CN109811382A - A kind of application of graphene oxide conductive paste in black holesization is directly electroplated - Google Patents
A kind of application of graphene oxide conductive paste in black holesization is directly electroplated Download PDFInfo
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- CN109811382A CN109811382A CN201910244507.4A CN201910244507A CN109811382A CN 109811382 A CN109811382 A CN 109811382A CN 201910244507 A CN201910244507 A CN 201910244507A CN 109811382 A CN109811382 A CN 109811382A
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Abstract
The invention discloses a kind of application of graphene oxide conductive paste in black holesization is directly electroplated, including prepare graphene oxide conductive paste and carry out black holesization using graphene oxide conductive paste obtained and be directly electroplated.The present invention is modified graphene oxide, its surface is set to contain isocyanate group, make graphene oxide conductive paste that there is very high mobility and film forming, graphene oxide compacted zone after attachment has stable continuity, the intensity of compacted zone can more be enhanced while increasing conductive capability, also it is less prone to micro-fractures or fracture when deformation occurs in electroplate, increases the service life of conductive plate;The present invention carries out the direct electroplating technique step of black holesization using graphene oxide conductive paste and significantly simplifies compared to existing black holes directly electroplating technology, and being only repeated once coating can be completed entire electroplating technology, easy to operate, high yield rate.
Description
Technical field
The present invention relates to the direct electroplating technology of black holesization more particularly to a kind of graphene oxide conductive paste are direct in black holesization
Application in plating.
Background technique
Printed wiring board (PCB, FPC) hole metallization technology is the key that one of printed board manufacturing technology, for a long time, people
Use electroless copper plating (PTH) always method, but containing the various chemical substances of harmful ecological environment in PTH solution, such as
EDTA, NTA, EDTP and it is easy carcinogenic formaldehyde, wastewater treatment is complicated, at high cost.In addition, PTH stability of solution is poor, it is molten
Analysis, the maintenance of liquid are complicated;The mechanical performance of PTH copper plate is poor simultaneously, and process flow is cumbersome, therefore industry is being sought always
New hole metallization technology is looked for, the direct electroplating technology of black holesization is exactly to come into being in this background.
The direct electroplating technology of black holesization is to form fine graphite or charcoal blacking (blank hole liquid) dip-coating on hole wall to lead
Then electric layer is directly electroplated.Its key technology is exactly the composition of black holes solution composition.First by fine graphite or carbon
Black powder is uniformly dispersed in medium in i.e. deionized water, makes the uniform graphite of solution or carbon using the surfactant in solution
Black suspension remained stable, and also possess good wettability, so that graphite or carbon black is sufficiently attracted to idioelectric hole
On wall surface, conductive layer forming uniform and delicate, being firmly combined.The direct electroplating technology raw material of black holesization is without decomposition in distress
EDTA, EDTP and the harmful substances such as formaldehyde that can be carcinogenic etc., environmental pollution is small, and wastewater treatment is simple, and processing cost reduces;Work
Skill processing procedure shortens, and production efficiency significantly improves, as long as black holes processing procedure 16 minutes, only about the 1/3 of PTH process time;It is black
Hole chemical industry skill is easy to control, easy to operate, and analysis, maintenance, the adjustment of solution are simple, and mixed economy cost compares electroless copper plating
(PTH) it is greatly reduced.
The core of the direct electroplating technology of black holesization is blank hole liquid, and blank hole liquid is the extremely strong fine carbon black of conductive capability or graphite
The dark solution of composition, with good stability, no hydrogen is precipitated in completing the adsorption process to the copper-clad plate after drilling,
Blank hole liquid in physical, does not chemically react in adsorption process, and also just there is no consume other ingredients because of chemical reaction
The phenomenon that, without analyzing and adjusting solution, it can be added completely according to the detraction of actual production, ensure that the stabilization of its work
Property.
The main component of existing blank hole liquid is short grained carbon black or graphite, and compacted zone need to be formed on electroplate just has
Electric conductivity, if conductive layer consistency is inadequate or has vacant position, electric conductivity can decline to a great extent, and electroplate once occurs slightly
Deformation, conductive layer be then likely to occur micro-fractures even be broken, cause wiring board not to be available.
