CN106229030B - A kind of electrically conductive composition, electrically conductive ink, conducting film, preparation method and application - Google Patents

A kind of electrically conductive composition, electrically conductive ink, conducting film, preparation method and application Download PDF

Info

Publication number
CN106229030B
CN106229030B CN201610534297.9A CN201610534297A CN106229030B CN 106229030 B CN106229030 B CN 106229030B CN 201610534297 A CN201610534297 A CN 201610534297A CN 106229030 B CN106229030 B CN 106229030B
Authority
CN
China
Prior art keywords
electrically conductive
carbon black
weight
graphite
conductive ink
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610534297.9A
Other languages
Chinese (zh)
Other versions
CN106229030A (en
Inventor
周宏明
王博益
李荐
简帅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changsha Kehui Furnace Technology Co., Ltd.
Original Assignee
Central South University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN201610534297.9A priority Critical patent/CN106229030B/en
Publication of CN106229030A publication Critical patent/CN106229030A/en
Application granted granted Critical
Publication of CN106229030B publication Critical patent/CN106229030B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • A24F47/008—
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • 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
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/18—Conductive material dispersed in non-conductive inorganic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic

Abstract

The invention discloses a kind of electrically conductive composition, by weight, comprising：Graphite 20~40；Carbon black 13~30；Titaniferous compound conducting particles 5~10；Glass dust 5~20.Present invention also offers electrically conductive ink comprising the electrically conductive composition and preparation method thereof.In addition, the application present invention also offers conducting film and the conducting film as made from the electrically conductive ink.Due to using flakey micron graphite in the present invention, spherical micron carbon black, spherical nano carbon black, highly conductive titaniferous compound particle these types different shape, the electrically conductive composition of different-grain diameter size mix, in follow-up sintering into after conducting film, big particle plays the role of chain, small particles play the role of filling the gap of big particle, so as to form close conductive channel, are conducive to increase the electric conductivity of obtained conducting film.

