CN109456645A - One kind exempting from surfactant graphene composite conductive ink - Google Patents
One kind exempting from surfactant graphene composite conductive ink Download PDFInfo
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- CN109456645A CN109456645A CN201811285182.6A CN201811285182A CN109456645A CN 109456645 A CN109456645 A CN 109456645A CN 201811285182 A CN201811285182 A CN 201811285182A CN 109456645 A CN109456645 A CN 109456645A
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- 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
Abstract
The invention discloses one kind to exempt from surfactant graphene composite conductive ink, is sufficiently mixed dispersion by the raw material components of following parts by weight and is made: CB@rGO conductive filler 1-50 parts by weight, binder 1-15 parts by weight and carbon atom are the alcoholic solvent 200-1000 parts by weight of 1-4.The present invention reduces contact resistance problem of the graphene nano material when forming conductive path by building " graphene-conductive black-graphene " conductive path effective solution graphene two conductive phase dispersion stabilization problems and agglomeration traits of graphene nanometer sheet in ink dispersion process.The present invention is added without additional surfactant, can disperse composite graphite alkene electrically conductive ink steadily in the long term, because of the surfactant of naked, can be reduced Thin-film anneal temperature and be promoted ink in the printing adaptability of all kinds of substrates.
Description
Technical field
The invention belongs to graphene applied technical fields, and in particular to one kind exempts from surfactant graphene composite conductive oil
Ink.
Background technique
Electrically conductive ink is a kind of composite material being made of conductive filler, binder, solvent and each analog assistant, wherein conductive
Filler is the key that electrically conductive ink performance phase.Have that countless conductive fillers is dispersed in binder and ink is molten in electrically conductive ink
In agent, the electrically conductive ink of liquid is in state of insulation, and the conductive pattern or printing film obtained after electrically conductive ink printing is annealed
The printing product obtained afterwards has certain electric conductivity.It is made by modes such as photoetching, chemical etching, chemical plating, vacuum depositions
There are many defects for standby conventional electronics and energy storage device: metal consumptive material valuableness, cumbersome, environmental pollution etc..20
The development first meeting clue of the nineties in century, electrically conductive ink have expedited the emergence of modern electricity in traditional silicon-based electronic IT innovation
Sub- printing technology-printing electrically conductive ink.All kinds of printing electrically conductive inks such as metal system electrically conductive ink, conductive polymer subsystem electrically conductive ink
And carbon series conductive ink is grown rapidly like the mushrooms after rain.
Although it is excellent and have certain application to study more mature conductive silver paste electric conductivity, Nano silver grain holds
Yi Fashengyin migration and sedimentation, and metallic silver is expensive is an impediment to its extensive use.And another kind of metallic conductive inks are conductive
Copper starches the electrically conductive ink more cheap as cost because copper nano particles inoxidizability is very poor, greatly limits its application and hair
Exhibition.In addition, conductive polymer subsystem (using PEDOT/PSS system as representative) electrically conductive ink stability is poor, electric conductivity is low, PEDOT/PSS
Conductive polymer ink need to suitably adulterate and weatherability is poor.Based on Graphene conductive ink preparation features electronic device compared with
There is its unique advantage in miscellaneous printing electrically conductive ink in the early time: corrosion-resistant, flexible, lightweight, cheaper, green
Environmental protection etc..With the development of graphene preparation technology, it includes: flexible electrical that Graphene conductive ink, which has set foot in every field application,
Sub- screen, function sensor, photovoltaic cell, print miniaturized circuitry and radio frequency identification devices (RFID) etc..Especially by
The extensive utilization of the RFID to attract attention both at home and abroad, rely on Graphene conductive ink product have low cost, can industrialization, environmentally protective
Etc. unique advantages, establish certain basis for the flexible electronic epoch.
