CN116598065A - 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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- CN116598065A CN116598065A CN202310553671.XA CN202310553671A CN116598065A CN 116598065 A CN116598065 A CN 116598065A CN 202310553671 A CN202310553671 A CN 202310553671A CN 116598065 A CN116598065 A CN 116598065A
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- graphene
- conductive paste
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 120
- 239000004332 silver Substances 0.000 title claims abstract description 120
- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 93
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 80
- 238000007639 printing Methods 0.000 claims abstract description 32
- 238000005516 engineering process Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000006835 compression Effects 0.000 claims abstract description 12
- 238000007906 compression Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims description 71
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 40
- 239000000758 substrate Substances 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000006185 dispersion Substances 0.000 claims description 23
- 238000001125 extrusion Methods 0.000 claims description 22
- 239000000853 adhesive Substances 0.000 claims description 21
- 230000001070 adhesive effect Effects 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 14
- 239000008103 glucose Substances 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 6
- 238000005452 bending Methods 0.000 abstract description 4
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- 239000007921 spray Substances 0.000 description 44
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000010793 electronic waste Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 238000012544 monitoring process Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- 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
-
- 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)
- General Physics & Mathematics (AREA)
- Theoretical Computer Science (AREA)
- Conductive Materials (AREA)
- Carbon And Carbon Compounds (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
Abstract
The invention discloses a graphene-silver composite conductive paste and a preparation method thereof, wherein the preparation method and the use process of the graphene-silver composite conductive paste are green and environment-friendly, and the graphene is added with silver while being harmless to the environment and the human health, so that the conductivity of an RFID antenna line is remarkably improved. The invention also provides an RFID antenna prepared by adopting the graphene-silver composite conductive paste, the preparation method of the antenna is based on a multilayer ink direct-writing printing technology of the graphene-silver composite conductive paste, the complex printing of an antenna line can be accurately controlled, the working time is short, the efficiency is high, the multilayer printing technology and the compression treatment enable the antenna line to have high adhesion degree, difficult falling off, good toughness and difficult breaking while improving the conductivity, and the antenna line is difficult to be subjected to physical abrasion and chemical oxidation, so that the service life is prolonged, the stability is good, and the influence of environmental factors such as bending wrinkles and the like on the resistance value of the antenna line is reduced.
Description
Technical Field
The invention belongs to the technical field of radio frequency identification (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 through information sensing devices such as Radio Frequency Identification (RFID), a positioning system and the like according to a contracted protocol, and performs information exchange and communication so as to realize intelligent identification, positioning, tracking, monitoring and management. Has been widely used in retail, transportation, military and other independent fields.
Radio frequency identification (radio frequency identifification, RFID) technology is a technology that uses Radio Frequency (RF) waves for two-way information transfer through spatial coupling to achieve intelligent identification of targets. The RFID has strong anti-interference capability and long communication distance, can adapt to various complex application environments, improves working efficiency, reduces 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 information of the RFID tag, so that the purpose of identifying articles and exchanging data can be achieved.
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 extremely easy to damage in the practical application of the Internet of things, and meanwhile, electronic waste is generated. Therefore, replacement of metals with environmentally friendly, highly conductive materials is extremely urgent.
Disclosure of Invention
The invention aims to provide graphene-silver composite conductive paste with good dispersibility and environmental friendliness, and the graphene-silver composite RFID electronic tag with good conductivity, high adhesion and good 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, there is provided a method for preparing a graphene-silver composite conductive paste, comprising the steps of:
s01, adding a graphene material into a solvent, and carrying out ultrasonic treatment and 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 graphene-silver composite conductive paste with uniform dispersion;
the preparation method of the graphene material in the step S01 comprises the steps of calcining graphite oxide at 350-450 ℃ under nitrogen, adding a mixed solution of ethylene glycol and water, uniformly dispersing under ultrasonic combined magnetic stirring, adding a mixed solution of NaOH and ethylene glycol, regulating the pH value to 10-12, sealing, heating by microwaves, cooling to room temperature under magnetic stirring, 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, immersing into ice water bath, and cooling. Then mixing natural crystalline flake graphite and potassium permanganate, pouring the mixture into mixed acid, stirring and reacting for about 2 hours, removing ice bath, and reacting in water bath at 42-48 ℃ for 25-35 minutes. Then transferring into ice bath again, adding deionized water dropwise under stirring, and then keeping the temperature at 42-48 ℃ for water bath stirring reaction for about 4 hours. After the reaction is finished, adding hydrogen peroxide solution, centrifuging, removing supernatant, performing ultrasonic dispersion, dialyzing, and drying at 60-80 ℃ to obtain the flaky graphite oxide.