Description

A kind of electrically conductive composition, electrically conductive ink, conducting film, preparation method and application
Technical field
The present invention relates to a kind of carbon heating film heating-body and its application, and in particular to carbon heating film heating-body is in electronic smoke Change the application in device.
Background technology
Electric radiant Heating Film constantly came out as the product of heating element in recent years, it has more clear advantage, such as thermal efficiency Height, energy saving, long lifespan, external form alternative is strong, applied widely, processing technology is simple, simple in structure, cost is low, nothing Naked light, safe and reliable etc..Metal system mainly is used in the prior art, carbon-based material makees the conductive filler of film, although metal based material Electrical conductivity is high, but it has the shortcomings that as is evident below：It is of high cost that membrane material is done using noble metal, is done membrane material using base metal and is resisted Oxidisability is bad, it is impossible to continual and steady work.Therefore, sight is gradually transferred to cheap by people, and electric conductivity is preferable, is not easy Oxidation, performance are stablized, in the carbon-based material of acid and alkali resistance and solvent corrosion.Current most of carbon heating films are all with carbonaceous conductive grain Son combines macromolecule resin film-forming mode.Such as, the Chinese patent literature of Publication No. CN101624468A discloses one kind Conductive film of coating of high molecular polymer, Main Components are aromatic polyurethane resins and conductive black, transfer coated by release liners Method is prepared, and the formula of its floating coat slurry therewith is as follows, in parts by weight：Aromatic polyurethane resins 100；Toluene 120 ~160；Dimethylformamide 50~140；Conductive black 8~20；Dispersant 0.5~2.The prior art is as a result of resin For binding agent, the temperature in use of conducting film is limited.
103146260 A of Publication No. CN disclose a kind of conductive ink composition, including component：Electrically conductive particles, propylene Acid resin binding agent, organic solvent and additive；The conductive ink composition includes the component of following mass fraction：It is described Electrically conductive particles are electrically conductive graphite and the mixture of conductive black；The additive includes levelling agent, antioxidant, cohesive force and promotes At least one of agent, auxiliary rheological agents.
In the prior art, it is general no more than 250 DEG C there is the limitation of heating film temperature in use；General Conductivity Ratio The shortcomings of metal film two to three orders of magnitude of difference.
The content of the invention
It is low to solve existing existing carbon system heating film (conducting film) temperature in use, it is of the invention the defects of poorly conductive Purpose is to provide a kind of electrically conductive composition (conductive filler)；Additionally provide the electrically conductive ink and its system for including the electrically conductive composition Preparation Method.
In addition, the application present invention also offers conducting film and the conducting film as made from the electrically conductive ink.
A kind of electrically conductive composition, by weight, comprising
The graphite is flaky graphite, and particle diameter is 1um~80um.
The carbon black is the spherical Nano carbon of spherical the micron carbon black and/or particle diameter 30nm~200nm of particle diameter 1um~60um It is black.
Preferably, the carbon black is mixed by spherical micron carbon black and spherical nano carbon black, spherical micron carbon black and The weight part ratio 10~20: 3~10 of spherical nano carbon black.
Titaniferous compound conducting particles is preferably titanium nitride and/or titanium diboride.
The present invention uses glass powder with low melting point, preferably, the glass powder temperature is 400 DEG C~500 DEG C.
Due to using flakey micron graphite, spherical micron carbon black, spherical nano carbon black, highly conductive titaniferous compound in the present invention Particle these types different shape, the electrically conductive composition of different-grain diameter size mix, in follow-up sintering into after conducting film, big particle Play the role of chain, small particles play the role of filling the gap of big particle, so as to form close conductive channel, are conducive to increase The electric conductivity of obtained conducting film.
Present invention also offers a kind of electrically conductive ink (conductive carbon pastes), the electrically conductive composition is included.
Based on electrically conductive ink parts by weight, the electrically conductive ink includes the micron graphite of 20~40 parts by weight, 10~20 weight Part micron carbon black, the nano carbon blacks of 3~10 parts by weight, the titaniferous compound conducting particles of 5~10 parts by weight, 5~20 parts by weight The organic carrier of glass dust and 30~60 parts by weight.
Preferably, the electrically conductive ink also includes organic carrier；In terms of electrically conductive ink percetage by weight 100%, have The percetage by weight of airborne body is 30%~60%.
The organic carrier includes solvent, thickener, thixotropic agent, flow control agent and surfactant；Wherein, solvent, Thickener, thixotropic agent, the mass parts ratio of flow control agent and surfactant are 86-94: 2-8: 8-14: 1-4: 1-4.
In the present invention, the solvent selected from terpinol, citric acid tri butyl ester, neck dibatyl phithalate at least one Kind.
Preferably, the solvent is terpinol.
In the present invention, the thickener is selected from least one of ethyl cellulose, nitrocellulose, vistanex.
Preferably, the thickener is ethyl cellulose.
In the present invention, the thixotropic agent is at least one of rilanit special, oleic acid, calcium silicates.
Preferably, the thixotropic agent is rilanit special.
In the present invention, the flow control agent is at least one of furancarboxylic acid, terephthalic acid (TPA), ammonium sulfate.
Preferably, the flow control agent is terephthalic acid (TPA).
In the present invention, the surfactant is at least one of ethanol, toluene, cyclohexanone.
Preferably, the surfactant is ethanol.
Preferably, the organic carrier includes terpinol, ethyl cellulose, rilanit special, terephthalic acid (TPA) and Ethanol.Under the preferred organic carrier, terpinol, ethyl cellulose, terephthalic acid (TPA), the mass parts ratio of ethanol and rilanit special Example is 90-93: 3-5: 1-3: 1-3: 8-12.
Still more preferably, by weight, the organic carrier for 92 parts of terpinols, 4 parts of ethyl celluloses, 2 parts it is right The composition of phthalic acid, 2 parts of ethanol and 10 parts of rilanit specials.
In the present invention, by be combineding with each other for each material of the different structure and particle diameter, can effectively improving use, this is led The electric conductivity of material prepared by electric composition, in the glass dust of fusion temperature described in coordinated, can effectively improve conductive oil The temperature in use of conducting film made from ink.
Present invention also offers a kind of preparation method of the electrically conductive ink, comprise the following steps：
Step (1)：Graphite, carbon black pretreatment；
Step (2)：Ball milling again after being mixed after pretreated carbon black ball milling with graphite, titaniferous compound conducting particles, obtains powder 1；
