CN106519804B - Graphene conductive ink and preparation method and application thereof - Google Patents
Graphene conductive ink and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses graphene conductive ink and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) ultrasonically dispersing a dispersing agent and a graphite sheet in a first solvent to obtain a mixture A; (2) performing first centrifugation on the mixture A, and performing second centrifugation on the upper-layer dispersion liquid after the first centrifugation to obtain a precipitate B; (3) dispersing the precipitate B in a second solvent to obtain a dispersion C; (4) adding a solvent and an auxiliary agent for the conductive ink into the dispersion liquid C; (5) and removing the second solvent to obtain the graphene conductive ink. The graphene is prepared in situ by the method, so that the influence of the existence of graphene defects on the electrical conductivity is avoided; high-concentration and high-conductivity graphene conductive ink can be obtained.
Description
Technical Field
the invention relates to graphene conductive ink and a preparation method and application thereof, and belongs to the field of electronic information materials and printed electronics.
Background
The conductive ink is a basic material for developing electronic components, is a key material for packaging, electrodes and interconnection, is a high-technology electronic functional material integrating metallurgy, chemical engineering and electronic technology, and is mainly used for manufacturing various fields of electronic industries such as thick film integrated circuits, Thin Film Transistors (TFTs), sensors, organic photovoltaics, solar cells, flexible displays, radio frequency identification tags (RFID), wearable electronic products, memories and the like. The conductive filler in the conductive ink is generally composed of noble metals Au, Ag or base metals Cu, Ni, Al, etc. Noble metals generally have good conductivity and are not easy to oxidize, but if a large amount of noble metals are used, the production cost is increased; base metals are easy to oxidize, and the conductive performance of the conductive ink is affected after the metals are oxidized. In addition, sintering of base metal slurries is typically carried out under nitrogen or vacuum conditions, which can add cost and complexity to the process.
The graphene material has the highest conductivity of 200,000cm2V.s.electricityStream density bearing up to 108A/cm2Maximum mechanical strength, best thermal conductivity and high temperature stability. And the manufacturing cost of the graphene is far lower than that of the nano metal particles.
patent US2015/0072162 a1 discloses a method for preparing high-concentration graphene conductive ink, which comprises the steps of preparing graphene by ultrasonic liquid phase stripping, precipitating the graphene by using an aqueous solution containing NaCl, cleaning the NaCl, drying, and dispersing the graphene to prepare 3.4mg/ml graphene conductive ink.
Disclosure of Invention
The technical problem to be solved by the invention is to improve the concentration of the graphene conductive ink and reduce the content of the dispersing agent in the graphene conductive ink. The method comprises the steps of preparing a graphene dispersion liquid in situ by using a dispersing agent, a solvent and graphite flakes, removing multiple layers of graphene in the graphene dispersion liquid through centrifugal separation, removing excessive dispersing agent in the graphene dispersion liquid through high-speed centrifugation, adding the solvent and the auxiliary agent for conductive ink, and obtaining the high-concentration graphene conductive ink through a solvent replacement method.
The technical scheme provided by the invention is that the preparation method of the graphene conductive ink comprises the following steps:
(1) dispersing a dispersing agent and a graphite sheet in a first solvent, and performing ultrasonic treatment to obtain a mixture A;
(2) Performing first centrifugation on the mixture A, and performing second centrifugation on the upper-layer dispersion liquid after the first centrifugation to obtain a precipitate B;
(3) Dispersing the precipitate B in a second solvent to obtain a dispersion C;
(4) Adding a solvent and an auxiliary agent for the conductive ink into the dispersion liquid C;
(5) And removing the second solvent to obtain the graphene conductive ink.
Wherein, the first centrifugation in the step (2) adopts low-speed centrifugation, and the centrifugation speed is the speed which can precipitate the multilayer graphite and graphite sheets in the mixture A and ensure that part of the graphene does not precipitate; and the second centrifugation adopts high-speed centrifugation, and the centrifugation speed is the speed capable of precipitating the graphene.
Preferably, the first solvent is a solvent capable of dissolving the dispersant; one or more alcohols such as water, ethanol, n-propanol, and isopropanol are preferable.
