CN114639504A - Graphene-silver composite RFID tag and preparation method and application thereof - Google Patents
Graphene-silver composite RFID tag and preparation method and application thereof Download PDFInfo
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- CN114639504A CN114639504A CN202210536917.8A CN202210536917A CN114639504A CN 114639504 A CN114639504 A CN 114639504A CN 202210536917 A CN202210536917 A CN 202210536917A CN 114639504 A CN114639504 A CN 114639504A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06K—GRAPHICAL DATA READING; PRESENTATION OF DATA; RECORD CARRIERS; HANDLING RECORD CARRIERS
- G06K19/00—Record carriers for use with machines and with at least a part designed to carry digital markings
- G06K19/06—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code
- G06K19/067—Record carriers with conductive marks, printed circuits or semiconductor circuit elements, e.g. credit or identity cards also with resonating or responding marks without active components
- G06K19/07—Record carriers with conductive marks, printed circuits or semiconductor circuit elements, e.g. credit or identity cards also with resonating or responding marks without active components with integrated circuit chips
- G06K19/077—Constructional details, e.g. mounting of circuits in the carrier
- G06K19/07749—Constructional details, e.g. mounting of circuits in the carrier the record carrier being capable of non-contact communication, e.g. constructional details of the antenna of a non-contact smart card
- G06K19/07773—Antenna details
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/12—Supports; Mounting means
- H01Q1/22—Supports; Mounting means by structural association with other equipment or articles
- H01Q1/2208—Supports; Mounting means by structural association with other equipment or articles associated with components used in interrogation type services, i.e. in systems for information exchange between an interrogator/reader and a tag/transponder, e.g. in Radio Frequency Identification [RFID] systems
- H01Q1/2225—Supports; Mounting means by structural association with other equipment or articles associated with components used in interrogation type services, i.e. in systems for information exchange between an interrogator/reader and a tag/transponder, e.g. in Radio Frequency Identification [RFID] systems used in active tags, i.e. provided with its own power source or in passive tags, i.e. deriving power from RF signal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/36—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith
- H01Q1/364—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith using a particular conducting material, e.g. superconductor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/36—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith
- H01Q1/38—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith formed by a conductive layer on an insulating support
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1241—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1283—After-treatment of the printed patterns, e.g. sintering or curing methods
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1283—After-treatment of the printed patterns, e.g. sintering or curing methods
- H05K3/1291—Firing or sintering at relative high temperatures for patterns on inorganic boards, e.g. co-firing of circuits on green ceramic sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
- B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
- B22F2301/255—Silver or gold
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Computer Networks & Wireless Communication (AREA)
- General Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
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- Theoretical Computer Science (AREA)
- Conductive Materials (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
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Abstract
The preparation method and the use process of the graphene-silver composite conductive paste are green and environment-friendly, and the graphene-silver composite conductive paste is harmless to the environment and human health, and meanwhile, silver is added into graphene, so that the conductivity of an RFID antenna circuit is remarkably improved. The invention also provides a method for preparing the RFID antenna by adopting the graphene-silver composite conductive paste, the method for preparing the RFID antenna is based on the multilayer ink direct-writing printing technology of the graphene-silver composite conductive paste, the complex printing of the antenna circuit can be accurately controlled, the working time is short, the efficiency is high, the multilayer printing technology and the compression treatment enable the antenna circuit to have high adhesion, difficult falling, good toughness, difficult fracture, difficult physical abrasion and chemical oxidation, prolonged service life, good stability and reduced influence of environmental factors such as bending wrinkles on the resistance value of the antenna circuit while improving the conductivity.
Description
Technical Field
The invention belongs to the technical field of Radio Frequency Identification (RFID), and particularly relates to graphene-silver composite conductive paste and a preparation method and application thereof.
Background
The Internet of Things (Internet of Things, IoT) connects any object with the Internet according to an agreed protocol through information sensing equipment such as Radio Frequency Identification (RFID) and a positioning system to perform information exchange and communication, so as to realize intelligent identification, positioning, tracking, monitoring and management. Has been widely used in various independent fields such as retail, transportation, military and the like.
Radio Frequency Identification (RFID) technology is a technology for implementing intelligent target identification by performing bidirectional information transfer through spatial coupling using Radio Frequency (RF) waves. Due to the strong anti-interference capability and long communication distance, the RFID can adapt to various complex application environments, improve the working efficiency and reduce the management cost, and is applied to various aspects including medical care, logistics, intelligent shopping, public security and the like. The RFID technology can be used for reading and writing the information of the RFID label, so that the purposes of article identification and data exchange can be realized.
The RFID antenna is generally made of metal materials such as copper and aluminum, and the mechanical, chemical and thermal stability of the metal tag is poor, so that the tag is easy to damage in the practical application of the Internet of things, and electronic waste is generated. Therefore, it is extremely urgent to replace metals with environmentally friendly, highly conductive materials.