Step (3)：By powder 1 and glass dust mixing and ball milling, powder 2 is obtained；
Step (4)：Powder 2 is mixed to prepare electrically conductive ink with organic carrier.
The method of the present invention uses substep ball milling mixing, greatly reducing the agglomeration of carbon black particle, while make difference Conductive filler mixing evenly, dispersiveness is more preferable, so as to contribute to the electrical conductivity of the follow-up obtained conducting film of increase.
In step (1), graphite, the respective pretreatment of carbon black, wherein preprocess method is identical.
Preprocess method is, for example,：Graphite or carbon black are placed in 50 DEG C~100 DEG C of alkali compounds aqueous solution (such as NaOH aqueous solutions) in and stir, mixing time is 10min~60min, after stirring with deionized water scouring stone ink, carbon black To neutrality, filter, 0.5h~3h is dried in vacuo in 60 DEG C~100 DEG C.
The concentration of the aqueous solution of alkali compounds chooses 5%~25%.For example, preprocessing process use weight concentration for 5%~25% NaOH aqueous solutions.
In step (2), first by carbon black pellet ball milling.The carbon black is spherical, the micron charcoal comprising the weight part ratio Black and nano carbon black.
Carbon black mechanical milling process can be：Pretreated spherical micron carbon black and spherical nano carbon black are mixed, added to existing There is in general ball-grinding machine (such as zirconia ball grinding jar), ratio of grinding media to material is, for example, 2: 1, then adds certain ball milling solvent (such as ethanol) carries out ball milling, is filtered after ball milling, and drying removes ball milling solvent to the solid portion of collection again,
In mechanical milling process, rotating speed 300-500r/min；Ball-milling Time is 6-10h.
In the present invention, by the gradation ball milling, the material of different-grain diameter can be uniformly mixed, help further to subtract Few agglomeration, plays the mutual synergistic effect of each material；So that follow-up sintering, into after conducting film, big particle plays the work of chain With small particles play the role of filling the gap of big particle, help to form the conductive channel of densification.
Continue ball-milling treatment, ball-milling treatment side after being mixed after carbon black ball milling, drying with graphite, titaniferous compound conducting particles Formula can be identical with carbon black ball grinding method, is filtered after ball milling, is dried to obtain powder 1.
Preferably, in step (2), the weight ratio of graphite, carbon black and titaniferous compound conducting particles for 20~40: 13~ 30: 5~10.
Titaniferous compound conducting particles is titanium nitride and/or titanium diboride, preferably titanium diboride.
By the powder 1 that ball milling obtains continue with glass dust mixing and ball milling, obtain powder 2；The ball grinding method of step (3) can be used for reference Carbon black ball grinding method.
In step (3), the glass powder temperature is 400 DEG C~500 DEG C, preferably 450 DEG C of melting glass frits.
In the method for the present invention, by the glass dust ball milling mixing into electrically conductive composition, compared to the carbon in most present situation Be conductive filler with resin solidification into film, the temperature in use for the film that electrically conductive ink of the invention sinters into can greatly improve.
Sieve is crossed after step (3) ball milling, drying, separates ball and material after ball milling, the sieve of sieving is, for example, 80 mesh, is collected The following particle of 80 mesh is powder 2.
In step (4), powder 2 and organic carrier are mixed to prepare electrically conductive ink.
Powder 2 is ground with organic carrier material using existing equipment, such as three-roll grinder.
The electrically conductive ink viscosity number is preferably 10000cp~40000cp.
Present invention also offers one kind using conducting film (carbon heating film heating-body) made from electrically conductive ink curing.
The electrically conductive ink is sprayed and/or is printed on carrier substrate, is cured up to conducting film.
By taking acid etching is coated with as an example, the conductive carbon pastes are sprayed on quartz glass by carrier substrate after acid etching Certain galvanic circle is formed on substrate, through drying, sintering, obtains carbon heating film heating-body.
Preferably, the carrier substrate is quartz glass, ceramics or resin substrate.
Preferably, the carrier substrate is preferably quartz glass.Favorably increased using pretreated quartz glass The bond strength of film and matrix.
The acid corrosion process uses existing conventional method, by taking quartz glass as an example, by quartz glass substrate successively with third Ketone, each supersound washing 5min~30min of deionized water, is then dried, then with certain density HF aqueous corrosions 0.5min~ 15min, is then washed with deionized to neutrality, dry.In HF aqueous solutions, HF concentration is chosen for 5%~40%.
Spraying process can use existing equipment (such as manual spray gun).Its carrier gas is industry N2, operating air pressure is set as 0.2MPa~0.4MPa, spraying number are 6~30 times.
After the completion of spraying, temperature programming curing is carried out, is solidificated under vacuum and carries out.Preferably, vacuum solidification Cheng Zhong, with 2 DEG C/min~10 DEG C/min heating rates to 150 DEG C~200 DEG C, keeps the temperature 5min~30min, then with 2 DEG C/min ~10 DEG C/min heating rates keep the temperature 10min~60min to 500 DEG C~600 DEG C.
In the present invention, a kind of preferable conducting film (carbon heating film heating-body) preparation method, comprises the following steps：
Step a：By carbon black and graphite be respectively placed in 50 DEG C~100 DEG C NaOH aqueous solutions stirring, then spend from Sub- water is rinsed to neutrality, is filtered, vacuum drying；
The carbon black is the micron carbon black of spherical particle diameter 1um~60um and the nano carbon black of particle diameter 30nm~200nm；It is micro- The weight part ratio 10~20: 3~10 of rice carbon black and spherical nano carbon black；
The graphite is flakey, and particle diameter is 1um~80um；
Step b：First will be conductive with the graphite and titaniferous compound after the carbon black in a solvent ball milling, filtering, drying Particle ball milling, filtering, dry powder 1 in a solvent；
Step c：By powder 1 and glass dust in a solvent ball milling, filtering, drying, sieve to obtain powder 2；
Wherein, graphite, carbon black, titaniferous compound conducting particles, glass dust add weight part ratio for 20~40: 13~30: 5~ 10: 5~20；
Step d：Powder 2 and organic carrier are mixed to prepare electrically conductive ink；Wherein, the organic carrier includes pine tar Alcohol, ethyl cellulose, rilanit special, terephthalic acid (TPA) and ethanol；Organic carrier accounts for the 30%~60% of electrically conductive ink weight；
Step e：The electrically conductive ink is sprayed on to the quartz glass substrate on piece after acid etching and forms galvanic circle, it is dry, Vacuum-sintering, obtains carbon heating film heating-body；During vacuum-sintering, with 2 DEG C/min~10 DEG C/min heating rates to 150 DEG C ~200 DEG C, 5min~30min is kept the temperature, then with 2 DEG C/min~10 DEG C/min heating rates to 500 DEG C~600 DEG C, insulation 10min~60min.