Preferably, the upper layer dispersion liquid after the first centrifugation is diluted and then subjected to second centrifugation; preferably, the solvent used for dilution is a first solvent; preferably, the dilution is more than 2 times; more preferably, the dilution is 5-10 fold.
preferably, the second solvent is a solvent capable of dispersing graphene; preferably, the second solvent is one or more of alcohols such as ethanol, n-propanol, isopropanol and the like.
Preferably, the graphite sheet is a naturally occurring graphite such as flake graphite, microcrystalline graphite, or the like.
Preferably, the second solvent is removed in the step (5) by rotary evaporation. The dispersing agent is a cellulose substance; one or more of ethyl cellulose, hydroxyethyl cellulose and hydroxypropyl methyl cellulose are preferably selected, and the dispersant plays a role in assisting intercalation.
Preferably, in the step (1), the weight ratio of the dispersant to the first solvent is 0.001-0.1: 1; the weight ratio of the graphite flakes to the first solvent is 0.001-0.2: 1.
Preferably, in the step (1), the ultrasonic time is 1-8 hours, and the ultrasonic frequency is 20-40 kHz. The centrifugation rate of the second centrifugation is greater than the centrifugation rate of the first centrifugation; preferably, the centrifugation speed of the first centrifugation is 5000-7500 r/min, and the centrifugation time is 5-25 min; the centrifugation rate of the first centrifugation is more than 11000 r/min, and the centrifugation time is 1-4 hours.
Preferably, the solvent for the conductive ink is a solvent which is miscible with the second solvent and can disperse graphene, such as one or more of terpineol, cyclohexanone and toluene. The auxiliary agent for the conductive ink is a thixotropic agent and other common auxiliary agents for the conductive ink.
The invention further provides the graphene conductive ink obtained by the preparation method.
The invention provides application of the graphene conductive ink in 3D ink-jet printing electronic circuits, solar cells, radio frequency identification tags, printed circuit boards and various flexible electronic products. The prepared high-concentration graphene conductive ink has the graphene concentration of 5-20mg/ml and the viscosity of below 30cp, is used for 3D ink-jet printing electronic circuits, has the sheet resistance of 1-150 omega/□ after sintering at 250 ℃, and can be applied to solar cells, radio frequency identification tags, printed circuit boards and various flexible electronic products.
According to the method, the graphene dispersion liquid is prepared in situ, excessive dispersing agent added in the graphene preparation process is removed through high-speed centrifugation, and then the high-concentration graphene conductive ink is obtained through a solvent replacement method.
The method for preparing the high-concentration graphene conductive ink in situ has the following advantages:
1. The graphene is prepared in situ, so that the influence of the existence of graphene defects on the electrical conductivity is avoided;
2. During high-speed centrifugation, the graphene sinks into the bottom layer, and the excessive dispersing agent is dispersed in the upper-layer solvent, so that the excessive dispersing agent can be removed by a high-speed centrifugation method, and the highly conductive graphene conductive ink can be obtained;
3. Solvent replacement is carried out by a rotary evaporation method, and graphene conductive ink with higher concentration can be obtained.
drawings
Fig. 1 shows a flowchart of a method for preparing graphene conductive ink according to example 2.
Detailed Description
The present invention will be further described with reference to the following examples.
in order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below. The examples are given solely for the purpose of illustration and are not intended to limit the scope of the invention.
example 1
Dissolving 1g of ethyl cellulose in 100ml of ethanol, adding 5g of crystalline flake graphite into the solution, performing ultrasonic treatment for 4 hours, taking 7500 r/m of upper layer solution for centrifugal separation for 15 minutes, taking 10 times of upper layer liquid after centrifugal separation for centrifugation for 2 hours under the centrifugal condition of 11000 r/m, pouring out the upper layer liquid, dispersing the centrifuged precipitate in 100ml of ethanol, adding 1ml of terpineol and 9ml of cyclohexanone, and evaporating the alcohol to dryness at 50 r/m and 50 ℃ to obtain the high-concentration graphene conductive ink, wherein the content of graphene is 10mg/ml, and the viscosity is 18 cps. The conductive ink is used for 3D ink-jet printing electronic circuits, and after sintering at 250 ℃, the sheet resistance is 98 omega/□.