Disclosure of Invention
The invention aims to provide the graphene-silver composite conductive paste which is good in dispersibility and environment-friendly, and the graphene-silver composite RFID electronic tag which is good in conductivity, high in adhesion and good in toughness is prepared by using the conductive paste through an ink direct writing technology.
The technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, a method for preparing a graphene-silver composite conductive paste is provided, which includes the following steps:
s01, adding the graphene material into a solvent, and carrying out ultrasonic stirring to obtain a uniform graphene dispersion liquid;
s02, after the graphene dispersion liquid in the step S01 is subjected to ultrasonic treatment, dropwise adding a silver-ammonia solution while stirring, and after ultrasonic treatment, obtaining uniformly dispersed graphene-silver composite conductive slurry;
and S01, calcining graphite oxide at 350-450 ℃ under nitrogen, adding a mixed solution of ethylene glycol and water, uniformly dispersing under ultrasonic and magnetic stirring, adding a mixed solution of NaOH and ethylene glycol to adjust the pH value to 10-12, sealing, carrying out microwave heating, carrying out magnetic stirring, cooling to room temperature, washing, filtering and drying to obtain the graphene material.
Further, the preparation method of the graphite oxide comprises the following steps: mixing concentrated sulfuric acid and concentrated phosphoric acid, and soaking in ice water bath for cooling. And then mixing the natural crystalline flake graphite and potassium permanganate, pouring the mixture into mixed acid, stirring the mixture for reaction for about 2 hours, removing the ice bath, and carrying out water bath reaction for 25 to 35 minutes at the temperature of 42 to 48 ℃. And then moving into an ice bath again, dropwise adding deionized water while stirring, and then carrying out water bath stirring reaction at constant temperature of 42-48 ℃ for about 4 hours. And after the reaction is finished, adding a hydrogen peroxide solution, centrifuging, removing a supernatant, ultrasonically dispersing, dialyzing, and drying at 60-80 ℃ to obtain the flake graphite oxide.
Preferably, the concentrated sulfuric acid and the concentrated phosphoric acid are mixed in a volume ratio of 8: 1.
Preferably, the natural flake graphite and potassium permanganate are mixed in a 1:3 weight ratio.
Preferably, the amount of deionized water added to the mixed solution is equal to the volume of concentrated sulfuric acid.
Preferably, the hydrogen peroxide solution is used at a concentration of 3%.
Preferably, the ice bath is removed after stirring the reaction for about 2 hours and the reaction is carried out in a water bath at 45 ℃ for 30 minutes.
Preferably, the reaction is stirred in a constant temperature 45 ℃ water bath for about 4 hours.
Preferably, the drying is oven drying at 70 ℃.
According to the preparation method of the first aspect of the present invention, preferably, the calcination is performed under a condition of raising the temperature to 350 to 450 ℃ at a rate of 10 ℃ per minute.
More preferably, the calcination is carried out under conditions such that the temperature is raised to 400 ℃ at a rate of 10 ℃ per minute.
Preferably, the calcining time is 3.5-4.5 h.
More preferably, the calcination time is 4 h.
Preferably, the nitrogen calcination is conducted in a tube furnace.
According to the preparation method of the first aspect of the present invention, preferably, the ultrasonic condition is 10 to 20 min.
According to the preparation method of the first aspect of the present invention, preferably, the microwave heating is performed under 680-720W for about 2min, and the heating is repeated 3 times.
More preferably, the microwave heating is performed under the condition that the power is 700W for about 2min, and the heating is repeated for 3 times.
Preferably, the concentration of the mixed solution of NaOH and glycol is 0.5 mol/L.
Preferably, the washing is stirring washing with deionized water and absolute ethyl alcohol respectively.
According to the preparation method of the first aspect of the present invention, preferably, the silver ammonia solution is prepared by: dissolving silver nitrate in deionized water, dropwise adding dilute ammonia water while stirring the solution, and clarifying after precipitation to obtain a silver-ammonia solution.
According to the preparation method of the first aspect of the present invention, preferably, the concentration of the graphene dispersion liquid is 10 to 20 mg/ml.
More preferably, the concentration of the graphene dispersion is 20 mg/ml.
According to the preparation method of the first aspect of the invention, preferably, the mass percentage of silver to graphene in the graphene-silver composite conductive paste is 5-20%.
More preferably, the mass percentage of the silver to the graphene in the graphene-silver composite conductive paste is 10-15%.
In a second aspect of the present invention, a graphene-silver composite conductive paste is provided, which is prepared by the preparation method of the first aspect of the present invention.
In a third aspect of the present invention, there is provided an application of the graphene-silver composite conductive paste according to the second aspect of the present invention in preparing a conductive antenna material.
In a fourth aspect of the present invention, an RFID antenna is provided, which is prepared from the graphene-silver composite conductive paste according to the second aspect of the present invention.