Step b is identical with step c mechanical milling process methods, and ratio of grinding media to material is also identical, and ball milling solvent is also identical, is, for example, ethanol.
Present invention additionally comprises a kind of application of obtained conducting film, and the conducting film is applied to electronic cigarette atomizing Device.
The temperature in use of of the invention designed and preparation conducting film can be more than or equal to 300 DEG C.
Beneficial effects of the present invention：
(1) present invention is due to using flakey micron graphite, spherical micron carbon black, spherical nano carbon black, highly conductive titanizing Thing particle these types different shape, the conductive filler of different-grain diameter size mix, and after sintering forms a film, big particle plays chain Effect, small particles play the role of filling the gap of big particle, so as to form close conductive channel, then electric conductivity greatly increases Add.
(2) present invention greatly reducing carbon black particle in hybrid conductive filler as a result of substep ball milling mixing Agglomeration, while different conductive filler is mixed evenly, dispersiveness is more preferable, so that the electrical conductivity after film forming is significantly Increase.
(3) present invention carries out low-temperature sintering film forming using carbon conductive filler and low-melting glass, compared in most present situation Carbon conductive filler and resin solidification into film, greatly improve the temperature in use of film.
(4) present invention takes slight erosion to handle matrix quartz glass, the favourable bond strength for increasing film and matrix.
Brief description of the drawings
Fig. 1 is the preparation flow figure of carbon heating film heating-body of the present invention；
Fig. 2 is the schematic diagram of the conductive channel of carbon heating film of the present invention；
Fig. 3 is that a kind of spraying of carbon heating film heating-body of the present invention is film-made schematic diagram.
Embodiment
Following embodiments are implemented by aforesaid operations method：
Following embodiments are using the preparation flow shown in Fig. 1.
Fig. 2 is the schematic diagram of the conductive channel of carbon heating film of the present invention, and the conductive channel of carbon heating film of the invention is distinguished By flakey micron graphite (a), spherical micron carbon black (b), spherical nano carbon black (c) composition, it can be seen that the heating film is by several Kind different shape, the conductive filler of different-grain diameter size mix, and after sintering forms a film, big particle plays the role of chain, granule Son plays the role of filling the gap of big particle, so as to form close conductive channel, then electric conductivity greatly increases.
As can be seen from Figure 3 air gun sprayed coating film mode of the present invention, 1 is spray gun, and 2 be base material, using quartz glass substrate Piece.
Embodiment 1：
Micron graphite, micron carbon black, nano carbon black are done into following pretreatment respectively：It is electric in 80 DEG C of 10%NaOH solution Magnetic stirs 15min, then with deionized water rinsing to neutrality, filters, 1h is dried in 80 DEG C of vacuum drying chambers.Pretreatment of raw material Afterwards, 17g microns of carbon blacks and 3g nano carbon blacks is taken to mix and be put into zirconia ball grinding jar, ratio of grinding media to material 2: 1, then adds a certain amount of Absolute ethyl alcohol, with the speed ball milling 8h of 300r/min, after ball milling is complete, filters, places into 80 DEG C of dry 2h in vacuum drying chamber, so Take out afterwards and obtain mixed powder 1 by above-mentioned ball milling drying mode with 40g micron graphites and 5g titanium diborides again, will then obtain Mixed powder 1 and 5g fusing points obtain mixed powder 2 by above-mentioned ball milling drying mode for 450 DEG C of glass dust, then cross 80 mesh sieves Son.
By terpinol: ethyl cellulose: terephthalic acid (TPA): ethanol: rilanit special weight part ratio is matched somebody with somebody for 92: 4: 2: 2: 10 Make the organic carrier needed for this experiment.It will take 30g organic carriers that 2h is mixed with the mixed powder 2 after above-mentioned sieving, then use Three-roll grinder grinds 5 times and obtains conductive carbon pastes repeatedly.
Quartz glass substrate is used into acetone successively, each supersound washing 5min of deionized water, is then placed in air dry oven 80 DEG C of dry 1h, then corrode 15min with 5%HF, then it is washed with deionized to neutrality, is put into air dry oven and does for 80 DEG C Dry 1h.
Processed quartz glass substrate is lain on experimental bench, with industrial N2For carrier gas, air pressure is set to 0.4MPa, adopts Conductive carbon pastes obtained above are sprayed on substrate with manual spray gun, circulation spraying 6 times, is then placed in vacuum drying chamber 80 DEG C of dry 1h.After drying, take out sample and be put into vacuum drying oven by following technique sintering：With 2 DEG C/min heating rates to 180 DEG C, 10min is kept the temperature, then with 2 DEG C/min heating rates to 550 DEG C, keeps the temperature 30min.
Obtained a kind of carbon heating film heating-body in embodiment is subjected to resistivity measurement, the performance of its result has excellent Electric conductivity, its resistivity are 1.6 × 10-4Ω·cm；Through Analysis of Heat Tolerance experimental test, its result performance temperature in use is at least super Cross 300 DEG C；Measured through attachment fastness, film is 1 grade with the attachment degree of matrix, and performance membrane is high with substrate combinating strength.
Embodiment 2：
Micron graphite, micron carbon black, nano carbon black are done into following pretreatment respectively：It is electric in 100 DEG C of 5%NaOH solution Magnetic stirs 10min, then with deionized water rinsing to neutrality, filters, 1h is dried in 80 DEG C of vacuum drying chambers.Pretreatment of raw material Afterwards, 20g microns of carbon blacks and 10g nano carbon blacks is taken to mix and be put into zirconia ball grinding jar, ratio of grinding media to material 2: 1, then adds a certain amount of Absolute ethyl alcohol, with the speed ball milling 8h of 300r/min, after ball milling is complete, filters, place into 80 DEG C of dry 2h in vacuum drying chamber, Then take out and obtain mixed powder 1 by above-mentioned ball milling drying mode with 20g micron graphites and 5g titanium diborides again, then incite somebody to action To mixed powder 1 and 8g fusing points obtain mixed powder 2 by above-mentioned ball milling drying mode for 500 DEG C of glass dust, then cross 80 mesh Sieve.
By terpinol: ethyl cellulose: terephthalic acid (TPA): ethanol: rilanit special weight part ratio is 91: 5: 3: 1: 10 systems Organic carrier needed for this experiment.The mixed powder 2 after 37g organic carriers and above-mentioned sieving will be taken to be mixed 2h, then with three Roller mill grinds 5 times and obtains conductive carbon pastes repeatedly.
Quartz glass substrate is used into acetone successively, each supersound washing 20min of deionized water, is then placed in air dry oven 80 DEG C of dry 1h, then corrode 5min with 20%HF, then it is washed with deionized to neutrality, is put into air dry oven and does for 80 DEG C Dry 1h.
