比为2:1，以保证硝酸银稍过量），立刻出现白色沉淀，避光搅拌2h，之后将沉淀洗涤、过滤，室温避光阴干，获得苹果酸银固体。(1) Preparation of silver malate, at room temperature, dissolve 1.3g of DL-sodium malate in 50mL of deionized water, then dissolve 2.5g of silver nitrate in 40mL of deionized water, slowly drop the silver nitrate aqueous solution into In the sodium malate aqueous solution (the molar ratio of silver nitrate to sodium malate is 2:1 to ensure a slight excess of silver nitrate), a white precipitate appears immediately, and it is stirred for 2 hours in the dark, then the precipitate is washed, filtered, and dried in the shade at room temperature. A silver malate solid is obtained.
（2）按质量百分比计，称取如下原料：20%步骤1获得的苹果酸银、3%氧化还原方法制备的石墨烯（厚度约为7nm，层数<10）、3%粘结剂（聚氨酯树脂）、52%有机银络合剂（二异丙胺）、16%溶剂（松油醇）、5.5%分散保护剂（司班-80）、0.5%消泡剂。(2) In terms of mass percentage, weigh the following raw materials: 20% silver malate obtained in step 1, 3% graphene prepared by redox method (thickness is about 7nm, number of layers <10), 3% binder ( Polyurethane resin), 52% organic silver complexing agent (diisopropylamine), 16% solvent (terpineol), 5.5% dispersion protective agent (Span-80), 0.5% defoamer.
（3）按比例将松油醇、二异丙胺以及步骤1获得的苹果酸银混合，在避光小于10 °C条件下以500 rpm的转速搅拌2 h、再以80 KHz超声分散2 h，获得均一的苹果酸银络合溶液。(3) Mix terpineol, diisopropylamine and silver malate obtained in step 1 in proportion, stir at 500 rpm for 2 h under the condition of avoiding light and less than 10 °C, and then disperse ultrasonically at 80 KHz for 2 h, A uniform silver malate complex solution was obtained.
（4）将石墨烯、聚氨酯树脂、松油醇、司班-80、消泡剂和步骤3获得的苹果酸银络合溶液在避光、温度低于10 °C的条件下 以800rpm的转速搅拌2 h、再以300rpm的转速球磨2min，所获得的均匀浆料混合物即为石墨烯苹果酸银导电油墨（石墨烯与单质银质量比约为80:20）。(4) Graphene, polyurethane resin, terpineol, Span-80, defoamer and the silver malate complex solution obtained in step 3 were kept at a speed of 800rpm under the condition of avoiding light and temperature below 10 °C Stir for 2 hours, and then ball mill for 2 minutes at a speed of 300rpm. The obtained homogeneous slurry mixture is the graphene silver malate conductive ink (the mass ratio of graphene to simple silver is about 80:20).
使用悬涂法将实施例1获得的石墨烯苹果酸银导电油墨印刷于聚酰亚胺薄膜上，200 °C处理1 h，四探针电阻测试仪测得方块电阻为0.9 Ω/□。The graphene silver malate conductive ink obtained in Example 1 was printed on a polyimide film using the suspension coating method, and treated at 200 °C for 1 h, and the sheet resistance measured by a four-probe resistance tester was 0.9 Ω/□.
实施例2 制备石墨烯柠檬酸银导电油墨Embodiment 2 Preparation of graphene silver citrate conductive ink
（1）制备柠檬酸银，室温下，将1.35g柠檬酸钠溶解在50mL去离子水中，再将2.5g硝酸银溶解在40mL去离子水中，用滴管将硝酸银水溶液缓慢滴加入柠檬酸钠水溶液中，立刻出现白色沉淀，避光搅拌2 h，之后将沉淀洗涤、过滤，室温避光阴干，制得柠檬酸银固体。(1) To prepare silver citrate, dissolve 1.35g of sodium citrate in 50mL of deionized water at room temperature, then dissolve 2.5g of silver nitrate in 40mL of deionized water, and slowly add the silver nitrate aqueous solution to sodium citrate with a dropper In the aqueous solution, a white precipitate appeared immediately, and it was stirred for 2 h in the dark, and then the precipitate was washed, filtered, and dried at room temperature in the dark to obtain a silver citrate solid.
（2）按质量百分比计，称取如下原料：34%步骤1获得的柠檬酸银、1%物理法制备的单层石墨烯、5%粘结剂（羟乙基纤维素）、57%有机银络合剂（1,2-丙二胺）、0.5%溶剂（异丙醇）、1.5%分散保护剂（司班-85）、0.5%消泡剂、0.5%稳定剂。(2) In terms of mass percentage, weigh the following raw materials: 34% silver citrate obtained in step 1, 1% single-layer graphene prepared by physical method, 5% binder (hydroxyethyl cellulose), 57% organic Silver complexing agent (1,2-propylenediamine), 0.5% solvent (isopropanol), 1.5% dispersion protection agent (Span-85), 0.5% defoamer, 0.5% stabilizer.