Further, according to the RFID antenna of the fourth aspect of the present invention, the manufacturing method of the antenna includes the steps of:
s11, printing an antenna circuit by the graphene-silver composite conductive paste of the second aspect of the invention through a multilayer ink direct writing technology;
s12, compressing the antenna circuit covered on the antenna substrate in the step S11;
and S13, putting the antenna substrate and the circuit into a glucose solution for water bath heating, taking out and drying, and uniformly coating conductive silver adhesive on the antenna circuit.
Preferably, according to the antenna of the fourth aspect of the present invention, the heating temperature of the antenna circuit printed by the multilayer ink direct writing technology in step S11 is 80 to 100 ℃, and the extrusion speed is 80 to 100 μ L/min.
Preferably, the compression treatment condition in the step S12 is 6-10 MPa pressure maintaining for 8-10 min.
More preferably, the compression treatment condition in step S12 is 10MPa holding pressure for 10 min;
preferably, the water bath heating in the step S13 is carried out at 50-70 ℃ for 3-5 min.
More preferably, the water bath heating in step S13 is performed at 60 ℃ for 3-5 min.
Preferably, the number of layers of the ink direct-write printing in the step S11 is 9-11.
And (3) printing continuous antenna lines with uniform thickness and good adhesion with the substrate on the substrate in multiple layers by adopting an ink direct writing technology. The direct-writing printing technology can accurately control the printing of complex circuit shapes, and has short working time and high efficiency. The proposed multilayer printing technique greatly improves the electrical conductivity of the lines.
More specifically, according to the antenna of the fourth aspect of the present invention, the specific steps of printing the antenna circuit by the multilayer ink direct writing technology in step S11 are as follows: placing the graphene-silver composite conductive paste in a charging barrel of an injector, connecting the charging barrel with a spray head, installing the charging barrel on a three-axis CNC platform, opening an air pressure control system, fixing an antenna substrate on a heating plate, setting the moving speed and the moving route of the spray head by using a computer, setting the paste extrusion speed, opening the heating plate, and extruding the graphene-silver composite conductive paste from the spray head through a spiral extrusion or pneumatic pressure control system and forming the graphene-silver composite conductive paste on the substrate after the operation is started.
Further, the ink jet head for ink direct write printing includes any one of 19, 20, and 21.
Further, the moving speed of the working table for ink direct-writing printing is any one of 5 to 8.
Typical manufacturing processes for RFID antennas include chemical etching and printed circuit boards, which are cumbersome and not environmentally friendly. The direct-writing technology is a forming technology which develops rapidly in recent years, can accurately control the complex printing of the antenna circuit, and has short working time, high efficiency and remarkable advantages. However, the direct writing parameters (pressure, speed) and the direct writing environment (temperature, direct writing medium) of the ink direct writing have great influence on the direct writing process, and the ink needs to be matched with proper direct writing parameters and the direct writing environment to construct a stable structure.
Preferably, according to the antenna of the fourth aspect of the present invention, the compression treatment condition in step S12 is 6 to 10MPa with pressure maintained for 8 to 10 min.
More specifically, the antenna circuit and the substrate after multilayer printing are covered with the same substrate and placed together on a manual press for compression.
Preferably, the antenna substrate in step S12 is selected from any one of PET, PVC, PP, PC, cardboard, offset paper, coated paper, glass cardboard, laser paper, kraft paper, fluorescent paper, aluminum foil paper, and anti-counterfeit paper.
More specifically, according to the antenna of the fourth aspect of the present invention,
preferably, according to the antenna of the fourth aspect of the present invention, the water bath heating in step S13 is performed under a condition of 50 to 70 ℃ for 3 to 5 min.
Preferably, the concentration of the glucose solution is 5%.
In a fifth aspect of the invention, an RFID electronic tag is provided, which comprises the RFID antenna according to the fourth aspect of the invention.
The beneficial effects of the invention are:
the invention also provides the graphene-silver composite conductive paste and the preparation method thereof, the silver ions in the antenna circuit are reduced by adopting the glucose solution to generate the silver, the reduction method is environment-friendly and simple to operate, and compared with other reduction modes, such as illumination reduction, the reduction time is greatly shortened. The preparation method and the use process of the graphene-silver composite conductive paste are both environment-friendly and harmless to the environment and human health, and the electric conductivity of the RFID antenna circuit is remarkably improved by adding silver into graphene.