Although the direct electroplating technology of black holesization substantially shortens compared to electroless copper plating processing step, black holesization is directly electroplated
Technical step is various, needs the repetitive operation coating, cold-hot wind dry and microetch, the operation of each step is required to stringent
Control, any of them step, which is made a fault, will lead to the failure of plating, reduce yield rate, increase cost.
Summary of the invention
The present invention is more for the direct electroplating technology step of existing black holesization and asks the consistency requirements of conductive layer are stringent
Topic provides a kind of application of graphene oxide conductive paste in black holesization is directly electroplated.
The technical scheme to solve the above technical problems is that a kind of graphene oxide conductive paste is direct in black holesization
Application in plating, including prepare graphene oxide conductive paste and use graphene oxide conductive paste obtained progress black holesization straight
Connect plating, which is characterized in that the steps include:
A, graphene oxide conductive paste is prepared
A1 it) prepares graphite oxide powder: 10g natural flake graphite is immersed into the mixed of the 100ml concentrated sulfuric acid and 20ml concentrated nitric acid
It closes in acid, is filtered after impregnating 12-18h under room temperature, after filter cake is washed with deionized to washing lotion pH value between 6-7, then will
Filter cake is placed in a vacuum drying oven, 60 DEG C -70 DEG C dry 4-6h, and graphite oxide powder is made;
A2 8-10h, mistake after immersion) modified graphite oxide: will be impregnated under graphite oxide powder room temperature in hydrazine hydrate
Filter, filter cake be washed with deionized after in drying box 60 DEG C of dry 4h, the obtained graphene oxide containing carboxyl and hydroxyl it is micro-
Piece;
A3) prepare graphene oxide conductive paste: step A2) gained graphene oxide microplate be put into sonic oscillation 1h in DMSO
Afterwards, it is transferred in 80 DEG C of -85 DEG C of water-baths, 100g diisocyanate is added, 60 DEG C -65 DEG C are stirred to react 4-6h, filtering, with two
Chloromethanes washs 2-3 times, and 45 DEG C of -50 DEG C of drying are placed in silane coupling agent and impregnate 6-8h, filters, 3- is washed with deionized
It is placed in the aqueous solution of organic amine for 5 times, 40 DEG C -60 DEG C are stirred to react 5h, suspension are made, by suspension colloid under room temperature
Mill carries out high speed shear and grinds 1-2h, and colloid mill revolving speed is 10000r/min, finally by the black suspension after grinding successively 120
Graphene oxide conductive paste is made after filtrate 20Hz ultrasonic disperse 0.5-2h in mesh and the filtering of 325 mesh;
B, black holesization is carried out using graphene oxide conductive paste to be directly electroplated
B1 it) cleans: electroplate being placed in 3-5min in 60 DEG C -70 DEG C of cleaning solution, is cleaned after taking-up with deionized water;
B2) whole hole: the electroplate after cleaning is placed in 3-5min in 60 DEG C -70 DEG C of conditioner, uses cold air drying after taking-up
It is dry;
B3 it) coats: the electroplate behind whole hole being immersed in graphene oxide conductive paste taken out after 3-5min at room temperature, hot wind
3-5min in graphene oxide conductive paste is again dipped into after drying, heated-air drying again after taking-up;
B4) microetch: immersing 2min in micro-corrosion liquid for the electroplate after coating at room temperature, is cleaned and is done with deionized water after taking-up
Only, it air-dries;
B5) electro-coppering: the plating plate surface after microetch is subjected to copper facing operation, graphene oxide conductive paste black holes is made
Change electroplate.
Wherein, step A3) diisocyanate is MDI or HDI;The organic amine is tetraethylenepentamine, triethylene four
Amine or triethanolamine, the concentration of aqueous solution of the organic amine are 5wt%-15wt%.