Processed quartz glass substrate is lain on experimental bench, with industrial N2For carrier gas, air pressure is set to 0.3MPa, adopts Conductive carbon pastes obtained above are sprayed on substrate with manual spray gun, circulation spraying 10 times, is then placed in vacuum drying chamber In 80 DEG C of dry 1h.After drying, take out sample and be put into vacuum drying oven by following technique sintering：With 5 DEG C/min heating rates to 200 DEG C, 10min is kept the temperature, then with 5 DEG C/min heating rates to 600 DEG C, keeps the temperature 10min.
Obtained a kind of carbon heating film heating-body in embodiment is subjected to resistivity measurement, the performance of its result has excellent Electric conductivity, its resistivity are 3.6 × 10-4Ω·cm；Through Analysis of Heat Tolerance experimental test, its result performance temperature in use is at least super Cross 300 DEG C；Measured through attachment fastness, film is 1 grade with the attachment degree of matrix, and performance membrane is high with substrate combinating strength.
Embodiment 3：
Micron graphite, micron carbon black, nano carbon black are done into following pretreatment respectively：It is electric in 50 DEG C of 25%NaOH solution Magnetic stirs 15min, then with deionized water rinsing to neutrality, filters, 1h is dried in 80 DEG C of vacuum drying chambers.Pretreatment of raw material Afterwards, 12g microns of carbon blacks and 5g nano carbon blacks is taken to mix and be put into zirconia ball grinding jar, ratio of grinding media to material 2: 1, then adds a certain amount of Absolute ethyl alcohol, with the speed ball milling 8h of 300r/min, after ball milling is complete, filters, places into 80 DEG C of dry 2h in vacuum drying chamber, so Take out afterwards and obtain mixed powder 1 by above-mentioned ball milling drying mode with 20g micron graphites, 5g titanium diborides, 5g titanium nitrides again, connect The mixed powder 1 that will be obtained and obtain mixed powder 2 by above-mentioned ball milling drying mode with 20g fusing points for 400 DEG C of glass dust, then Cross 80 mesh sieve.
By terpinol: ethyl cellulose: terephthalic acid (TPA): ethanol: rilanit special weight part ratio is matched somebody with somebody for 93: 3: 2: 2: 12 Make the organic carrier needed for this experiment.It will take 33g organic carriers that 2h is mixed with the mixed powder 2 after above-mentioned sieving, then use Three-roll grinder grinds 5 times and obtains conductive carbon pastes repeatedly.
Quartz glass substrate is used into acetone successively, each supersound washing 30min of deionized water, is then placed in air dry oven 80 DEG C of dry 1h, then corrode 0.5min with 40%HF, then it is washed with deionized to neutrality, is put into air dry oven 80 DEG C Dry 1h.
Processed quartz glass substrate is lain on experimental bench, with industrial N2For carrier gas, air pressure is set to 0.25MPa, Conductive carbon pastes obtained above are sprayed on substrate using manual spray gun, circulation spraying 15 times, is then placed in vacuum drying 80 DEG C of dry 1h in case.After drying, take out sample and be put into vacuum drying oven by following technique sintering：Arrived with 2 DEG C/min heating rates 150 DEG C, 30min is kept the temperature, then with 2 DEG C/min heating rates to 500 DEG C, keeps the temperature 60min.
Obtained a kind of carbon heating film heating-body in embodiment is subjected to resistivity measurement, the performance of its result has excellent Electric conductivity, its resistivity are 3.0 × 10-4Ω·cm；Through Analysis of Heat Tolerance experimental test, its result performance temperature in use is at least super Cross 300 DEG C；Measured through attachment fastness, film is 1 grade with the attachment degree of matrix, and performance membrane is high with substrate combinating strength.
Embodiment 4：
Micron graphite, micron carbon black, nano carbon black are done into following pretreatment respectively：It is electric in 60 DEG C of 15%NaOH solution Magnetic stirs 60min, then with deionized water rinsing to neutrality, filters, 1h is dried in 80 DEG C of vacuum drying chambers.Pretreatment of raw material Afterwards, 10g microns of carbon blacks and 3g nano carbon blacks is taken to mix and be put into zirconia ball grinding jar, ratio of grinding media to material 2: 1, then adds a certain amount of Absolute ethyl alcohol, with the speed ball milling 8h of 300r/min, after ball milling is complete, filters, places into 80 DEG C of dry 2h in vacuum drying chamber, so Take out afterwards and obtain mixed powder 1 by above-mentioned ball milling drying mode with 20g micron graphites and 5g titanium diborides again, then incite somebody to action To mixed powder 1 and 5g fusing points obtain mixed powder 2 by above-mentioned ball milling drying mode for 480 DEG C of glass dust, then cross 80 mesh Sieve.
By terpinol: ethyl cellulose: terephthalic acid (TPA): ethanol: rilanit special weight part ratio is matched somebody with somebody for 90: 4: 3: 3: 8 Make the organic carrier needed for this experiment.It will take 57g organic carriers that 2h is mixed with the mixed powder 2 after above-mentioned sieving, then use Three-roll grinder grinds 5 times and obtains conductive carbon pastes repeatedly.
Quartz glass substrate is used into acetone successively, each supersound washing 10min of deionized water, is then placed in air dry oven 80 DEG C of dry 1h, then corrode 10min with 5%HF, then it is washed with deionized to neutrality, is put into air dry oven and does for 80 DEG C Dry 1h.
Processed quartz glass substrate is lain on experimental bench, with industrial N2For carrier gas, air pressure is set to 0.2MPa, adopts Conductive carbon pastes obtained above are sprayed on substrate with manual spray gun, circulation spraying 30 times, is then placed in vacuum drying chamber In 80 DEG C of dry 1h.After drying, take out sample and be put into vacuum drying oven by following technique sintering：With 2 DEG C/min heating rates to 180 DEG C, 10min is kept the temperature, then with 2 DEG C/min heating rates to 580 DEG C, keeps the temperature 30min.
Obtained a kind of carbon heating film heating-body in embodiment is subjected to resistivity measurement, the performance of its result has excellent Electric conductivity, its resistivity are 5.4 × 10-4Ω·cm；Through Analysis of Heat Tolerance experimental test, its result performance temperature in use is at least super Cross 300 DEG C；Measured through attachment fastness, film is 1 grade with the attachment degree of matrix, and performance membrane is high with substrate combinating strength.
Comparative example 1
Micron graphite, micron carbon black, nano carbon black are done into following pretreatment respectively：It is electric in 80 DEG C of 10%NaOH solution Magnetic stirs 15min, then with deionized water rinsing to neutrality, filters, 1h is dried in 80 DEG C of vacuum drying chambers.Pretreatment of raw material Afterwards, 17g microns of carbon blacks and 3g nano carbon blacks is taken to mix and be put into zirconia ball grinding jar, ratio of grinding media to material 2: 1, then adds a certain amount of Absolute ethyl alcohol, with the speed ball milling 8h of 300r/min, after ball milling is complete, filters, places into 80 DEG C of dry 2h in vacuum drying chamber, so Take out afterwards and obtain mixed powder 1 by above-mentioned ball milling drying mode with 40g micron graphites again, the mixed powder 1 that will then obtain Mixed powder 2 is obtained by above-mentioned ball milling drying mode for 450 DEG C of glass dust with 5g fusing points, then crosses 80 mesh sieve.
By terpinol: ethyl cellulose: terephthalic acid (TPA): ethanol: rilanit special weight part ratio is matched somebody with somebody for 80: 8: 6: 6: 12 Make the organic carrier needed for this experiment.It will take 30g organic carriers that 2h is mixed with the mixed powder 2 after above-mentioned sieving, then use Three-roll grinder grinds 5 times and obtains conductive carbon pastes repeatedly.