The invention also provides a method for preparing the RFID antenna by adopting the graphene-silver composite conductive paste, and the preparation method of the antenna is based on the multilayer ink direct-writing printing technology of the graphene-silver composite conductive paste, can accurately control the complex printing of the antenna circuit, and has short working time and high efficiency. The silver ion mixing operation and the reduction method are environment-friendly and simple to operate, and compared with other reduction modes, such as illumination reduction, the reduction time is greatly shortened. The antenna circuit is high in adhesion degree, not prone to falling off, good in toughness, not prone to breaking off, not prone to physical abrasion and chemical oxidation, long in service life, good in stability and capable of reducing influences of environmental factors such as bending wrinkles on the resistance value of the antenna circuit when the conductivity of the antenna circuit is improved through the multi-layer printing technology and the compression treatment. The lines were compressed using a manual press in consideration of the connection tightness between graphene sheets due to multi-layer printing. The compression treatment improves the conductivity and effectively improves the adhesion between the circuit and the substrate.
Drawings
Fig. 1 is a real object diagram of a graphene-silver composite conductive paste multilayer direct-write printed RFID antenna.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments and accompanying drawings. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Preparation of graphene-silver composite conductive paste
S1, preparation of graphene:
mixing concentrated sulfuric acid and concentrated phosphoric acid in the volume ratio of 8:1, and soaking in an ice water bath for cooling. Then, the natural crystalline flake graphite and the potassium permanganate are evenly mixed according to the weight ratio of 1:3 and then poured into mixed acid, the mixed acid is stirred for reaction for 2 hours, then the ice bath is removed, and the water bath reaction is carried out for 30 minutes at the temperature of 45 ℃. Then, the mixture is moved into an ice bath again, deionized water with the same volume as concentrated sulfuric acid is added dropwise under stirring, and after dropwise addition, the mixture is stirred in a water bath at the constant temperature of 45 ℃ for reaction for 4 hours. After the reaction was complete, a 3% hydrogen peroxide solution was added until the liquid turned from tan to light yellow and no more gas was produced. And centrifuging, removing supernatant, adding deionized water with the same volume, performing ultrasonic dispersion, dialyzing, and drying in a 70 ℃ oven to obtain the flake graphite oxide.
Placing the ground graphite oxide into a quartz boat, placing the quartz boat in a tube furnace, heating the quartz boat to 400 ℃ at the rate of 10 ℃ per minute under the protection of nitrogen, maintaining the temperature for 4 hours, slowly cooling the quartz boat to room temperature to obtain incompletely stripped Expanded Graphite (EG), and storing the incompletely stripped Expanded Graphite (EG) in a drying box at 80 ℃ for later use. Weighing a certain amount of expanded graphite, adding a proper amount of mixed solution of ethylene glycol and water, uniformly dispersing the expanded graphite by ultrasonic and magnetic stirring, and adjusting the pH value to 11 by using 0.5 mol/L NaOH ethylene glycol solution in the process; after the system is sealed, the system is put into a microwave oven and heated for 2 minutes under the power of 700W, and the heating is repeated for three times. And (3) slowly cooling to room temperature by magnetic stirring, respectively stirring and washing with deionized water and absolute ethyl alcohol, performing suction filtration, and drying in a forced air drying oven at the temperature of 80 ℃ to obtain a graphene sample for later use.
S2 preparation of graphene dispersion liquid
Mixing graphene and Dimethylformamide (DMF) according to a weight ratio of 1: 99. 1: 49. 1: 32, and obtaining uniform graphene dispersion solutions of 10mg/ml, 20mg/ml and 30mg/ml respectively by ultrasonic mixing and stirring.
S3 preparation of graphene-silver composite conductive paste
Dissolving silver nitrate in deionized water, dropwise adding 23% dilute ammonia water while stirring the solution, and clarifying after precipitation to obtain a silver-ammonia solution. After a certain amount of graphene dispersion liquid in the step S2 is taken, ultrasonic treatment is carried out, the graphene dispersion liquid is stirred while a silver-ammonia solution is added dropwise, and mixed solutions with the mass percentages of silver and graphene being 5%, 10%, 15%, 20% and 25% are respectively prepared. Then the solution is subjected to ultrasound. And obtaining the uniformly dispersed graphene-silver composite conductive paste.
Example 1
A preparation method of graphene-silver composite conductive paste comprises the following steps: weighing 4g of 10mg/ml graphene dispersion liquid, preparing 10 mass percent of graphene-silver composite conductive slurry of silver and graphene according to the step S3, putting the graphene-silver composite conductive slurry into a syringe charging barrel, connecting the graphene-silver composite conductive slurry with a nozzle, installing the graphene-silver composite conductive slurry on a three-axis CNC platform, opening an air pressure control system, fixing a PET substrate on a heating plate, setting the moving speed of the nozzle to be 5.5 by using a computer, setting a moving route of the nozzle, setting the extrusion speed of the slurry to be 90 microliters per minute, opening the heating plate, setting the temperature of the heating plate to be 100 ℃, starting to operate after the temperature of the heating plate rises and is stabilized at 100 ℃, and extruding the graphene conductive slurry from the nozzle through a spiral extrusion or pneumatic pressure control system and forming the graphene conductive slurry on the substrate. The printing was repeated 4 to 11 times to obtain an antenna line.