Preferably, the concentrated sulfuric acid and the concentrated phosphoric acid are mixed in a volume ratio of 8:1.
Preferably, the natural crystalline flake graphite and potassium permanganate are mixed in a 1:3 weight ratio.
Preferably, the deionized water is added to the mixed solution in an amount equal to the volume of concentrated sulfuric acid.
Preferably, the hydrogen peroxide solution is used at a concentration of 3%.
Preferably, after stirring for about 2 hours, the ice bath is removed and the reaction is carried out in a 45℃water bath for 30 minutes.
Preferably, the reaction is stirred in a water bath at a constant temperature of 45℃for about 4 hours.
Preferably, the drying is in an oven at 70 ℃.
According to the preparation method of the first aspect of the present invention, preferably, the calcination is carried out under such conditions that the temperature is raised to 350 to 450 ℃ at a rate of 10 ℃ per minute.
More preferably, the calcination conditions are such that the temperature is raised to 400 ℃ at a rate of 10 ℃ per minute.
Preferably, the calcination time is 3.5 to 4.5 hours.
More preferably, the calcination time is 4 hours.
Preferably, the nitrogen calcination is performed in a tube furnace.
According to the preparation method of the first aspect of the present invention, preferably, the condition of the ultrasound is 10 to 20 minutes.
According to the preparation method of the first aspect of the present invention, preferably, the microwave heating is performed under the condition of 680 to 720W for about 2 minutes, and the heating is repeated 3 times.
More preferably, the microwave heating is performed at a power of 700W for about 2min, and the heating is repeated 3 times.
Preferably, the concentration of the mixed solution of NaOH and glycol is 0.5 mol/L.
Preferably, the washing is stirring washing by adopting deionized water and absolute ethyl alcohol respectively.
According to the preparation method of the first aspect of the present invention, preferably, the preparation method of the silver-ammonia solution comprises the following steps: dissolving silver nitrate in deionized water, dropwise adding dilute ammonia water while stirring the solution until precipitation occurs, and clarifying to obtain silver ammonia solution.
According to the production method of the first aspect of the present invention, preferably, the concentration of the graphene dispersion is 10 to 20mg/ml.
More preferably, the concentration of the graphene dispersion is 20mg/ml.
According to the preparation method of the first aspect of the present 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 silver to graphene in the graphene-silver composite conductive paste is 10-15%.
In a second aspect of the invention, a graphene-silver composite conductive paste is provided, and the graphene-silver composite conductive paste is prepared by the preparation method in the first aspect of the invention.
In a third aspect, the invention provides an application of the graphene-silver composite conductive paste in the second aspect in preparing a conductive antenna material.
In a fourth aspect of the invention, an RFID antenna is provided, which is prepared from the graphene-silver composite conductive paste in the second aspect of the invention.
Further, according to the RFID antenna of the fourth aspect of the present invention, the method for manufacturing the antenna includes the steps of:
s11, printing an antenna circuit from the graphene-silver composite conductive paste according to the second aspect of the invention through a multilayer ink direct-writing technology;
s12, performing compression treatment on the antenna circuit covered on the antenna substrate in the step S11;
and S13, placing 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 line printed by the multilayer ink direct writing technique in step S11 is 80 to 100 ℃ and the extrusion speed is 80 to 100 μl/min.
Preferably, the compression treatment condition in the step S12 is 6-10 MPa, and the pressure is maintained for 8-10 min.
More preferably, the compression treatment condition in step S12 is 10MPa for 10min;
preferably, the water bath heating condition in the step S13 is 50-70 ℃ for 3-5 min.
More preferably, the water bath heating in step S13 is performed at 60℃for 3 to 5 minutes.