（3）按比例将异丙醇、1,2-丙二胺以及柠檬酸银混合，在避光小于10 °C条件下搅拌(500 r/min)12 h、超声（80 KHz）分散2 h，获得均一的柠檬酸银络合溶液。(3) Mix isopropanol, 1,2-propylenediamine and silver citrate in proportion, stir (500 r/min) for 12 h, and disperse by ultrasonic (80 KHz) for 2 h under the condition of avoiding light and less than 10 °C , to obtain a uniform silver citrate complex solution.
（4）将石墨烯、粘结剂、溶剂、分散保护剂、消泡剂、稳定剂和步骤3获得的柠檬酸银络合溶液在避光、温度低于10 °C的条件下搅拌(800 r/min)2 h、超声（80 KHz）分散0.5 h、再以300rpm的转速球磨5 min，将石墨烯柠檬酸银混合均匀，即得到石墨烯柠檬酸银导电油墨（石墨烯与单质银质量比约为4:96）。(4) Stir graphene, binder, solvent, dispersion protection agent, defoamer, stabilizer and the silver citrate complex solution obtained in step 3 under the condition of avoiding light and temperature below 10 ° C (800 r/min) for 2 h, ultrasonic (80 KHz) dispersion for 0.5 h, and ball milling at a speed of 300 rpm for 5 min to mix graphene silver citrate evenly to obtain graphene silver citrate conductive ink (graphene and simple silver mass The ratio is about 4:96).
将实施例2获得的石墨烯柠檬酸银导电油墨经丝网印刷于聚酰亚胺薄膜上，200 °C处理1 h，四探针电阻测试仪测得方块电阻为0.03 Ω/□。The graphene silver citrate conductive ink obtained in Example 2 was screen-printed on a polyimide film, treated at 200 °C for 1 h, and the sheet resistance measured by a four-probe resistance tester was 0.03 Ω/□.
实施例3 制备石墨烯柠檬酸银导电油墨Embodiment 3 Preparation of graphene silver citrate conductive ink
（1）制备柠檬酸银，室温下，将1.35g柠檬酸钠溶解在50mL去离子水中，再将2.5g硝酸银溶解在40mL去离子水中，用滴管将硝酸银水溶液缓慢滴加入柠檬酸钠水溶液中，立刻出现白色沉淀，避光搅拌2 h，之后将沉淀洗涤、过滤，室温避光阴干，制得柠檬酸银固体。(1) To prepare silver citrate, dissolve 1.35g of sodium citrate in 50mL of deionized water at room temperature, then dissolve 2.5g of silver nitrate in 40mL of deionized water, and slowly add the silver nitrate aqueous solution to sodium citrate with a dropper In the aqueous solution, a white precipitate appeared immediately, and it was stirred for 2 h in the dark, and then the precipitate was washed, filtered, and dried at room temperature in the dark to obtain a silver citrate solid.
（2）按质量百分比计，称取如下原料：36%步骤1获得的柠檬酸银、3%的化学方法制备的石墨烯、3%粘结剂（改性丙烯酸树脂）、54%有机银络合剂（1,2-丙二胺）、1.5%溶剂（异丙醇）、1.5%分散保护剂（司班-85）、0.5%消泡剂、0.5%稳定剂。(2) In terms of mass percentage, weigh the following raw materials: 36% silver citrate obtained in step 1, 3% graphene prepared by chemical methods, 3% binder (modified acrylic resin), 54% organic silver complex Mixture (1,2-propylenediamine), 1.5% solvent (isopropanol), 1.5% dispersion protection agent (Span-85), 0.5% defoamer, 0.5% stabilizer.
（3）按比例将异丙醇、1,2-丙二胺以及柠檬酸银混合，在避光小于10 °C条件下搅拌(500 r/min)12 h、超声（80 KHz）分散2 h，获得均一的柠檬酸银络合溶液。(3) Mix isopropanol, 1,2-propylenediamine and silver citrate in proportion, stir (500 r/min) for 12 h, and disperse by ultrasonic (80 KHz) for 2 h under the condition of avoiding light and less than 10 °C , to obtain a uniform silver citrate complex solution.
（4）将石墨烯、粘结剂、溶剂、分散保护剂、消泡剂、稳定剂和步骤3获得的柠檬酸银络合溶液在避光、温度低于10 °C的条件下搅拌(800 r/min)2 h、超声（80 KHz）分散0.5 h、再以300rpm的转速球磨3 min，将石墨烯柠檬酸银混合均匀，即得到石墨烯柠檬酸银导电油墨（石墨烯与单质银质量比约为8:92）。(4) Stir graphene, binder, solvent, dispersion protection agent, defoamer, stabilizer and the silver citrate complex solution obtained in step 3 under the condition of avoiding light and temperature below 10 ° C (800 r/min) for 2 h, ultrasonic (80 KHz) dispersion for 0.5 h, and ball milling at a speed of 300 rpm for 3 min to mix graphene silver citrate evenly to obtain graphene silver citrate conductive ink (graphene and simple silver mass The ratio is about 8:92).