And (3) placing the molded antenna circuit covering substrate into a manual press, setting the pressure to be 10MPa, maintaining the pressure for 10 minutes, and then placing the antenna substrate and the circuit into 5% glucose solution for water bath heating at the heating temperature of 60 ℃ for 5 minutes. Taking out and drying, uniformly coating conductive silver adhesive on the antenna circuit, and testing the conductivity after the conductive silver adhesive is cured, wherein the test results are shown in table 1.
Table 1 influence of the number of times of repeated printing of graphene-silver conductive paste on conductivity in example 1
As can be seen from the results in table 1, the conductivity improvement effect is very small in the 11-layer direct writing compared to the 10-layer direct writing. The effect of writing directly for more layers is close, the time cost is too high, and the efficiency is reduced, so the optimal number of layers for multi-layer printing is 10-11.
Example 2
A preparation method of graphene-silver composite conductive paste comprises the following steps: weighing 4g of 10mg/ml graphene dispersion liquid, preparing graphene-silver composite conductive slurry with the mass percentage of silver to graphene being 10% according to the step S3, putting the graphene-silver composite conductive slurry into a syringe charging barrel, connecting the graphene-silver composite conductive slurry with a nozzle, installing the graphene-silver composite conductive slurry on a three-axis CNC platform, opening an air pressure control system, fixing a PP (polypropylene) substrate on a heating plate, setting the moving speed of the nozzle to be 5.5 by using a computer, setting a moving route of the nozzle, setting the extrusion speed of the slurry to be 90 microliters per minute, opening the heating plate, setting the temperature of the heating plate to be 100 ℃, starting to operate after the temperature of the heating plate rises and is stabilized at 100 ℃, and extruding the graphene conductive slurry from the nozzle through a spiral extrusion or pneumatic pressure control system and forming the graphene conductive slurry on the substrate. The printing was repeated 10 times to obtain an antenna line.
And (3) placing the molded antenna circuit covering substrate into a manual press, setting the pressure to be 10MPa, maintaining the pressure for 10 minutes, and then placing the antenna substrate and the circuit into 5% glucose solution for water bath heating at the heating temperature of 60 ℃ for 5 minutes. Taking out and drying, uniformly coating conductive silver adhesive on the antenna circuit, and testing the conductivity after the conductive silver adhesive is cured, wherein the test results are shown in table 2.
Example 3
A preparation method of graphene-silver composite conductive paste comprises the following steps: weighing 4g of 20mg/ml graphene dispersion liquid, preparing graphene-silver composite conductive slurry with the mass percentage of silver and graphene being 10% according to the step S3, putting the graphene-silver composite conductive slurry into a syringe charging barrel, connecting the graphene-silver composite conductive slurry with a spray head, installing the graphene-silver composite conductive slurry on a three-axis CNC platform, opening a pneumatic control system, fixing a PP (polypropylene) substrate on a heating plate, setting the moving speed of the spray head to be 5.5 by using a computer, setting the movement route of the spray head, setting the extrusion speed of the slurry to be 90 microliters per minute, opening the heating plate, setting the temperature of the heating plate to be 100 ℃, starting to operate after the temperature of the heating plate is raised and stabilized at 100 ℃, and extruding the graphene conductive slurry from the spray head through a spiral extrusion or pneumatic pressure control system and forming the graphene conductive slurry on the substrate. The printing was repeated 10 times to obtain an antenna line.
And (3) placing the molded antenna circuit covering substrate into a manual press, setting the pressure to be 10MPa, maintaining the pressure for 10 minutes, and then placing the antenna substrate and the circuit into 5% glucose solution for water bath heating at the heating temperature of 60 ℃ for 5 minutes. Taking out and drying, uniformly coating conductive silver adhesive on the antenna circuit, and testing the conductivity after the conductive silver adhesive is cured, wherein the test results are shown in table 2.
Table 2 test results of conductivity of antennas with different graphene concentrations
From the results in table 2 it can be seen that: the graphene-silver composite conductive paste prepared with the graphene concentration within the range of 10-20 mg/ml can obviously improve the conductivity of the graphene RFID tag antenna. After the graphene concentration exceeds 20mg/ml, the graphene concentration is high, the graphene is polymerized with silver ions, and the silver ions are not uniformly dispersed, so that the conductivity is low.
Example 4
A preparation method of graphene-silver composite conductive paste comprises the following steps: weighing 4g of 20mg/ml graphene dispersion, preparing 5% by mass of graphene-silver composite conductive slurry according to the step S3, putting the graphene-silver composite conductive slurry into a syringe cylinder, connecting with a spray head, installing the syringe cylinder on a three-axis CNC platform, opening an air pressure control system, fixing a coated paper substrate on a heating plate, setting the moving speed of the spray head to be 5.5 by using a computer, setting a movement route of the spray head, setting the extrusion speed of the slurry to be 90 microliters per minute, opening the heating plate, setting the temperature of the heating plate to be 100 ℃, starting to operate after the temperature of the heating plate is increased and stabilized at 100 ℃, and extruding the graphene conductive slurry from the spray head through a spiral extrusion or pneumatic pressure control system and forming on the substrate. The printing was repeated 10 times to obtain an antenna line.