Preferably, the number of layers of the ink direct writing printing in step S11 is 9 to 11.
The antenna circuit which is continuous, uniform in thickness and good in adhesion with the substrate is printed on the substrate in a multilayer manner by adopting the ink direct writing technology. The direct writing printing technology can accurately control the printing of complex line shapes, and has short working time and high efficiency. The proposed multilayer printing technique greatly improves the line conductivity.
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: the graphene-silver composite conductive paste of the second aspect of the invention is placed into a charging barrel of an injector, is connected with a spray head and is arranged on a triaxial CNC platform, an air pressure control system is opened, then an antenna substrate is fixed on a heating plate, a computer is used for setting the moving speed and the moving route of the spray head, the paste extrusion speed is set, the heating plate is opened, and after the operation is started, the graphene-silver composite conductive paste is extruded from the spray head through a screw extrusion or pneumatic pressure control system and is formed on the substrate.
Further, the inkjet head for ink direct-writing printing includes any one of 19 gauge, 20 gauge, 21 gauge.
Further, the movement speed of the stage for ink direct writing printing is any one of 5 to 8.
Common manufacturing processes for RFID antennas include chemical etching and printed circuit boards, which are cumbersome and not environmentally friendly. The direct writing technology is used as a forming technology which is developed faster in recent years, can accurately control the complex printing of the antenna circuit, and has the advantages of short working time, high efficiency and remarkable advantages. However, the direct-writing parameters (pressure and speed) and the direct-writing environment (temperature and direct-writing medium) of the ink direct-writing process can greatly influence 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 processing condition in step S12 is 6-10 mpa and pressure is maintained for 8-10 min.
More specifically, the antenna circuit and the substrate after the multilayer printing are covered with the same substrate, and are placed on a manual press together for compression.
Preferably, the antenna substrate in step S12 is selected from any one of PET, PVC, PP, PC, cardboard, offset paper, coated paper, cellophane, laser paper, kraft paper, fluorescent paper, aluminum foil paper and security paper.
More specifically, according to the antenna of the fourth aspect of the invention,
preferably, according to the antenna of the fourth aspect of the present invention, the heating condition of the water bath in step S13 is 50-70 ℃ for 3-5 min.
Preferably, the concentration of the glucose solution is 5%.
In a fifth aspect of the present invention, there is provided an RFID electronic tag comprising the RFID antenna according to the fourth aspect of the present invention.
The beneficial effects of the invention are as follows:
the invention also provides the graphene-silver composite conductive paste and the preparation method thereof, and the method adopts glucose solution to reduce silver ions in the antenna circuit to generate silver, so that 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 green and environment-friendly, and the graphene is added with silver while being harmless to the environment and the human health, so that the conductivity of the RFID antenna line is remarkably improved.
The invention also provides a preparation method of the RFID antenna by adopting the graphene-silver composite conductive paste, which is based on a multilayer ink direct-writing printing technology of the graphene-silver composite conductive paste, can accurately control the complex printing of an antenna line, and has the advantages of short working time and high efficiency. The provided silver ion mixing operation and reduction method are environment-friendly and simple in operation, and compared with other reduction modes, such as illumination reduction, the reduction time is greatly shortened. The multilayer printing technology and the compression treatment enable the antenna circuit to have high adhesion degree, good toughness and difficult breakage when improving the conductivity, and not easy to be worn out and oxidized by physics and chemistry, thereby prolonging the service life, having good stability and reducing the influence of environmental factors such as bending wrinkles and the like on the resistance value of the antenna circuit. The lines were compressed using a manual press in consideration of the connection tightness between graphene sheets caused by the multi-layer printing. The compression treatment improves the conductivity and simultaneously also effectively improves the cohesiveness of the circuit and the matrix.
Drawings
Fig. 1 is a physical diagram of a multi-layer direct-write printed RFID antenna of a graphene-silver composite conductive paste.