将实施例3获得的石墨烯柠檬酸银导电油墨经丝网印刷于聚酰亚胺薄膜上，150 °C处理1 h，四探针电阻测试仪测得方块电阻为17 Ω/□。The graphene silver citrate conductive ink obtained in Example 3 was screen-printed on a polyimide film, treated at 150 °C for 1 h, and the sheet resistance measured by a four-probe resistance tester was 17 Ω/□.
实施例4 制备石墨烯醋酸银导电油墨Embodiment 4 Preparation of graphene silver acetate conductive ink
（1）制备醋酸银，室温下，将0.6g 醋酸钠溶解在50mL去离子水中，2.5g硝酸银溶解在40mL去离子水中，用滴管将硝酸银水溶液缓慢滴加入醋酸钠水溶液中，（硝酸银与醋酸钠的摩尔比为3:1，以保证硝酸银稍过量），立刻出现白色沉淀，避光搅拌2 h，之后将沉淀洗涤、过滤，室温避光阴干，制得醋酸银固体。(1) To prepare silver acetate, at room temperature, dissolve 0.6g sodium acetate in 50mL deionized water, dissolve 2.5g silver nitrate in 40mL deionized water, slowly drop the silver nitrate aqueous solution into the sodium acetate aqueous solution with a dropper, (nitric acid The molar ratio of silver to sodium acetate is 3:1 to ensure a slight excess of silver nitrate), a white precipitate appeared immediately, and stirred for 2 h in the dark, then the precipitate was washed, filtered, and dried in the shade at room temperature to obtain a solid silver acetate.
（2）按质量百分比计，称取如下原料：4.5%步骤1获得的醋酸银、35.5%物理法制备的单层石墨烯、10%树脂粘结剂（丙烯酸树脂）、25%有机银络合剂（2-（甲氨基）乙醇）、20 %溶剂（环己酮）、4.7%司班-80（分散保护剂）、0.3%消泡剂。(2) In terms of mass percentage, weigh the following raw materials: 4.5% silver acetate obtained in step 1, 35.5% single-layer graphene prepared by physical method, 10% resin binder (acrylic resin), 25% organic silver complexed Agent (2-(methylamino)ethanol), 20% solvent (cyclohexanone), 4.7% Span-80 (dispersion protectant), 0.3% defoamer.
（3）按比例将环己酮、2-（甲氨基）乙醇以及醋酸银混合，在避光小于10 °C条件下搅拌(500 r/min)12 h、超声（80 KHz）分散2 h，获得均一的醋酸银络合溶液。(3) Mix cyclohexanone, 2-(methylamino)ethanol and silver acetate in proportion, stir (500 r/min) for 12 h, and ultrasonically (80 KHz) disperse for 2 h under the condition of avoiding light and less than 10 °C. A uniform silver acetate complex solution was obtained.
（4）将石墨烯、粘结剂、溶剂、分散保护剂、消泡剂和步骤3获得的醋酸银络合溶液在避光、温度低于10 °C的条件下搅拌(800 r/min)2 h、超声（80 KHz）分散0.5h,再以300rpm的转速球磨3 min，将石墨烯醋酸银混合均匀，即得到石墨烯醋酸银导电油墨（石墨烯与单质银质量比约为92:8）。(4) Stir the graphene, binder, solvent, dispersion protection agent, defoamer and the silver acetate complex solution obtained in step 3 (800 r/min) under the condition of avoiding light and temperature below 10 °C 2 h. Ultrasonic (80 KHz) dispersion for 0.5 h, and ball milling at 300 rpm for 3 min to mix graphene silver acetate evenly to obtain graphene silver acetate conductive ink (mass ratio of graphene to simple silver is about 92:8 ).
将实施例4获得的石墨烯醋酸银导电油墨经丝网印刷于玻璃上，250 °C处理1 h，四探针电阻测试仪测得方块电阻为8 Ω/□。The graphene silver acetate conductive ink obtained in Example 4 was screen-printed on glass, treated at 250 °C for 1 h, and the sheet resistance measured by a four-probe resistance tester was 8 Ω/□.