Conductive material of the graphene as a new generation, has impayable high charge mobility, big from Colombia
It is 2.5 × 105cm that Kirill Bolotin measures its charge mobility from the graphene of structural integrity2/ (Vs) be
As many as 100 times of single crystal silicon material and its charge mobility are not influenced by temperature.Each carbon atom mentions in graphene-structured
Pi-electron for a non-bonding can simultaneously be moved freely in graphene plane of crystal, assign the electron mobility of its superelevation.Therefore
Graphene shows it widely in numerous areas such as energy storage, signal transmission, sensor detection, composite materials as conductive material
Application prospect.
The preparation method of Graphene conductive ink is broadly divided into liquid phase stripping method preparation Graphene conductive ink and oxygen at present
Change reduction method and prepares Graphene conductive ink.Liquid phase stripping method is mainly reflected in utilize the surface energy between graphene and organic solvent
(Es) existing mechanism between difference and the interlaminar action power of graphene: the Van der Waals i.e. between the lower graphene layer of surface energy differential value is made
Firmly smaller, wherein graphene surface can (Es-G≈70.0mJ·m-2) and dimethylformamide surface energy (DMF) (ES-DMF≈
65.0mJ·m-2) can (NMP) (E with N-Methyl pyrrolidone surfaces-NMP≈68.2mJ·m-2) between be closer to.Therefore liquid
Phase stripping method is mainly carried out speed shearing removing acquisition graphene conductive filler to natural graphite using this kind of solvent and is prepared with this
Graphene conductive ink.However this method prepares inefficient, graphene sheet layer distribution is big, and piece diameter is not of uniform size, and DMF and NMP
Solvent toxicity causes it to be not particularly suited for commercial applications greatly.Recently also occur removing grapheme material using mixed solvent liquid phase
The report for preparing Graphene conductive ink obtains surface energy and graphene by the proportion between regulation green solvent ethyl alcohol and water
Similar mixed solvent simultaneously is removed to obtain graphene with this.This method process is relatively easy, and avoids poisonous and harmful solvent, however
The addition of dispersion problem or the surfactant excessively to insulate for graphene will all hinder liquid phase stripping method in conduction
The application of ink area.Stripping method preparation Graphene conductive ink is aoxidized then from the dispersion for solving Graphene conductive ink, GO
It is scattered in electrically conductive ink directly as conductive presoma, can be obtained the green electrically conductive ink of aqueous high stable dispersion, however
GO electrically conductive ink prints resulting conductive film and further work-up is needed to obtain the material for having certain electric conductivity, post-processing
It is handled including thermal reduction processing or electronation processing and rolling, and all kinds of post-processing methods will all be damaged also to a certain degree
Former graphene oxide film.And it is big by rGO film brittleness prepared by GO electrically conductive ink, reelability is poor.It studies at present intimately
Still there is more apparent defect in the preparation method of two class Graphene conductive inks, if therefore being avoided that higher boiling toxic solvent
With the use of the surfactant of insulation, prepares one kind and have solvent safety environmental protection, surfactant-free, high stable dispersion, height
Electric conductivity, the Graphene conductive ink of printable fexible film will push the development of next-generation flexible electronic device.
Summary of the invention
It is an object of the invention to overcome prior art defect, one kind is provided and exempts from surfactant graphene composite conductive oil
Ink.
Technical scheme is as follows:
One kind exempting from surfactant graphene composite conductive ink, is sufficiently mixed dispersion by the raw material components of following parts by weight
It is made:
CB@rGO conductive filler 1-50 parts by weight
Binder 1-15 parts by weight
Carbon atom is the alcoholic solvent 200-1000 parts by weight of 1-4；
After above-mentioned CB@rGO conductive filler is by graphene oxide and carbon black mixing, then through ethylene glycol and p-phenylenediamine reduction system
At.
In a preferred embodiment of the invention, the preparation method of the CB@rGO conductive filler includes following step
It is rapid:
(1) graphene oxide, carbon black are mixed with water, after sonicated, obtains GO/CB dispersion liquid；
(2) GO/CB dispersion liquid is subjected to freeze-drying process, obtains GO interlayer CB conduction presoma；
(3) GO interlayer CB conduction forerunner, ethylene glycol and p-phenylenediamine are mixed, then also in 70-100 DEG C of progress hot bath
Former 1-24h；
(4) step (3) resulting material is obtained into the CB@rGO conductive filler by alcoholic solution washing.