Detailed Description
The present invention will be described in further detail with reference to specific examples and drawings. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
Preparation of graphene-silver composite conductive paste
S1, preparing graphene:
concentrated sulfuric acid and concentrated phosphoric acid are mixed in a volume ratio of 8:1 and immersed in an ice water bath for cooling. And then uniformly mixing natural crystalline flake graphite and potassium permanganate in a weight ratio of 1:3, pouring the mixture into mixed acid, stirring and reacting for 2 hours, removing an ice bath, and reacting in a 45 ℃ water bath for 30 minutes. Then transferring into ice bath again, adding deionized water with the same volume as concentrated sulfuric acid dropwise under stirring, and stirring in a water bath with the constant temperature of 45 ℃ for reaction for 4 hours after the dropwise addition. After the reaction was completed, a 3% hydrogen peroxide solution was added until the liquid turned from tan to pale yellow and no gas was generated any more. And centrifuging, removing supernatant, adding deionized water with the same volume, performing ultrasonic dispersion, dialyzing, and drying in a 70 ℃ oven to obtain the flaky graphite oxide.
Grinding graphite oxide, placing the ground graphite oxide into a quartz boat, placing the quartz boat into a tube furnace, heating to 400 ℃ at a rate of 10 ℃ per minute under the protection of nitrogen, maintaining the temperature for 4 hours, slowly cooling to room temperature to obtain incompletely peeled Expanded Graphite (EG), and storing the incompletely peeled Expanded Graphite (EG) in an 80 ℃ drying oven for later use. Weighing a certain amount of expanded graphite, adding a proper amount of mixed solution of glycol and water, and stirring by ultrasonic and magnetic force to uniformly disperse the mixed solution, wherein in the process, 0.5 mol/L NaOH glycol solution is used for regulating the pH value to 11; after the system is sealed, the mixture is put into a microwave oven and heated for 2 minutes under 700W power, and the process is repeated for three times. And (3) magnetically stirring, slowly cooling to room temperature, respectively stirring and washing with deionized water and absolute ethyl alcohol, carrying out suction filtration, and drying in a blowing drying oven at 80 ℃ to obtain a graphene sample for later use.
S2, preparation of graphene dispersion liquid
Graphene and Dimethylformamide (DMF) are mixed according to a weight ratio of 1: 99. 1: 49. 1:32, and respectively obtaining uniform graphene dispersion liquid of 10mg/ml, 20mg/ml and 30 mg/ml.
S3, preparation of graphene-silver composite conductive slurry
And (3) dissolving silver nitrate in deionized water, dropwise adding 23% dilute ammonia water while stirring the solution until precipitation occurs, and clarifying to obtain a silver ammonia solution. And (2) taking a certain amount of graphene dispersion liquid in the step (S2), and stirring the graphene dispersion liquid while dropwise adding silver-ammonia solution after ultrasonic treatment to prepare mixed solutions of 5%, 10%, 15%, 20% and 25% of silver and graphene by mass percent respectively. And then carrying out ultrasonic treatment on the solution. 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 graphene-silver composite conductive paste with the mass percent of silver to graphene being 10% according to the step S3, placing the graphene-silver composite conductive paste into a charging barrel of an injector, connecting the charging barrel with a spray nozzle, installing the charging barrel on a triaxial CNC platform, opening a pneumatic control system, fixing a PET (polyethylene terephthalate) matrix on a heating plate, setting the moving speed of the spray nozzle to be 5.5 by using a computer, setting the moving route of the spray nozzle, setting the paste extrusion speed 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 ℃, extruding the graphene conductive paste from the spray nozzle through a spiral extrusion or pneumatic pressure control system, and forming the graphene conductive paste on the matrix. The printing was repeated 4 to 11 times to obtain an antenna wiring.
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 temperature of 60 ℃ for 5 minutes. And (3) taking out, drying, uniformly coating conductive silver adhesive on the antenna circuit, and testing the conductivity after the conductive silver adhesive is solidified, wherein the test result is shown in table 1.