And (3) placing the molded antenna circuit covering substrate into a manual press, setting the pressure to be 10MPa, maintaining the pressure for 10 minutes, and then placing the antenna substrate and the circuit into 5% glucose solution for water bath heating at the heating temperature of 60 ℃ for 5 minutes. Taking out and drying, uniformly coating conductive silver adhesive on the antenna circuit, and testing the conductivity after the conductive silver adhesive is cured, wherein the test results are shown in Table 3.
Example 5
A preparation method of graphene-silver composite conductive paste comprises the following steps: weighing 4g of 20mg/ml graphene dispersion liquid, preparing graphene-silver composite conductive slurry with the mass percentage of silver and graphene being 15% according to the step S3, putting the graphene-silver composite conductive slurry into a syringe charging barrel, connecting with a spray head, installing the graphene-silver composite conductive slurry on a three-axis CNC platform, opening an air pressure control system, fixing a coated paper substrate on a heating plate, setting the moving speed of the spray head to be 5.5 by using a computer, setting a movement route of the spray head, setting the extrusion speed of the slurry to be 90 microliter per minute, opening the heating plate, setting the temperature of the heating plate to be 100 ℃, starting to operate after the temperature of the heating plate is raised and stabilized at 100 ℃, and extruding the graphene conductive slurry from the spray head through a spiral extrusion or pneumatic pressure control system and forming the graphene conductive slurry on the substrate. The printing was repeated 10 times to obtain an antenna line.
And (3) placing the formed antenna circuit covering substrate into a manual press, setting the pressure to be 10MPa, maintaining the pressure for 10 minutes, and then placing the antenna substrate and the circuit into 5% glucose solution for water bath heating at the heating temperature of 60 ℃ for 5 minutes. Taking out and drying, uniformly coating conductive silver adhesive on the antenna circuit, and testing the conductivity after the conductive silver adhesive is cured, wherein the test results are shown in Table 3.
Example 6
A preparation method of graphene-silver composite conductive paste comprises the following steps: weighing 4g of 20mg/ml graphene dispersion liquid, preparing graphene-silver composite conductive slurry with the mass percentage of silver and graphene being 20% according to the step S3, putting the graphene-silver composite conductive slurry into a syringe charging barrel, connecting the graphene-silver composite conductive slurry with a nozzle, installing the graphene-silver composite conductive slurry on a three-axis CNC platform, opening an air pressure control system, fixing a coated paper substrate on a heating plate, setting the moving speed of the nozzle to be 5.5 by using a computer, setting a nozzle movement route, setting the slurry extrusion speed to be 90 microliter per minute, opening the heating plate, setting the temperature of the heating plate to be 100 ℃, starting to operate after the temperature of the heating plate is raised and stabilized at 100 ℃, and extruding the graphene conductive slurry from the nozzle through a spiral extrusion or pneumatic pressure control system and forming the graphene conductive slurry on the substrate. The printing was repeated 10 times to obtain an antenna line.
And (3) placing the molded antenna circuit covering substrate into a manual press, setting the pressure to be 10MPa, maintaining the pressure for 10 minutes, and then placing the antenna substrate and the circuit into 5% glucose solution for water bath heating at the heating temperature of 60 ℃ for 5 minutes. Taking out and drying, uniformly coating conductive silver adhesive on the antenna circuit, and testing the conductivity after the conductive silver adhesive is cured, wherein the test results are shown in Table 3.
Table 3 results of conductivity tests for examples 3-6, comparative example 2 with different silver/graphene mass ratios
From the results in table 3 it can be seen that: the mass percent of the silver to the graphene is 15-20%, the conductivity of the antenna can be remarkably improved, the conductivity improvement effect is not good when the mass percent of the silver to the graphene is lower than 15%, and after the mass percent of the silver to the graphene is higher than 20%, the silver ions are polymerized with the graphene due to higher concentration of the silver ions, and are not uniformly dispersed, so that the conductivity is lower.
Comparative example 1
A preparation method of graphene-silver composite conductive paste comprises the following steps: weighing 4g of 30mg/ml graphene dispersion liquid, preparing graphene-silver composite conductive slurry with the mass percentage of silver and graphene being 10% according to the step S3, putting the graphene-silver composite conductive slurry into a syringe charging barrel, connecting the graphene-silver composite conductive slurry with a nozzle, installing the graphene-silver composite conductive slurry on a three-axis CNC platform, opening an air pressure control system, fixing a PET (polyethylene terephthalate) substrate on a heating plate, setting the moving speed of the nozzle to be 5.5 by using a computer, setting a nozzle movement route, setting the extrusion speed of the slurry to be 90 microliters per minute, opening the heating plate, setting the temperature of the heating plate to be 100 ℃, starting to operate after the temperature of the heating plate rises and is stabilized at 100 ℃, and extruding the graphene conductive slurry from the nozzle through a spiral extrusion or pneumatic pressure control system and forming the graphene conductive slurry on the substrate. The printing was repeated 10 times to obtain an antenna line.