It is further preferred that the mass ratio of the graphene oxide, carbon black and water is 1-10: 1-10: 100-1000.
It is further preferred that the mass ratio of the GO interlayer CB conduction forerunner, ethylene glycol and p-phenylenediamine are 1-10: 10-
1000∶1-100。
It is further preferred that the carbon black is at least one of acetylene black, furnace black, channel black, channel black and lampblack.
It is further preferred that the particle diameter of the carbon black is 10-200nm, initial conductivity 5-200S/m.
Still more preferably, the graphene oxide is prepared by traditional Hummers method, graphene oxide
It is using crystalline flake graphite as raw material, with KMnO4Oxidation intercalation is carried out to original crystalline flake graphite as strong oxidizer with the concentrated sulfuric acid.
Still more preferably, the binder is polyvinyl alcohol, polyethylene glycol, acrylic resin, epoxy resin, poly- ammonia
At least one of ester resin, hydroxypropyl methyl cellulose and nitrocellulose.
Still more preferably, the alcoholic solvent be ethyl alcohol, ethylene glycol, glycerine, isopropanol and n-butanol at least
It is a kind of.
The beneficial effects of the present invention are:
1, the present invention is existed by building " graphene-conductive black-graphene " conductive path effective solution graphene
Two conductive phase dispersion stabilization problems and the agglomeration traits of graphene nanometer sheet, reduce graphene and receive in ink dispersion process
Contact resistance problem of the rice material when forming conductive path.
2, the present invention is added without additional surfactant, can disperse composite graphite alkene electrically conductive ink steadily in the long term, because
The surfactant of naked can reduce Thin-film anneal temperature and promote ink in the printing adaptability of all kinds of substrates.
3, alcoholic solvent of the invention selectivity multiplicity, including ethylene glycol, glycerine, isopropanol, n-butanol etc..Different viscosities
Solvent selection can get different viscosities electrically conductive ink so that Graphene conductive ink be adapted to all kinds of mode of printings (drop coating,
The modes such as spin coating, inkjet printing and silk-screen printing).
4, the reducing agent p-phenylenediamine in the present invention is provided simultaneously with the effect of reduction GO and dispersed electro-conductive filler, and reaction is completed
The pi-conjugated effect of π-is formed between the oxidation product (OPPD) and rGO nanometer sheet of p-phenylenediamine afterwards, with aqueous functional group
OPPD can effectively form stable dispersion system between conductive filler CB rGO.Electrically conductive ink surfactant-free of the present invention adds
Add, high stable dispersion, the advantages such as high conductivity, excellent printing adaptability, excellent flexible conductive film are expected to be applied to print
Brush all kinds of flexible electronic devices.
Detailed description of the invention
Fig. 1 is the schematic illustration that surfactant graphene composite conductive ink is exempted from present invention preparation；
Fig. 2 be the present invention exempt from surfactant graphene composite conductive ink (20mg/mL) using different solvents as divide
Dispersion liquid carries out dispersion performance test, stands dispersed Comparative result picture after two months；
Fig. 3 is the conductivity test result figure for exempting from surfactant graphene composite conductive ink of the invention, wherein
It (a) is the conductivity test result comparison of different graphenes prepared in case 1,2 of the present invention/carbon black proportion conductive film
Figure, (b) the conductive film conductivity test result comparison diagram prepared for the embodiment of the present invention 1 by Different treatments；
Fig. 4 is the test result figure for exempting from surfactant graphene composite conductive ink of the invention, wherein (a) is this
The prepared ink of inventive embodiments 1,2 is printed on the graphene composite conductive film obtained in paper substrates, and film is connected
Among conductive path, the light bulb in circuit can be made to shine；(b) graphene composite conductive film and pure carbon black conductive film is soft
Property test chart.