TABLE 1 influence of the number of repeated printing of graphene-silver conductive pastes on conductivity in example 1
As can be seen from the results in table 1, 11-layer write-through conductivity improvement effect is extremely small compared with 10-layer write-through. The direct writing effect of more layers is close, the time cost is too high, and the efficiency is reduced, so that the optimal number of layers of the multilayer 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 paste with the mass percent of silver to graphene being 10% according to the step S3, placing the graphene-silver composite conductive paste into a charging barrel of an injector, connecting the charging barrel with a spray nozzle, installing the charging barrel on a triaxial CNC platform, opening a pneumatic control system, fixing a PP matrix on a heating plate, setting the moving speed of the spray nozzle to be 5.5 by using a computer, setting the moving route of the spray nozzle, setting the paste extrusion speed 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 ℃, extruding the graphene conductive paste from the spray nozzle through a spiral extrusion or pneumatic pressure control system, and forming the graphene conductive paste on the matrix. The printing was repeated 10 times to obtain an antenna wiring.
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 temperature of 60 ℃ for 5 minutes. And (3) taking out, drying, uniformly coating conductive silver adhesive on the antenna circuit, and testing the conductivity after the conductive silver adhesive is solidified, wherein the test result is 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 paste with the mass percent of silver to graphene being 10% according to the step S3, placing the graphene-silver composite conductive paste into a charging barrel of an injector, connecting the charging barrel with a spray nozzle, installing the charging barrel on a triaxial CNC platform, opening a pneumatic control system, fixing a PP matrix on a heating plate, setting the moving speed of the spray nozzle to be 5.5 by using a computer, setting the moving route of the spray nozzle, setting the paste extrusion speed 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 ℃, extruding the graphene conductive paste from the spray nozzle through a spiral extrusion or pneumatic pressure control system, and forming the graphene conductive paste on the matrix. The printing was repeated 10 times to obtain an antenna wiring.
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 temperature of 60 ℃ for 5 minutes. And (3) taking out, drying, uniformly coating conductive silver adhesive on the antenna circuit, and testing the conductivity after the conductive silver adhesive is solidified, wherein the test result is shown in Table 2.
Table 2 test results of antenna conductivity for different graphene concentrations
From the results in table 2, it can be seen that: the graphene-silver composite conductive paste prepared by the graphene concentration within the range of 10 mg/ml-20 mg/ml can remarkably improve the conductivity of the graphene RFID tag antenna. After the concentration of the graphene exceeds 20mg/ml, the graphene is polymerized with silver ions due to the higher concentration of the graphene, and the silver ions are not uniformly dispersed, so that the conductivity is lower.
Example 4
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 paste with the mass percent of silver to graphene being 5% according to the step S3, placing the graphene-silver composite conductive paste into a charging barrel of an injector, connecting the charging barrel with a spray nozzle, installing the charging barrel on a triaxial CNC platform, opening a pneumatic control system, fixing a coated paper substrate on a heating plate, setting the moving speed of the spray nozzle to be 5.5 by using a computer, setting the moving route of the spray nozzle, setting the paste extrusion speed 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 ℃, extruding the graphene conductive paste from the spray nozzle through a spiral extrusion or pneumatic pressure control system, and forming the graphene conductive paste on the substrate. The printing was repeated 10 times to obtain an antenna wiring.
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 temperature of 60 ℃ for 5 minutes. And (3) taking out, drying, uniformly coating conductive silver adhesive on the antenna circuit, and testing the conductivity after the conductive silver adhesive is solidified, wherein the test result is 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 paste with 15 mass percent of silver and graphene according to the step S3, placing the graphene-silver composite conductive paste into a syringe charging barrel, connecting with a spray head, installing the spray head on a triaxial CNC platform, opening a pneumatic 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 the moving route of the spray head, setting the paste extrusion speed 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 ℃, extruding the graphene conductive paste from the spray head through a screw extrusion or pneumatic pressure control system, and forming the graphene conductive paste on the substrate. The printing was repeated 10 times to obtain an antenna wiring.
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 temperature of 60 ℃ for 5 minutes. And (3) taking out, drying, uniformly coating conductive silver adhesive on the antenna circuit, and testing the conductivity after the conductive silver adhesive is solidified, wherein the test result is 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 paste with the mass percent of 20% of silver and graphene according to the step S3, placing the graphene-silver composite conductive paste into a charging barrel of an injector, connecting the charging barrel with a spray nozzle, installing the charging barrel on a triaxial CNC platform, opening a pneumatic control system, fixing a coated paper substrate on a heating plate, setting the moving speed of the spray nozzle to be 5.5 by using a computer, setting the moving route of the spray nozzle, setting the paste extrusion speed 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 ℃, extruding the graphene conductive paste from the spray nozzle through a spiral extrusion or pneumatic pressure control system, and forming the graphene conductive paste on the substrate. The printing was repeated 10 times to obtain an antenna wiring.