example 2
dissolving 1g of hydroxyethyl cellulose in 100ml of water, adding 5g of crystalline flake graphite into the solution after dissolving, performing ultrasonic treatment for 4 hours, taking 7500 r/m of upper layer solution for centrifugal separation for 15 minutes, taking 10 times of upper layer liquid after centrifugal separation for centrifugation for 2 hours under the centrifugal condition of 11000 r/m, pouring out the upper layer liquid, dispersing the centrifuged precipitate in 100ml of ethanol, adding 1ml of terpineol and 9ml of cyclohexanone, and evaporating the ethanol to dryness under the conditions of 50 r/m and 50 ℃ to obtain the high-concentration graphene conductive ink, wherein the content of graphene is 10mg/ml, and the viscosity is 18 cps. The conductive ink is used for 3D ink-jet printing electronic circuits, and after sintering at 250 ℃, the sheet resistance is 98 omega/□.
Example 3
Dissolving 2g of ethyl cellulose in 100ml of ethanol, adding 10g of crystalline flake graphite into the solution, performing ultrasonic separation for 4 hours, taking 7500 r/m of upper layer solution, performing centrifugal separation for 15 minutes, diluting the upper layer liquid after centrifugal separation by 10 times, centrifuging for 2 hours under the centrifugal condition of 11000 r/m, pouring out the upper layer liquid, dispersing the centrifuged precipitate in 100ml of ethanol, adding 1ml of terpineol and 9ml of cyclohexanone, and evaporating the alcohol to dryness at 50 r/m and 50 ℃ to obtain the high-concentration graphene conductive ink, wherein the content of graphene is 15mg/ml, and the viscosity is 25 cps. The conductive ink is used for 3D ink-jet printing electronic circuits, and the sheet resistance is 90 omega/□ after sintering at 250 ℃.
Example 4
Dissolving 2g of hydroxyethyl cellulose in 100ml of water, adding 10g of crystalline flake graphite into the solution after dissolving, performing ultrasonic treatment for 4 hours, taking 7500 r/m of upper layer solution for centrifugal separation for 15 minutes, taking 10 times of upper layer liquid after centrifugal separation for dilution, centrifuging for 2 hours under the centrifugal condition of 11000 r/m, pouring out the upper layer liquid, dispersing the centrifuged precipitate in 100ml of ethanol, adding 1ml of terpineol and 9ml of cyclohexanone, and evaporating the ethanol to dryness under the conditions of 50 r/m and 50 ℃ to obtain the high-concentration graphene conductive ink, wherein the content of graphene is 15mg/ml, and the viscosity is 25 cps. The conductive ink is used for 3D ink-jet printing electronic circuits, and the sheet resistance is 90 omega/□ after sintering at 250 ℃.
the steps of the above methods are divided for clarity, and the implementation may be combined into one step or split some steps, and the steps are divided into multiple steps, so long as the steps contain the same logical relationship, which is within the protection scope of the present patent; it is within the scope of the patent to add insignificant modifications to the algorithms or processes or to introduce insignificant design changes to the core design without changing the algorithms or processes.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples for carrying out the invention, and that various changes in form and details may be made therein without departing from the spirit and scope of the invention in practice.
Claims (13)
1. A preparation method of graphene conductive ink is characterized by comprising the following steps:
(1) Dispersing a dispersing agent and a graphite sheet in a first solvent, and performing ultrasonic treatment to obtain a mixture A;
(2) Performing first centrifugation on the mixture A, and performing second centrifugation on the upper-layer dispersion liquid after the first centrifugation to obtain a precipitate B; the centrifugation speed of the first centrifugation is 5000-7500 r/min, and the centrifugation time is 5-25 min; the centrifugation rate of the second centrifugation is more than 11000 r/min, and the centrifugation time is 1-4 hours;
(3) dispersing the precipitate B in a second solvent to obtain a dispersion C; the second solvent is one or more of water, ethanol, n-propanol and isopropanol;
(4) adding a solvent and an auxiliary agent for the conductive ink into the dispersion liquid C; the solvent for the conductive ink is one or more of terpineol, cyclohexanone and toluene; the conductive ink additive is a thixotropic agent;
(5) And removing the second solvent by adopting a rotary evaporation mode to obtain the graphene conductive ink.