实施例5 制备金属银修饰石墨烯柠檬酸银导电油墨Example 5 Preparation of metallic silver modified graphene silver citrate conductive ink
(1)制备柠檬酸银，室温下，将1.35g 柠檬酸钠溶解在50mL去离子水中，再将2.5g硝酸银溶解在40mL去离子水中，用滴管将硝酸银水溶液缓慢滴加入柠檬酸钠水溶液中，（硝酸银与柠檬酸钠的摩尔比为3:1，以保证硝酸银稍过量），立刻出现白色沉淀，避光搅拌2 h，之后将沉淀洗涤、过滤，室温避光阴干，制得柠檬酸银固体。(1) To prepare silver citrate, at room temperature, dissolve 1.35g of sodium citrate in 50mL of deionized water, then dissolve 2.5g of silver nitrate in 40mL of deionized water, and slowly add the aqueous solution of silver nitrate to sodium citrate with a dropper In the aqueous solution, (the molar ratio of silver nitrate and sodium citrate is 3:1 to ensure a slight excess of silver nitrate), a white precipitate appears immediately, and it is stirred for 2 hours in the dark. After that, the precipitate is washed, filtered, and dried in the shade at room temperature. Silver citrate solid was obtained.
(2)制备金属银修饰石墨烯,室温下,将56mg的氧化石墨烯和144mg的硝酸银分散在400mL去离子水中，超声（80 KHz）分散1 h。将混合溶液置于三口烧瓶中，室温下搅拌20h，再加入5mL的80%水合肼，95 °C下还原24 h。用去离子水和无水乙醇洗涤产物至中性，将产物在30 °C下真空干燥，制得金属银修饰石墨烯。(2) To prepare metallic silver-modified graphene, 56 mg of graphene oxide and 144 mg of silver nitrate were dispersed in 400 mL of deionized water at room temperature, and dispersed by ultrasonic (80 KHz) for 1 h. The mixed solution was placed in a three-necked flask, stirred at room temperature for 20 h, then added 5 mL of 80% hydrazine hydrate, and reduced at 95 °C for 24 h. The product was washed with deionized water and absolute ethanol until neutral, and the product was vacuum-dried at 30 °C to obtain metallic silver-modified graphene.
（3）按质量百分比计，称取如下原料：34.5%步骤1获得的柠檬酸银、5.5%步骤2获得的金属银修饰石墨烯、5%树脂粘结剂（聚脂树脂）、45%有机银络合剂（1,2-丙二胺）、5%溶剂（异丙醇）、4.2%司班-80（分散保护剂）、0.3%消泡剂、0.5%稳定剂。(3) In terms of mass percentage, weigh the following raw materials: 34.5% silver citrate obtained in step 1, 5.5% metallic silver-modified graphene obtained in step 2, 5% resin binder (polyester resin), 45% organic Silver complexing agent (1,2-propylenediamine), 5% solvent (isopropanol), 4.2% Span-80 (dispersion protection agent), 0.3% defoamer, 0.5% stabilizer.
（4）按比例将异丙醇和1,2-丙二胺混合，在避光小于10 °C条件下搅拌(500 r/min)12 h、超声（80 KHz）分散2 h，获得均一的柠檬酸银络合溶液。(4) Mix isopropanol and 1,2-propylenediamine in proportion, stir (500 r/min) for 12 h, and disperse ultrasonically (80 KHz) for 2 h under the condition of avoiding light and less than 10 °C to obtain uniform lemon Acid silver complex solution.
（5）将石墨烯、粘结剂、溶剂、分散保护剂助剂、消泡剂、稳定剂和步骤4获得的柠檬酸银络合溶液在避光、温度低于10 °C的条件下搅拌(800 r/min)2 h、超声（80 KHz）分散1h，再以400rpm的转速球磨5 min，将石墨烯柠檬酸银混合均匀，即得到金属银修饰石墨烯柠檬酸银导电油墨（修饰的石墨烯与单质银质量比约为20:80）。(5) Stir graphene, binder, solvent, dispersion protective agent additive, defoamer, stabilizer and the silver citrate complex solution obtained in step 4 under the condition of avoiding light and temperature below 10 °C (800 r/min) for 2 h, ultrasonic (80 KHz) dispersion for 1 h, and ball milling at 400 rpm for 5 min to mix graphene silver citrate evenly to obtain metallic silver modified graphene silver citrate conductive ink (modified The mass ratio of graphene to elemental silver is about 20:80).
使用悬涂法将实施例5获得的金属银修饰石墨烯柠檬酸银导电油墨印刷于玻璃上，250 °C处理1 h，四探针电阻测试仪测得方块电阻为0.4 Ω/□。The metallic silver-modified graphene silver citrate conductive ink obtained in Example 5 was printed on glass by the suspension coating method, and treated at 250 °C for 1 h, and the sheet resistance measured by a four-probe resistance tester was 0.4 Ω/□.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, and it should be pointed out that for those of ordinary skill in the art, some improvements and modifications can be made without departing from the principle of the present invention. It should be regarded as the protection scope of the present invention.
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