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 temperature of 60 ℃ for 5 minutes. And (3) taking out, drying, uniformly coating conductive silver adhesive on the antenna circuit, and testing the conductivity after the conductive silver adhesive is solidified, wherein the test result is shown in Table 3.
TABLE 3 results of conductivity tests for different silver/graphene mass ratios for examples 3-6, comparative example 2
From the results in table 3, it can be seen that: the mass percent of silver and graphene can obviously improve the conductivity of the antenna within the range of 15% -20%, the conductivity improvement effect is poor when the mass percent of silver and graphene is lower than 15%, and after the mass percent of silver and graphene is higher than 20%, the silver ions are polymerized with the graphene due to higher concentration of silver ions, and the silver ions 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 paste with the mass percent of silver to graphene being 10% according to the step S3, placing the graphene-silver composite conductive paste into a charging barrel of an injector, connecting the charging barrel with a spray nozzle, installing the charging barrel on a triaxial CNC platform, opening a pneumatic control system, fixing a PET (polyethylene terephthalate) matrix on a heating plate, setting the moving speed of the spray nozzle to be 5.5 by using a computer, setting the moving route of the spray nozzle, setting the extruding speed of the paste 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 ℃, extruding the graphene conductive paste from the spray nozzle through a spiral extruding or pneumatic pressure control system, and forming the graphene conductive paste on the matrix. The printing was repeated 10 times to obtain an antenna wiring.
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 temperature of 60 ℃ for 5 minutes. And (3) taking out, drying, uniformly coating conductive silver adhesive on the antenna circuit, and testing the conductivity after the conductive silver adhesive is solidified, wherein the test result is shown in Table 2. The results in Table 2 show that, due to the higher graphene concentration (30 mg/ml), polymerization with silver ions occurs, and silver ions are not uniformly dispersed, resulting in lower 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 paste with the mass percent of 25% of silver and graphene according to the step S3, placing the graphene-silver composite conductive paste into a charging barrel of an injector, connecting the charging barrel with a spray nozzle, installing the charging barrel on a triaxial CNC platform, opening a pneumatic control system, fixing a coated paper substrate on a heating plate, setting the moving speed of the spray nozzle to be 5.5 by using a computer, setting the moving route of the spray nozzle, setting the paste extrusion speed 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 ℃, extruding the graphene conductive paste from the spray nozzle through a spiral extrusion or pneumatic pressure control system, and forming the graphene conductive paste on the substrate. The printing was repeated 10 times to obtain an antenna wiring.
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 temperature of 60 ℃ for 5 minutes. And (3) taking out, drying, uniformly coating conductive silver adhesive on the antenna circuit, and testing the conductivity after the conductive silver adhesive is solidified, wherein the test result is shown in Table 3. The results in table 3 show that the polymerization with graphene occurs due to the too high concentration of silver ions, which are not uniformly dispersed, resulting in lower 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 paste with the mass percent of 20% of silver and graphene according to the step S3, placing the graphene-silver composite conductive paste into a syringe charging barrel, connecting with a spray nozzle, installing the syringe charging barrel on a triaxial CNC platform, opening a pneumatic control system, fixing a PET (polyethylene terephthalate) matrix on a heating plate, setting the moving speed of the spray nozzle to be 5.5 by using a computer, setting the moving route of the spray nozzle, setting the paste extrusion speed 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 ℃, extruding the graphene conductive paste from the spray nozzle through a spiral extrusion or pneumatic pressure control system, and forming the graphene conductive paste on the matrix. The printing was repeated 10 times to obtain an antenna wiring.
Then the antenna substrate and the circuit are put into 5% glucose solution for water bath heating, the heating temperature is 60 ℃, and the heating time is 5min. And (4) taking out, drying, uniformly coating conductive silver adhesive on the antenna circuit, and testing the conductivity after the conductive silver adhesive is solidified, wherein the test result is shown in Table 4.