2. The method according to claim 1, wherein the first solvent is a solvent capable of dissolving the dispersant.
3. The preparation method according to claim 2, wherein the first solvent is one or more of water, ethanol, n-propanol and isopropanol.
4. The method according to any one of claims 1 to 3, wherein the supernatant dispersion after the first centrifugation is diluted and then subjected to the second centrifugation.
5. The method of claim 4, wherein the solvent used for dilution is the first solvent.
6. The method according to claim 4, wherein the centrifuged supernatant dispersion is diluted at least 2-fold.
7. The method according to claim 4, wherein the centrifuged supernatant dispersion is diluted 5 to 10 times.
8. The production method according to any one of claims 1 to 3, wherein the dispersant is a cellulose-based substance.
9. The method according to claim 8, wherein the cellulose-based substance is one or more selected from ethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl methyl cellulose.
10. The production method according to any one of claims 1 to 3, wherein in the step (1), the weight ratio of the dispersant to the first solvent is from 0.001 to 0.1: 1; the weight ratio of the graphite flakes to the first solvent is 0.001-0.2: 1.
11. The production method according to any one of claims 1 to 3, wherein in the step (1), the ultrasonic time is 1 to 8 hours and the ultrasonic frequency is 20 to 40 kHz.
12. The graphene conductive ink obtained by the preparation method according to any one of claims 1 to 11, wherein the graphene concentration in the graphene conductive ink is 5 to 20mg/ml, and the viscosity is below 30 cps.
13. use of the graphene conductive ink according to claim 12 in 3D inkjet printing electronic circuits, solar cells, radio frequency identification tags, printed circuit boards, and various flexible electronic products.
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| CN107197545A (en) * | 2017-06-20 | 2017-09-22 | 广西大学 | Nano-cellulose graphene complex electrocaloric film and its green preparation process |
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| CN109817382B (en) * | 2017-11-21 | 2020-09-29 | 山东欧铂新材料有限公司 | Preparation method of high-stability graphene conductive paste |
| CN109830512A (en) * | 2019-01-30 | 2019-05-31 | 合肥鑫晟光电科技有限公司 | Display base plate, the preparation method of display base plate, display device |
| CN110183908B (en) * | 2019-03-19 | 2022-03-22 | 浙江省海洋开发研究院 | Conductive ink containing graphene compound and preparation method thereof |
| CN110165366B (en) * | 2019-04-22 | 2021-02-19 | 浙江大学 | Thermal transfer printing graphene antenna and preparation method and application thereof |
| CN110117440B (en) * | 2019-05-10 | 2021-11-05 | 齐鲁工业大学 | Conductive ink and preparation method thereof |
| CN110895998A (en) * | 2019-11-22 | 2020-03-20 | 西安交通大学 | Electrode material ink, preparation method and method for preparing miniature super capacitor by using electrode material ink |
| CN111560188B (en) * | 2020-06-01 | 2022-02-18 | 南京林业大学 | Nano-silver/graphene composite electromagnetic shielding ink and preparation method thereof |
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| CN104370283A (en) * | 2014-10-23 | 2015-02-25 | 江阴碳谷科技有限公司 | Graphene stripping kettle, graphene production system and graphene production method |
| CN105949884A (en) * | 2016-06-07 | 2016-09-21 | 江南大学 | Preparation method of liquid phase stripping high-concentration graphene ink |
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| CN103113786A (en) * | 2013-03-07 | 2013-05-22 | 苏州牛剑新材料有限公司 | Graphene conductive ink and preparation method thereof |
| CN104370283A (en) * | 2014-10-23 | 2015-02-25 | 江阴碳谷科技有限公司 | Graphene stripping kettle, graphene production system and graphene production method |
| CN105949884A (en) * | 2016-06-07 | 2016-09-21 | 江南大学 | Preparation method of liquid phase stripping high-concentration graphene ink |
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| CN107197545A (en) * | 2017-06-20 | 2017-09-22 | 广西大学 | Nano-cellulose graphene complex electrocaloric film and its green preparation process |
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