Quartz glass substrate is used into acetone successively, each supersound washing 5min of deionized water, is then placed in air dry oven 80 DEG C of dry 1h, then corrode 15min with 5%HF, then it is washed with deionized to neutrality, is put into air dry oven and does for 80 DEG C Dry 1h.
Processed quartz glass substrate is lain on experimental bench, with industrial N2For carrier gas, air pressure is set to 0.4MPa, adopts Conductive carbon pastes obtained above are sprayed on substrate with manual spray gun, circulation spraying 6 times, is then placed in vacuum drying chamber 80 DEG C of dry 1h.After drying, take out sample and be put into vacuum drying oven by following technique sintering：With 2 DEG C/min heating rates to 180 DEG C, 10min is kept the temperature, then with 2 DEG C/min heating rates to 550 DEG C, keeps the temperature 30min.
Obtained a kind of carbon heating film heating-body in comparative example is subjected to resistivity measurement, its result shows as general lead Electrically, its resistivity is 5.2 × 10-3Ω·cm；Through Analysis of Heat Tolerance experimental test, its result show temperature in use at least over 300℃；Measured through attachment fastness, film is I grade with the attachment degree of matrix, performance membrane and substrate combinating strength height.
Comparative example 2
Micron graphite, micron carbon black are done into following pretreatment respectively：The electromagnetic agitation in 80 DEG C of 10%NaOH solution 15min, then with deionized water rinsing to neutrality, filters, 1h is dried in 80 DEG C of vacuum drying chambers.After pretreatment of raw material, take 20g microns of carbon blacks, 40g micron graphites, the mixing of 5g titanium diborides are put into zirconia ball grinding jar, and ratio of grinding media to material 2: 1, then adds one Quantitative absolute ethyl alcohol, with the speed ball milling 8h of 300r/min, after ball milling is complete, filters, places into vacuum drying chamber and do for 80 DEG C Dry 2h obtains mixed powder 1, is then 450 DEG C of glass dust by above-mentioned ball milling drying side by obtained mixed powder 1 and 5g fusing points Formula obtains mixed powder 2, then crosses 80 mesh sieve.
By terpinol: ethyl cellulose: terephthalic acid (TPA): ethanol: rilanit special weight part ratio is matched somebody with somebody for 80: 8: 6: 6: 12 Make the organic carrier needed for this experiment.It will take 30g organic carriers that 2h is mixed with the mixed powder 2 after above-mentioned sieving, then use Three-roll grinder grinds 5 times and obtains conductive carbon pastes repeatedly.
Quartz glass substrate is used into acetone successively, each supersound washing 5min of deionized water, is then placed in air dry oven 80 DEG C of dry 1h, then corrode 15min with 5%HF, then it is washed with deionized to neutrality, is put into air dry oven and does for 80 DEG C Dry 1h.
Processed quartz glass substrate is lain on experimental bench, with industrial N2For carrier gas, air pressure is set to 0.4MPa, adopts Conductive carbon pastes obtained above are sprayed on substrate with manual spray gun, circulation spraying 6 times, is then placed in vacuum drying chamber 80 DEG C of dry 1h.After drying, take out sample and be put into vacuum drying oven by following technique sintering：With 2 DEG C/min heating rates to 180 DEG C, 10min is kept the temperature, then with 2 DEG C/min heating rates to 550 DEG C, keeps the temperature 30min.
Obtained a kind of carbon heating film heating-body in comparative example is subjected to resistivity measurement, its result shows as general lead Electrically, its resistivity is 8.2 × 10-3Ω·cm；Through Analysis of Heat Tolerance experimental test, its result show temperature in use at least over 300℃；Measured through attachment fastness, film is I grade with the attachment degree of matrix, performance membrane and substrate combinating strength height.
Comparative example 3
Micron graphite, micron carbon black, nano carbon black are done into following pretreatment respectively：It is electric in 80 DEG C of 10%NaOH solution Magnetic stirs 15min, then with deionized water rinsing to neutrality, filters, 1h is dried in 80 DEG C of vacuum drying chambers.Pretreatment of raw material Afterwards, 17g microns of carbon blacks and 3g nano carbon blacks is taken to mix and be put into zirconia ball grinding jar, ratio of grinding media to material 2: 1, then adds a certain amount of Absolute ethyl alcohol, with the speed ball milling 8h of 300r/min, after ball milling is complete, filters, places into 80 DEG C of dry 2h in vacuum drying chamber, so Take out afterwards and obtain mixed powder 1 by above-mentioned ball milling drying mode with 40g micron graphites and 5g titanium diborides again, then cross 80 mesh Sieve.
By terpinol: ethyl cellulose: terephthalic acid (TPA): ethanol: rilanit special weight part ratio is 70: 26: 2: 2: 10 Prepare the organic carrier needed for this experiment.It will take 30g organic carriers that 2h is mixed with the mixed powder 1 after above-mentioned sieving, then Ground repeatedly with three-roll grinder 5 times and obtain conductive carbon pastes.
Quartz glass substrate is used into acetone successively, each supersound washing 5min of deionized water, is then placed in air dry oven 80 DEG C of dry 1h, then corrode 15min with 5%HF, then it is washed with deionized to neutrality, is put into air dry oven and does for 80 DEG C Dry 1h.
Processed quartz glass substrate is lain on experimental bench, with industrial N2For carrier gas, air pressure is set to 0.4MPa, adopts Conductive carbon pastes obtained above are sprayed on substrate with manual spray gun, circulation spraying 6 times, is then placed in vacuum drying chamber 120 DEG C cure dry 1h.
Obtained a kind of carbon heating film heating-body in comparative example is subjected to resistivity measurement, its result shows as poor conduction Property, its resistivity is 4.8 × 10-2Ω·cm；Through Analysis of Heat Tolerance experimental test, its result performance temperature in use is no more than 160 ℃；Measured through attachment fastness, film is III level with the attachment degree of matrix, shows membrane and substrate combinating strength is not high.
It can be seen that the carbon heating film good conductivity of the present invention from embodiment 1-4, film use environment temperature is high, adhesive strength The advantages that high.
If not it can be seen that from embodiment 1 and comparative example 1-2 using the ball of flaky graphite and different-grain diameter in the present invention Shape carbon black and titaniferous compound mix the conducting particles of composition, and organic carrier ratio formula not using the present invention, then shape Into heating film electric conductivity it is poor the shortcomings that；If not this it appears that being used in the carbon heating film use present invention in comparative example 3 Low-melting glass sintering film forming mode, the film use environment temperature of formation limited significantly, and with the attachment of base material Intensity degradation.
Although the foregoing describing the embodiment of the present invention, it will be appreciated by those of skill in the art that these It is merely illustrative of, after the above of the present invention has been read, those skilled in the art can make the present invention various change Dynamic or modification, these equivalent forms also fall within the scope of the appended claims of the present application.