Specific embodiment
Technical solution of the present invention is further explained and described below by way of specific embodiment combination attached drawing.
Embodiment 1
(1) raw material of following mass parts: 1 part of graphene oxide, 1 part of acetylene carbon black is accurately weighed, at high frequency ultrasound
Reason, dispersion remove graphene oxide (GO) nanometer sheet and by carbon black particle (CB) intercalation stannic oxide/graphene nano pieces, obtain steady
Fixed graphene oxide/carbon black (GO/CB) dispersion liquid；
(2) resulting GO/CB dispersion liquid is subjected to freeze-drying process, obtains CB interlayer GO conduction presoma；
(3) raw material of following mass parts: 0.5 part/5 parts of p-phenylenediamine (PPD), 1 part of persursor material, second two is accurately weighed
100 parts of alcohol, high frequency ultrasound 1min after mixing, CB@rGO clad structures then are obtained to acquisition 80 DEG C of water bath processings of dispersion liquid constant temperature
Material.Extra p-phenylenediamine and free carbon black particle are removed by filtering, washing, centrifugally operated, obtains low reduction degree
The conductive filler of (LCB@rGO) and high reduction degree (HCB@rGO), the preparation principle of conductive filler are as shown in Figure 2.
(4) raw material of following mass parts: 5 parts of CB@rGO conductive filler, 1 part of water-based acrylic resin, second two is accurately weighed
100 parts of alcohol mixing carry out high frequency ultrasound processing to mixed liquor, obtain graphene composite conductive ink.
(5) electrically conductive ink is spun on glass slide by spin-coating method, and is placed in 80 DEG C of constant temperature convection ovens and heats
Drying, obtains composite graphite alkene conductive graphene membrane, the formation of Thin film conductive access, as shown in Figure 2.
(6) all kinds of characterization tests, including the test of four probe resistances, scanning electricity are carried out to acquisition conductive filler, conductive film
Sub- microscope (SEM), performance test and characterization are as shown in Figure 1,2,3, 4.
Embodiment 2
(1) raw material of following mass parts is accurately weighed: 1 part of graphene oxide, 4 parts/2 parts/1 part/0.5 part of acetylene carbon black/
0.25 part of (MGO/MCB=4/1,2/1,1/1,1/2,1/4), handled by high frequency ultrasound, dispersion removing graphene oxide (GO) receive
Rice piece and by carbon black particle (CB) intercalation stannic oxide/graphene nano piece, obtains stable graphene oxide/carbon black (GO/CB) point
Dispersion liquid；
(2) resulting GO/CB dispersion liquid is subjected to freeze-drying process, obtains CB interlayer GO conduction presoma；
(3) raw material of following mass parts: 5 parts of p-phenylenediamine (PPD), persursor material (M is accurately weighedGO/MCB=4/1,
2/1,1/1,1/2,1/4) each 1 part, 100 parts of ethylene glycol, high frequency ultrasound 1min after mixing, then to 80 DEG C of dispersion liquid constant temperature of acquisition
Water bath processing obtains CB@rGO clad structure material.Extra p-phenylenediamine and trip are removed by filtering, washing, centrifugally operated
From carbon black particle, obtain the HCB@rGO conductive filler of high reduction degree；
(4) raw material of following mass parts: CB@rGO (M is accurately weighedGO/MCa=4/1,2/1,1/1,1/2,1/4) conduction is filled out
Expect each 5 parts, 1 part of water-based acrylic resin, 100 parts of ethylene glycol mixing, high frequency ultrasound processing is carried out to mixed liquor, obtains (MGO/
MCB=4/1,2/1,1/1,1/2,1/4) five parts of graphene composite conductive ink；
(5) electrically conductive ink is spun on glass slide by spin-coating method, and is placed in 80 DEG C of constant temperature convection ovens and heats
Drying, obtains graphene composite conductive graphene film；
(6) all kinds of characterization tests are carried out (except the test of four probe resistances utilizes CB@rGO to acquisition conductive filler, conductive film
Conductive filler (MGO/MCB=4/1,2/1,1/1,1/2,1/4) sample resistance test is outer, remaining performance test uses CB@rGO
Conductive filler (MGO/MCB=1/1) material), including the test of four probe resistances, SEM performance test and characterization are such as the institute of Fig. 1,2,3,4