And (3) placing the molded antenna circuit covering substrate into a manual press, setting the pressure to be 10MPa, maintaining the pressure for 10 minutes, and then placing the antenna substrate and the circuit into 5% glucose solution for water bath heating at the heating temperature of 60 ℃ for 5 minutes. Taking out and drying, uniformly coating conductive silver adhesive on the antenna circuit, and testing the conductivity after the conductive silver adhesive is cured, wherein the test results are shown in table 2. From the results in table 2, it was shown that, due to the high concentration of graphene (30 mg/ml), polymerization occurred with silver ions, which were not uniformly dispersed, resulting in low conductivity.
Comparative example 2
A preparation method of graphene-silver composite conductive paste comprises the following steps: weighing 4g of 20mg/ml graphene dispersion liquid, preparing graphene-silver composite conductive slurry with the mass percentage of silver to graphene being 25% according to the step S3, putting the graphene-silver composite conductive slurry into a syringe charging barrel, connecting the graphene-silver composite conductive slurry with a nozzle, installing the graphene-silver composite conductive slurry on a three-axis CNC platform, opening an air pressure control system, fixing a coated paper substrate on a heating plate, setting the moving speed of the nozzle to be 5.5 by using a computer, setting a nozzle movement route, setting the slurry extrusion speed to be 90 microliter per minute, opening the heating plate, setting the temperature of the heating plate to be 100 ℃, starting to operate after the temperature of the heating plate is raised and stabilized at 100 ℃, and extruding the graphene conductive slurry from the nozzle through a spiral extrusion or pneumatic pressure control system and forming the graphene conductive slurry on the substrate. The printing was repeated 10 times to obtain an antenna line.
And (3) placing the molded antenna circuit covering substrate into a manual press, setting the pressure to be 10MPa, maintaining the pressure for 10 minutes, and then placing the antenna substrate and the circuit into 5% glucose solution for water bath heating at the heating temperature of 60 ℃ for 5 minutes. Taking out and drying, uniformly coating conductive silver adhesive on the antenna circuit, and testing the conductivity after the conductive silver adhesive is cured, wherein the test results are shown in Table 3. As shown in table 3, since the concentration of silver ions is too high, polymerization occurs with graphene, and the silver ions are not uniformly dispersed, resulting in low conductivity.
Comparative example 3
A preparation method of graphene-silver composite conductive paste comprises the following steps: weighing 4g of 20mg/ml graphene dispersion liquid, preparing graphene-silver composite conductive slurry with the mass percentage of silver and graphene being 20% according to the step S3, putting the graphene-silver composite conductive slurry into a syringe charging barrel, connecting the graphene-silver composite conductive slurry with a nozzle, installing the graphene-silver composite conductive slurry on a three-axis CNC platform, opening an air pressure control system, fixing a PET (polyethylene terephthalate) substrate on a heating plate, setting the moving speed of the nozzle to be 5.5 by using a computer, setting the moving route of the nozzle, setting the extrusion speed of the slurry to be 90 microliters per minute, opening the heating plate, setting the temperature of the heating plate to be 100 ℃, starting to operate after the temperature of the heating plate rises and is stabilized at 100 ℃, and extruding the graphene conductive slurry from the nozzle through a spiral extrusion or pneumatic pressure control system and forming the graphene conductive slurry on the substrate. The printing was repeated 10 times to obtain an antenna line.
Then, the antenna substrate and the circuit are placed into 5% glucose solution for water bath heating, the heating temperature is 60 ℃, and the heating time is 5 min. Taking out and drying, uniformly coating conductive silver adhesive on the antenna circuit, and testing the conductivity after the conductive silver adhesive is cured, wherein the test results are shown in Table 4.
Table 4 test results of antenna conductivity before and after compression treatment
As can be seen from table 4, the conductive performance of the antenna can be significantly improved by the compression treatment.