The beneficial effects of the present invention are:
It 1) is in hexagonal annular between graphite oxide olefinic carbon atoms of the invention, resistivity is low, and electron transfer rate is exceedingly fast, tool
There is good electric conductivity, improve electroplating efficiency, graphene oxide of the invention uses nanofabrication technique, graphene oxide energy
It is sufficiently attracted to idioelectric electrode surface, the conductive layer uniform and delicate of formation is firmly combined;
2) graphene oxide performance of the invention is stablized, and can prevent from sinking poly- phenomenon without carrying out circulation stirring in the quiescent state
Generation, be electroplated with graphene oxide of the invention, complete to hydrogen-free air elutriation in the copper-clad plate adsorption process after drilling
Out, solid guarantee is provided to the interlayer quality interconnection for improving printed board;
3) graphene oxide of the invention is applied to blank hole liquid electroplating technology, does not chemically react in adsorption process,
Also the phenomenon that just there is no other compositions are consumed because of chemical reaction completely can be according to reality without analyzing and adjusting solution
The detraction of production adds new liquid, the operation and maintenance of graphene oxide of the invention to solution in solution tank, not only simple but also can
It leans on;
4) present invention is modified graphene oxide, its surface is made to contain isocyanate group, keeps graphene oxide conductive
Slurry has very high mobility and film forming, increases the compatibility of graphene oxide and electroplate, band on graphene oxide
There is negative electrical charge charge attraction can occur with the positive charge in circuit board apertures, is obtained in hole to stablize and be attached to circuit board, shape
At conductor metal aperture, time and expense are saved for subsequent plating work;
5) present invention is directly electroplated using carbon black or graphite the progress black holesization of the graphene oxide substitute particles of line style, attached
After graphene oxide compacted zone have stable continuity, increase conductive capability while can more enhance the strong of compacted zone
Degree, is also less prone to micro-fractures or fracture, increases the service life of conductive plate when deformation occurs in electroplate;
6) due to graphene oxide conductive paste good film-forming property produced by the present invention, so that the present invention is led using graphene oxide
Plasma-based carries out the direct electroplating technique step of black holesization and significantly simplifies compared to existing black holes directly electroplating technology, and conductive paste is used
Amount is few, and being only repeated once coating can be completed entire electroplating technology, easy to operate, high yield rate;
7) graphene oxide of the invention is with good stability, and no replacement is required in bath solution 1 year, saves working hour,
Material consumption is reduced in water and electric saving, effectively controls the discharge amount of waste water, and tank liquor is free of harmful substance, and environmental pollution is small, gives up
Water process is simple, reduces costs.
Detailed description of the invention
Fig. 1-Fig. 3 is the transmission electron microscope picture of graphene oxide prepared by the present invention;
Fig. 4 is that the present invention uses graphene oxide conductive paste progress black holesization that table before electroplate copper facing obtained is directly electroplated
The scanning electron microscope (SEM) photograph in face.
Specific embodiment
Below in conjunction with example, present invention is described, and the given examples are served only to explain the present invention, is not intended to limit this
The range of invention.
Embodiment 1
A kind of application of graphene oxide conductive paste in black holesization is directly electroplated, including prepare graphene oxide conductive paste
It is directly electroplated, the steps include: with using graphene oxide conductive paste obtained to carry out black holesization
A, graphene oxide conductive paste is prepared
A1 it) prepares graphite oxide powder: 10g natural flake graphite is immersed into the mixed of the 100ml concentrated sulfuric acid and 20ml concentrated nitric acid
It closes in acid, is filtered after impregnating 12h under room temperature, after filter cake is washed with deionized to washing lotion pH value between 6-7, then by filter cake
It is placed in a vacuum drying oven, 70 DEG C of dry 4h, graphite oxide powder is made;
A2) modified graphite oxide: will impregnate 10h under graphite oxide powder room temperature in hydrazine hydrate, filter after immersion,
Filter cake be washed with deionized after in drying box 60 DEG C of dry 4h, be made the graphene oxide microplate containing carboxyl and hydroxyl;
A3) prepare graphene oxide conductive paste: step A2) gained graphene oxide microplate be put into sonic oscillation 1h in DMSO
Afterwards, it is transferred in 85 DEG C of water-baths, 100g diisocyanate MDI is added, 60 DEG C are stirred to react 6h, and filtering is washed with methylene chloride
It washs 2-3 times, 50 DEG C of drying are placed in silane coupling agent and impregnate 6h, filter, and are washed with deionized 3-5 times and are placed on concentration and are
In the aqueous solution of 5wt% tetraethylenepentamine, 40 DEG C are stirred to react 5h, and suspension is made, under room temperature by suspension colloid mill into
Row high speed shear grind 2h, colloid mill revolving speed be 10000r/min, finally by the black suspension after grinding successively 120 mesh and
Graphene oxide conductive paste is made after filtrate 20Hz ultrasonic disperse 0.5h in the filtering of 325 mesh;
B, black holesization is carried out using graphene oxide conductive paste to be directly electroplated
B1 it) cleans: electroplate being placed in 5min in 60 DEG C of cleaning solution, is cleaned after taking-up with deionized water;
B2) whole hole: the electroplate after cleaning is placed in 3min in 70 DEG C of conditioner, uses cold air drying after taking-up;
B3 it) coats: the electroplate behind whole hole being immersed in graphene oxide conductive paste taken out after 5min at room temperature, hot air drying
3min in graphene oxide conductive paste is again dipped into after dry, heated-air drying again after taking-up;
B4) microetch: immersing 2min in micro-corrosion liquid for the electroplate after coating at room temperature, is cleaned and is done with deionized water after taking-up
Only, it air-dries;
B5) electro-coppering: the plating plate surface after microetch is subjected to copper facing operation, graphene oxide conductive paste black holes is made
Change electroplate.