Show；
As shown in Figure 1, being obtained by the graphene composite conductive ink preparation principle figure of the embodiment of the present invention 1 by cryochem
Conductive filler conduction presoma be CB intercalation GO structure, this structure presoma restore during, graphene can be prevented
Because surface free energy reduction caused by reunite, and rGO nanometer sheet extra in reduction process also because surface can reduction
And it is coated on the structure (CB@rGO) that presoma surface forms complete graphene package carbon black particle intercalation object.Stone in Fig. 2
Black alkene composite conducting ink can disperse steadily in the long term in ethylene glycol, glycerine, n-butanol, isopropanol, DMF, NMP.In Fig. 3
RACB@rGO conductive film resistivity reach 5091S/m, the conductive film of acquisition has splendid electric conductivity.Such as Fig. 4 (a)
The shown all kinds of patterns and Crush tests obtained by graphene composite conductive film printing (b) are graphene composite guide
Conductive film undergo still retain after thousands of time foldings 85% conductivity, and common carbon black conductive ink is then because of conductive path
Destruction, fold 200 times after lose electric conductivity.
In conclusion illustrating a kind of surfactant graphene composite conductive ink of exempting from of the present invention without additional surface-active
Agent addition, can be realized dispersion steady in a long-term.Because of the surfactant of naked, Thin-film anneal temperature can be reduced and promote ink
In the printing adaptability of all kinds of substrates.The solvent selectivity multiplicity of electrically conductive ink, including ethylene glycol, glycerine, isopropanol, positive fourth
Alcohol, DMF, NMP etc..The selection of different viscosities solvent can get the electrically conductive ink of different viscosities, so that Graphene conductive ink is suitable
It should be in all kinds of mode of printings (modes such as drop coating, spin coating, inkjet printing and silk-screen printing).The present invention also constructs " graphene-conduction
Carbon black-graphene " conductive path solves agglomeration traits of the grapheme material in reduction process and reduces graphene and receives
Contact resistance problem of the rice material when forming conductive path.Simultaneously by aqueous p-phenylenediamine oxidation product (OPPD) with
The pi-conjugated effect of π-is formed between rGO nanometer sheet to form stable dispersion system between conductive filler CB rGO and OPPD.This hair
Bright electrically conductive ink surfactant-free addition, high stable dispersion, high conductivity, excellent printing adaptability, excellent flexibility are led
The advantages such as conductive film are expected to be applied to print all kinds of flexible electronic devices.
Those of ordinary skill in the art still are able to it is found that when technical solution of the present invention changes in following ranges
To same as the previously described embodiments or similar technical effect, protection scope of the present invention is still fallen within:
One kind exempting from surfactant graphene composite conductive ink, is sufficiently mixed dispersion by the raw material components of following parts by weight
It is made:
CB@rGO conductive filler 1-50 parts by weight
Binder 1-15 parts by weight
Carbon atom is the alcoholic solvent 200-1000 parts by weight of 1-4；
After above-mentioned CB@rGO conductive filler is by graphene oxide and carbon black mixing, then through ethylene glycol and p-phenylenediamine reduction system
At.
The preparation method of the CB@rGO conductive filler includes the following steps:
(1) graphene oxide, carbon black are mixed with water, after sonicated, obtains GO/CB dispersion liquid；
(2) GO/CB dispersion liquid is subjected to freeze-drying process, obtains GO interlayer CB conduction presoma；
(3) GO interlayer CB conduction forerunner, ethylene glycol and p-phenylenediamine are mixed, then carries out hot bath reduction in 20-200
1-48h；
(4) step (3) resulting material is obtained into the CB@rGO conductive filler by alcoholic solution washing.