Table 4 results of antenna conductivity testing before and after compression
As can be seen from table 4, the conductivity of the antenna can be significantly improved after the compression treatment.
Example 7
Preparing graphene-silver composite conductive slurry: weighing 4g of 20mg/ml graphene dispersion liquid, preparing graphene-silver composite conductive paste with the mass percent of 20% of silver and graphene according to the step S3, placing the graphene-silver composite conductive paste into a syringe charging barrel, connecting with a spray nozzle, installing the syringe charging barrel on a triaxial CNC platform, opening a pneumatic control system, fixing a PET (polyethylene terephthalate) matrix on a heating plate, setting the moving speed of the spray nozzle to be 5.5 by using a computer, setting the moving route of the spray nozzle, setting the paste extrusion speed 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 ℃, extruding the graphene conductive paste from the spray nozzle through a spiral extrusion or pneumatic pressure control system, and forming the graphene conductive paste on the matrix. The printing was repeated 10 times to obtain an antenna wiring.
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 temperature of 60 ℃ for 5 minutes. Taking out and drying.
The antenna circuit was continuously bent and folded in half, and the conductivity and the adhesive force thereof were tested, and the test results are shown in tables 5 and 6.
Table 5 test results of conductivity and adhesion after the antenna was bent and folded 100 times at different angles
Table 6 test results of conductivity and adhesion after 90 ° different bending and folding of antenna
As can be seen from the results in tables 5 and 6, the prepared antenna circuit has the advantages of high adhesiveness, low probability of falling, good toughness, low probability of breakage, long service life, good stability and reduced influence of environmental factors such as bending wrinkles on the resistance value. A physical diagram of the RFID antenna with the graphene-silver composite conductive paste multilayer direct-writing printing is shown in 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 be used for obviously assisting in improving the conductivity of the RFID tag antenna. In addition, the production efficiency can be effectively improved, the cost can be reduced, and the time can be saved in mass production.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the graphene-silver composite conductive paste comprises the following steps:
s01, adding a graphene material into a solvent, and carrying out ultrasonic treatment and 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 graphene-silver composite conductive paste with uniform dispersion;
the preparation method of the graphene material in the step S01 comprises the following steps: calcining graphite oxide at 350-450 ℃ under nitrogen for 3.5-4.5 h, adding a mixed solution of ethylene glycol and water, uniformly dispersing under ultrasonic combined magnetic stirring, adding a mixed solution of NaOH and ethylene glycol to adjust the pH value to 10-12, sealing, heating by microwaves, magnetically stirring, cooling to room temperature, 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 method according to claim 1, wherein the microwave heating is performed at 680-720W for about 2min, and the heating is repeated 3 times.
3. The method according to claim 1, wherein the concentration of the graphene dispersion is 10 to 20mg/ml.
4. The preparation method of claim 1, wherein the mass percentage of silver to graphene in the graphene-silver composite conductive paste is 10-20%.
5. A graphene-silver composite conductive paste prepared by the preparation method of any one of claims 1 to 4.
6. The 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 method of manufacturing the antenna comprises the steps of:
s11, printing an antenna circuit from the graphene-silver composite conductive paste according to claim 5 by a multilayer ink direct writing technology;
s12, performing compression treatment on the antenna circuit covered on the antenna substrate in the step S11;
and S13, placing 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 antenna wire printed by the multilayer ink direct writing technique in step S11 is 80-100 ℃, and the extrusion speed is 80-100 μl/min; the compression treatment condition in the step S12 is 6-10 MPa, and the pressure is maintained for 8-10 min; the water bath heating condition in the step S13 is 50-70 ℃ for 3-5 min.
10. An RFID electronic tag comprising an RFID antenna as claimed in any one of claims 7 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117677061A (en) * | 2024-01-29 | 2024-03-08 | 深圳特新界面科技有限公司 | Preparation method and system of environment-friendly aqueous conductive paste printed electronic tag |
| CN117677061B (en) * | 2024-01-29 | 2024-04-09 | 深圳特新界面科技有限公司 | Preparation method and system of environment-friendly aqueous conductive paste printed electronic tag |
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| CN114639504A (en) | 2022-06-17 |
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