Example 7
Preparing graphene-silver composite conductive slurry: weighing 4g of 20mg/ml graphene dispersion liquid, preparing graphene-silver composite conductive slurry with the mass percentage of silver and graphene being 20% according to the step S3, putting the graphene-silver composite conductive slurry into a syringe charging barrel, connecting the graphene-silver composite conductive slurry with a nozzle, installing the graphene-silver composite conductive slurry on a three-axis CNC platform, opening an air pressure control system, fixing a PET (polyethylene terephthalate) substrate on a heating plate, setting the moving speed of the nozzle to be 5.5 by using a computer, setting the moving route of the nozzle, setting the extrusion speed of the slurry to be 90 microliters per minute, opening the heating plate, setting the temperature of the heating plate to be 100 ℃, starting to operate after the temperature of the heating plate rises and is stabilized at 100 ℃, and extruding the graphene conductive slurry from the nozzle through a spiral extrusion or pneumatic pressure control system and forming the graphene conductive slurry on the substrate. The printing was repeated 10 times to obtain an antenna line.
And (3) placing the molded antenna circuit covering substrate into a manual press, setting the pressure to be 10MPa, maintaining the pressure for 10 minutes, and then placing the antenna substrate and the circuit into 5% glucose solution for water bath heating at the heating temperature of 60 ℃ for 5 minutes. Taking out and drying.
The antenna circuit was continuously bent and folded in half, and the conductivity and adhesion thereof were measured, and the results are shown in tables 5 and 6.
TABLE 5 test results of conductivity and adhesion of antenna after being bent and folded at different angles for 100 times
TABLE 6 test results of conductivity and adhesion after 90-degree bending and folding of the antenna for different times
As can be seen from the results in tables 5 and 6, the prepared antenna line has high adhesion, is not easy to fall off, has good toughness, is not easy to break, has a long service life, has good stability, and reduces the influence of environmental factors such as bending wrinkles on the resistance value. A real object diagram of the RFID antenna printed by multilayer direct-writing of the graphene-silver composite conductive paste is shown in an attached figure 1.
In conclusion, the graphene-silver composite conductive paste and the multilayer ink direct-writing printing technology based on the graphene-silver composite conductive paste provided by the invention are environment-friendly and can obviously assist in improving the conductivity of the RFID tag antenna. And the production efficiency can be effectively improved, the cost is reduced and the time is saved in large-scale production.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of graphene-silver composite conductive paste comprises the following steps:
s01, adding the graphene material into a solvent, and carrying out ultrasonic stirring to obtain a uniform graphene dispersion liquid;
s02, after the graphene dispersion liquid in the step S01 is subjected to ultrasonic treatment, a silver ammonia solution is added dropwise while stirring, and after ultrasonic treatment, uniformly dispersed graphene-silver composite conductive slurry is obtained;
the preparation method of the graphene material in the step S01 includes: calcining graphite oxide at 350-450 ℃ under nitrogen for 3.5-4.5 hours, adding a mixed solution of ethylene glycol and water, uniformly dispersing under ultrasonic and magnetic stirring, adding a mixed solution of NaOH and ethylene glycol to adjust the pH value to 10-12, sealing, carrying out microwave heating, cooling to room temperature under magnetic stirring, washing, filtering and drying to obtain the graphene material;
the solvent in step S01 is preferably at least one of N-methylpyrrolidone (NMP) and Dimethylformamide (DMF).
2. The preparation method according to claim 1, wherein the microwave heating is performed under conditions of 680-720W for about 2min, and the heating is repeated 3 times.
3. The preparation method according to claim 1, wherein the concentration of the graphene dispersion is 10-20 mg/ml.
4. The preparation method according to claim 1, wherein the mass percentage of the silver to the graphene in the graphene-silver composite conductive paste is 10-20%.
5. A graphene-silver composite electroconductive paste prepared by the preparation method of any one of claims 1 to 4.
6. Use of the graphene-silver composite conductive paste of claim 5 in the preparation of a conductive antenna material.
7. An RFID antenna prepared from the graphene-silver composite conductive paste of claim 5.
8. The RFID antenna of claim 7, wherein the antenna is prepared by a method comprising the steps of:
s11, printing the graphene-silver composite conductive paste of claim 5 into an antenna circuit by a multilayer ink direct writing technology;
s12, compressing the antenna circuit covered on the antenna base body in the step S11;
and S13, putting the antenna substrate and the circuit into a glucose solution for water bath heating, taking out and drying, and uniformly coating conductive silver adhesive on the antenna circuit.
9. The RFID antenna of claim 8, wherein the heating temperature of the printed antenna circuit by the multilayer ink direct writing technology in step S11 is 80-100 ℃, and the extrusion speed is 80-100 μ L/min; the compression treatment condition in the step S12 is 6-10 MPa, and the pressure is maintained for 8-10 min; and the water bath heating in the step S13 is carried out for 3-5 min at 50-70 ℃.
10. An RFID electronic tag comprising an RFID antenna as claimed in any of claims 7 to 9.
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| JP5934576B2 (en) * | 2012-05-18 | 2016-06-15 | 三菱製紙株式会社 | Method for manufacturing conductive member |
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| CN117735536A (en) * | 2024-02-02 | 2024-03-22 | 广州优刻谷科技有限公司 | Graphene RFID tag and preparation method and application thereof |
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