The mass ratio of the graphene oxide, carbon black and water is 1-10: 1-10: 100-1000.The GO interlayer CB is conductive
The mass ratio of forerunner, ethylene glycol and p-phenylenediamine are 1-10: 10-1000: 1-100.The carbon black be acetylene black, furnace black, channel black,
At least one of channel black and lampblack.The particle diameter of the carbon black is 10-200nm, initial conductivity 5-200S/m.
The graphene oxide is prepared by traditional Hummers method, and graphene oxide is to be with crystalline flake graphite
Raw material, with KMnO4Oxidation intercalation is carried out to original crystalline flake graphite as strong oxidizer with the concentrated sulfuric acid.The binder is polyethylene
In alcohol, polyethylene glycol, acrylic resin, epoxy resin, polyurethane resin, hydroxypropyl methyl cellulose and nitrocellulose extremely
Few one kind.The alcoholic solvent is at least one of ethyl alcohol, ethylene glycol, glycerine, isopropanol and n-butanol.
The foregoing is only a preferred embodiment of the present invention, the range that the present invention that therefore, it cannot be limited according to is implemented, i.e.,
Equivalent changes and modifications made in accordance with the scope of the invention and the contents of the specification should still be within the scope of the present invention.
Claims (9)
1. one kind exempts from surfactant graphene composite conductive ink, it is characterised in that: filled by the raw material components of following parts by weight
Mixing dispersion is divided to be made:
CB@rGO conductive filler 1-50 parts by weight
Binder 1-15 parts by weight
Carbon atom is the alcoholic solvent 200-1000 parts by weight of 1-4；
After above-mentioned CB@rGO conductive filler is by graphene oxide and carbon black mixing, then restores and be made through ethylene glycol and p-phenylenediamine.
2. one kind as described in claim 1 exempts from surfactant graphene composite conductive ink, it is characterised in that: the CB@
The preparation method of rGO conductive filler includes the following steps:
(1) graphene oxide, carbon black are mixed with water, after sonicated, obtains GO/CB dispersion liquid；
(2) GO/CB dispersion liquid is subjected to freeze-drying process, obtains GO interlayer CB conduction presoma；
(3) GO interlayer CB conduction forerunner, ethylene glycol and p-phenylenediamine are mixed, then restores 1- in 70-100 DEG C of progress hot bath
24h；
(4) step (3) resulting material is obtained into the CB@rGO conductive filler by alcoholic solution washing.
3. one kind as claimed in claim 2 exempts from surfactant graphene composite conductive ink, it is characterised in that: the oxidation
The mass ratio of graphene, carbon black and water is 1-10: 1-10: 100-1000.
4. one kind as claimed in claim 2 exempts from surfactant graphene composite conductive ink, it is characterised in that: the GO folder
The mass ratio of layer CB conduction forerunner, ethylene glycol and p-phenylenediamine are 1-10: 10-1000: 1-100.
5. one kind as claimed in claim 2 exempts from surfactant graphene composite conductive ink, it is characterised in that: the carbon black
For at least one of acetylene black, furnace black, channel black, channel black and lampblack.
6. one kind as claimed in claim 2 exempts from surfactant graphene composite conductive ink, it is characterised in that: the carbon black
Particle diameter be 10-200nm, initial conductivity 5-200S/m.
7. one kind as described in any claim in claim 1 to 6 exempts from surfactant graphene composite conductive ink,
Be characterized in that: the graphene oxide is prepared by traditional Hummers method, and graphene oxide is to be with crystalline flake graphite
Raw material, with KMnO4Oxidation intercalation is carried out to original crystalline flake graphite as strong oxidizer with the concentrated sulfuric acid.
8. one kind as described in any claim in claim 1 to 6 exempts from surfactant graphene composite conductive ink,
Be characterized in that: the binder is polyvinyl alcohol, polyethylene glycol, acrylic resin, epoxy resin, polyurethane resin, hydroxypropyl
At least one of methylcellulose and nitrocellulose.