Embodiment 2
A kind of application of graphene oxide conductive paste in black holesization is directly electroplated, including prepare graphene oxide conductive paste
It is directly electroplated, the steps include: with using graphene oxide conductive paste obtained to carry out black holesization
A, graphene oxide conductive paste is prepared
A1 it) prepares graphite oxide powder: 10g natural flake graphite is immersed into the mixed of the 100ml concentrated sulfuric acid and 20ml concentrated nitric acid
It closes in acid, is filtered after impregnating 16h under room temperature, after filter cake is washed with deionized to washing lotion pH value between 6-7, then by filter cake
It is placed in a vacuum drying oven, 65 DEG C of dry 5h, graphite oxide powder is made;
A2) modified graphite oxide: will impregnate 9h under graphite oxide powder room temperature in hydrazine hydrate, filter after immersion,
Filter cake be washed with deionized after in drying box 60 DEG C of dry 4h, be made the graphene oxide microplate containing carboxyl and hydroxyl;
A3) prepare graphene oxide conductive paste: step A2) gained graphene oxide microplate be put into sonic oscillation 1h in DMSO
Afterwards, it is transferred in 85 DEG C of water-baths, 100g diisocyanate MDI is added, 60 DEG C are stirred to react 4h, and filtering is washed with methylene chloride
It washs 2-3 times, 50 DEG C of drying are placed in silane coupling agent and impregnate 6-8h, filter, are washed with deionized 3-5 times and are placed on concentration
In aqueous solution for 10wt% triethylene tetramine, 50 DEG C are stirred to react 5h, obtained suspension, by suspension colloid mill under room temperature
It carries out high speed shear and grinds 1.5h, colloid mill revolving speed is 10000r/min, finally by successively 120 mesh of the black suspension after grinding
It is filtered with 325 mesh, after filtrate 20Hz ultrasonic disperse 1h, graphene oxide conductive paste is made;
B, black holesization is carried out using graphene oxide conductive paste to be directly electroplated
B1 it) cleans: electroplate being placed in 4min in 65 DEG C of cleaning solution, is cleaned after taking-up with deionized water;
B2) whole hole: the electroplate after cleaning is placed in 4min in 65 DEG C of conditioner, uses cold air drying after taking-up;
B3 it) coats: the electroplate behind whole hole being immersed in graphene oxide conductive paste taken out after 4min at room temperature, hot air drying
4min in graphene oxide conductive paste is again dipped into after dry, heated-air drying again after taking-up;
B4) microetch: immersing 2min in micro-corrosion liquid for the electroplate after coating at room temperature, is cleaned and is done with deionized water after taking-up
Only, it air-dries;
B5) electro-coppering: the plating plate surface after microetch is subjected to copper facing operation, graphene oxide conductive paste black holes is made
Change electroplate.