Claims (8)

  1. A kind of 1. electrically conductive composition, it is characterised in that：By weight, comprising
    Graphite 20 ~ 40；
    Carbon black 13 ~ 30；
    Titaniferous compound conducting particles 5 ~ 10；
    Glass dust 5 ~ 20；
    The graphite is flaky graphite, and particle diameter is 1um ~ 80um；The carbon black is the spherical micron charcoal of particle diameter 1um ~ 60um The black and spherical nano carbon black of particle diameter 30nm ~ 200nm；
    Titaniferous compound conducting particles is titanium nitride and/or titanium diboride；
    The weight part ratio 10 ~ 20 of spherical micron carbon black and spherical nano carbon black：3~10.
  2. 2. electrically conductive composition as claimed in claim 1, it is characterised in that：The glass powder temperature is 400 DEG C ~ 500 ℃。
  3. 3. a kind of electrically conductive ink, it is characterised in that include claim 1-2 any one of them electrically conductive compositions.
  4. 4. electrically conductive ink as claimed in claim 3, it is characterised in that：Based on electrically conductive ink parts by weight, the electrically conductive ink bag Micron graphite containing 20 ~ 40 parts by weight, the micron carbon black of 10 ~ 20 parts by weight, the nano carbon black of 3 ~ 10 parts by weight, 5 ~ 10 parts by weight Titaniferous compound conducting particles, the glass dust of 5 ~ 20 parts by weight and the organic carrier of 30 ~ 60 parts by weight.
  5. 5. electrically conductive ink as claimed in claim 4, it is characterised in that：The organic carrier includes solvent, thickener, thixotroping Agent, flow control agent and surfactant；Wherein, the matter of solvent, thickener, thixotropic agent, flow control agent and surfactant It is 86-94 to measure part ratio：2-8：8-14：1-4：1-4；
    The thixotropic agent is at least one of rilanit special, oleic acid, calcium silicates.
  6. 6. such as the preparation method of claim 3-5 any one of them electrically conductive inks, it is characterised in that：Comprise the following steps：
    Step（1）：Graphite, carbon black pretreatment；
    Step（2）：Ball milling again after being mixed after pretreated carbon black ball milling with graphite, titaniferous compound conducting particles, obtains powder 1；
    Step（3）：By powder 1 and glass dust mixing and ball milling, powder 2 is obtained；
    Step（4）：Powder 2 is mixed to prepare electrically conductive ink with organic carrier.
  7. A kind of 7. preparation method of conducting film, it is characterised in that：Claim 3-5 any one of them electrically conductive ink is sprayed And/or be printed on carrier substrate, cure under vacuum to obtain the final product；During vacuum solidification, with 2 DEG C/min ~ 10 DEG C/min liters Warm speed keeps the temperature 5min ~ 30min, then with 2 DEG C/min ~ 10 DEG C/min heating rates to 500 DEG C ~ 600 to 150 DEG C ~ 200 DEG C DEG C, keep the temperature 10min ~ 60min.
  8. 8. the application of conducting film made from a kind of claim 7, it is characterised in that the conducting film is applied to electronic smoke Change device.
CN201610534297.9A 2016-07-08 2016-07-08 A kind of electrically conductive composition, electrically conductive ink, conducting film, preparation method and application Active CN106229030B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610534297.9A CN106229030B (en) 2016-07-08 2016-07-08 A kind of electrically conductive composition, electrically conductive ink, conducting film, preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610534297.9A CN106229030B (en) 2016-07-08 2016-07-08 A kind of electrically conductive composition, electrically conductive ink, conducting film, preparation method and application