9. one kind as described in any claim in claim 1 to 6 exempts from surfactant graphene composite conductive ink,
Be characterized in that: the alcoholic solvent is at least one of ethyl alcohol, ethylene glycol, glycerine, isopropanol and n-butanol.
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| CN111004546A (en) * | 2019-11-28 | 2020-04-14 | 华瑞墨石丹阳有限公司 | Graphite nanosheet conductive ink and preparation method and application thereof |
| CN111117369A (en) * | 2020-02-05 | 2020-05-08 | 广州特种承压设备检测研究院 | Polyaniline functionalized graphene conductive ink and preparation method thereof |
| CN111432509A (en) * | 2020-04-15 | 2020-07-17 | 广东康烯科技有限公司 | Titanium quantum dot doped graphene-based electric heating plate and electric heating device |
| CN112011228A (en) * | 2020-08-31 | 2020-12-01 | 上海电力大学 | Conductive film coating for improving oxidation resistance of copper plate and preparation method thereof |
| CN112500741A (en) * | 2020-10-29 | 2021-03-16 | 宁波石墨烯创新中心有限公司 | Graphene composite conductive ink and preparation method and application thereof |
| CN113249762A (en) * | 2021-05-28 | 2021-08-13 | 黑龙江科技大学 | Preparation method of graphene high-temperature heating aluminum plate |
| US20220044879A1 (en) * | 2020-08-07 | 2022-02-10 | Beijing University Of Chemical Technology | Large-Area Continuous Flexible Free-Standing Electrode And Preparation Method And Use Thereof |
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| CN112500741B (en) * | 2020-10-29 | 2024-04-19 | 宁波石墨烯创新中心有限公司 | Graphene composite conductive ink and preparation method and application thereof |
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| CN111004546A (en) * | 2019-11-28 | 2020-04-14 | 华瑞墨石丹阳有限公司 | Graphite nanosheet conductive ink and preparation method and application thereof |
| CN111117369A (en) * | 2020-02-05 | 2020-05-08 | 广州特种承压设备检测研究院 | Polyaniline functionalized graphene conductive ink and preparation method thereof |
| CN111117369B (en) * | 2020-02-05 | 2022-11-15 | 广州特种承压设备检测研究院 | Polyaniline functionalized graphene conductive ink and preparation method thereof |
| CN111432509A (en) * | 2020-04-15 | 2020-07-17 | 广东康烯科技有限公司 | Titanium quantum dot doped graphene-based electric heating plate and electric heating device |
| CN111432509B (en) * | 2020-04-15 | 2022-02-11 | 广东康烯科技有限公司 | Titanium quantum dot doped graphene-based electric heating plate and electric heating device |
| US20220044879A1 (en) * | 2020-08-07 | 2022-02-10 | Beijing University Of Chemical Technology | Large-Area Continuous Flexible Free-Standing Electrode And Preparation Method And Use Thereof |
| CN112011228A (en) * | 2020-08-31 | 2020-12-01 | 上海电力大学 | Conductive film coating for improving oxidation resistance of copper plate and preparation method thereof |
| CN112011228B (en) * | 2020-08-31 | 2022-01-07 | 上海电力大学 | Conductive film coating for improving oxidation resistance of copper plate and preparation method thereof |
| CN112500741A (en) * | 2020-10-29 | 2021-03-16 | 宁波石墨烯创新中心有限公司 | Graphene composite conductive ink and preparation method and application thereof |
| CN112500741B (en) * | 2020-10-29 | 2024-04-19 | 宁波石墨烯创新中心有限公司 | Graphene composite conductive ink and preparation method and application thereof |
| CN113249762A (en) * | 2021-05-28 | 2021-08-13 | 黑龙江科技大学 | Preparation method of graphene high-temperature heating aluminum plate |
| CN114235902A (en) * | 2021-11-15 | 2022-03-25 | 湖北亿纬动力有限公司 | Method for testing dispersion stability of carbon black |
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