Publications (2)

Publication Number Publication Date
CN106229030A CN106229030A (en) 2016-12-14
CN106229030B true CN106229030B (en) 2018-04-20

Family

ID=57519205

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610534297.9A Active CN106229030B (en) 2016-07-08 2016-07-08 A kind of electrically conductive composition, electrically conductive ink, conducting film, preparation method and application

Country Status (1)

Country Link
CN (1) CN106229030B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113851251B (en) * 2021-11-30 2022-03-29 西安宏星电子浆料科技股份有限公司 Transitional pore filling slurry for connecting upper and lower gold and silver layers of membrane tape in LTCC substrate

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1845956A (en) * 2003-07-29 2006-10-11 阿克伦大学 Electrically-conducting polymers, a method for preparing electrically-conducting polymers, and a method for controlling electrical conductivity of polymers
CN101868064A (en) * 2010-06-21 2010-10-20 陕西科技大学 Environment-friendly graphite resistance paste and preparation method thereof
CN102443320A (en) * 2011-10-18 2012-05-09 张文知 Carbon water-based conductive ink

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5153993B2 (en) * 2004-03-24 2013-02-27 三菱樹脂株式会社 Conductive thermoplastic resin film
KR20130110960A (en) * 2012-03-30 2013-10-10 삼성전자주식회사 Conductive paste composition and solar cell using the same
US8815125B2 (en) * 2012-06-20 2014-08-26 E. I. Du Pont De Nemours And Company Method of manufacturing a resistor paste
CN103146260B (en) * 2013-03-20 2015-04-29 中国人民解放军国防科学技术大学 Conductive printing ink composition, conductive film layer as well as preparation method of conductive film layer and application of conductive printing ink composition
CN103531814B (en) * 2013-10-28 2015-03-25 深圳格林德能源有限公司 Composite conductive agent and dispersion method thereof as well as positive plate and lithium ion battery
CN105440879B (en) * 2014-08-21 2017-11-07 中国石油天然气集团公司 A kind of static conductive coating

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1845956A (en) * 2003-07-29 2006-10-11 阿克伦大学 Electrically-conducting polymers, a method for preparing electrically-conducting polymers, and a method for controlling electrical conductivity of polymers
CN101868064A (en) * 2010-06-21 2010-10-20 陕西科技大学 Environment-friendly graphite resistance paste and preparation method thereof
CN102443320A (en) * 2011-10-18 2012-05-09 张文知 Carbon water-based conductive ink

Also Published As

Publication number Publication date
CN106229030A (en) 2016-12-14

Similar Documents

Publication Publication Date Title
CN101620893B (en) All-silver electronic paste and preparation method thereof
CN105017831B (en) Water-based electric heating nano paint composition and coating and its preparation method and application
CN103811130B (en) Preparation method of graphene compound silver paste and graphene compound silver paste
CN109671942A (en) A kind of lithium-ion battery silicon-carbon anode material and preparation method thereof
CN109698040B (en) Water-based electronic paste and preparation method thereof
EP3783068B1 (en) Granular conductive carbon black and preparation method thereof
CN104801709B (en) Nickel-coated copper clad metal powder and preparation method and application thereof
CN106205935A (en) A kind of amorphous state soft magnetism composite magnetic powder core and preparation method thereof
CN109003826A (en) N and S codope graphene-graphene nanobelt aeroge preparation method
CN114453578A (en) Modified copper powder, modification method thereof and conductive paste
KR20090110739A (en) Printing paste composition for electrode of solar cell and electrode forming method using the same
CN110706842B (en) Front silver paste and preparation method thereof
CN108962425A (en) A kind of preparation method of graphene conductive slurry
CN106229030B (en) A kind of electrically conductive composition, electrically conductive ink, conducting film, preparation method and application
CN101950597B (en) Silver aluminum slurry for electromagnetic shielding and preparation method thereof
CN111148345A (en) Blue dielectric paste for thick film circuit and preparation method and application thereof
CN104538084A (en) High-temperature-resistant electric conducting silver paste
CN101409153B (en) Preparation method for first cathode layer of solid electrolyte capacitor
CN110698071B (en) Preparation method of composite glass powder and conductive silver paste
CN110416513B (en) Preparation method of carbon-silicon composite material, carbon-silicon composite electrode and battery comprising carbon-silicon composite electrode
CN103824653A (en) Method for preparing back-field slurry of high-performance crystal silicon solar cell
CN107424845A (en) A kind of preparation method of used by dye sensitization solar battery to electrode material
CN110449572A (en) The preparation method of the functional silver powder of electric slurry
CN101037555A (en) Inorganic nonmetal magnetic conducting coating and preparation method thereof
CN110942842A (en) Conductor paste and conductor material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20191028

Address after: No. 1018, xinkaipu Road, Tianxin District, Changsha City, Hunan Province

Patentee after: Changsha Kehui Furnace Technology Co., Ltd.

Address before: Yuelu District City, Hunan province 410083 Changsha Lushan Road No. 932

Patentee before: Central South University