Embodiment 3
A kind of application of graphene oxide conductive paste in black holesization is directly electroplated, including prepare graphene oxide conductive paste
It is directly electroplated, the steps include: with using graphene oxide conductive paste obtained to carry out black holesization
A, graphene oxide conductive paste is prepared
A1 it) prepares graphite oxide powder: 10g natural flake graphite is immersed into the mixed of the 100ml concentrated sulfuric acid and 20ml concentrated nitric acid
It closes in acid, is filtered after impregnating 18h under room temperature, after filter cake is washed with deionized to washing lotion pH value between 6-7, then by filter cake
It is placed in a vacuum drying oven, 60 DEG C of dry 6h, graphite oxide powder is made;
A2) modified graphite oxide: will impregnate 8h under graphite oxide powder room temperature in hydrazine hydrate, filter after immersion,
Filter cake be washed with deionized after in drying box 60 DEG C of dry 4h, be made the graphene oxide microplate containing carboxyl and hydroxyl;
A3) prepare graphene oxide conductive paste: step A2) gained graphene oxide microplate be put into sonic oscillation 1h in DMSO
Afterwards, it is transferred in 80 DEG C of water-baths, 100g diisocyanate HDI is added, 65 DEG C are stirred to react 4h, and filtering is washed with methylene chloride
It washs 2-3 times, 45 DEG C of drying are placed in silane coupling agent and impregnate 8h, filter, and are washed with deionized 3-5 times and are placed on concentration and are
In the aqueous solution of 15wt% triethanolamine, 60 DEG C are stirred to react 5h, and suspension is made, carries out suspension with colloid mill under room temperature
High speed shear grinds 1h, and colloid mill revolving speed is 10000r/min, finally by successively 120 mesh and 325 of the black suspension after grinding
Graphene oxide conductive paste is made after filtrate 20Hz ultrasonic disperse 2h in mesh filtering;
B, black holesization is carried out using graphene oxide conductive paste to be directly electroplated
B1 it) cleans: electroplate being placed in 3min in 70 DEG C of cleaning solution, is cleaned after taking-up with deionized water;
B2) whole hole: the electroplate after cleaning is placed in 5min in 60 DEG C of conditioner, uses cold air drying after taking-up;
B3 it) coats: the electroplate behind whole hole being immersed in graphene oxide conductive paste taken out after 3min at room temperature, hot air drying
5min in graphene oxide conductive paste is again dipped into after dry, heated-air drying again after taking-up;
B4) microetch: immersing 2min in micro-corrosion liquid for the electroplate after coating at room temperature, is cleaned and is done with deionized water after taking-up
Only, it air-dries;
B5) electro-coppering: the plating plate surface after microetch is subjected to copper facing operation, graphene oxide conductive paste black holes is made
Change electroplate.
Fig. 1-Fig. 3 is the transmission electron microscope picture of graphene oxide prepared by the present invention, it can be seen from the figure that graphene oxide
Still there is complete structure after modified;Fig. 4 is that the present invention uses graphene oxide conductive paste progress black holesization that system is directly electroplated
Electroplate copper facing front surface scanning electron microscope (SEM) photograph, graphene oxide structural integrity in figure, orientation is obvious, has compacted zone
Stronger mechanical property and good conductive capability.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (3)
1. a kind of application of graphene oxide conductive paste in black holesization is directly electroplated, including prepare graphene oxide conductive paste and
It carries out black holesization using graphene oxide conductive paste obtained to be directly electroplated, which is characterized in that the steps include:
A, graphene oxide conductive paste is prepared
A1 it) prepares graphite oxide powder: 10g natural flake graphite is immersed to the mixed acid of the 100ml concentrated sulfuric acid and 20ml concentrated nitric acid
In, it is filtered after impregnating 12-18h under room temperature, after filter cake is washed with deionized to washing lotion pH value between 6-7, then by filter cake
It is placed in a vacuum drying oven, 60 DEG C -70 DEG C dry 4-6h, graphite oxide powder is made;
A2) modified graphite oxide: will impregnate 8-10h under graphite oxide powder room temperature in hydrazine hydrate, filter after immersion, filter
Cake be washed with deionized after in drying box 60 DEG C of dry 4h, be made the graphene oxide microplate containing carboxyl and hydroxyl;
A3) prepare graphene oxide conductive paste: step A2) gained graphene oxide microplate be put into DMSO after sonic oscillation 1h,
It is transferred in 80 DEG C of -85 DEG C of water-baths, 100g diisocyanate is added, 60 DEG C -65 DEG C are stirred to react 4-6h, and dichloro is used in filtering
Methane wash 2-3 times, 45 DEG C of -50 DEG C of drying are placed in silane coupling agent and impregnate 6-8h, filter, 3-5 is washed with deionized
Secondary to be placed in the aqueous solution of organic amine, 40 DEG C -60 DEG C are stirred to react 5h, obtained suspension, by suspension colloid under room temperature
Mill carries out high speed shear and grinds 1-2h, and colloid mill revolving speed is 10000r/min, finally by the black suspension after grinding successively 120
Graphene oxide conductive paste is made after filtrate 20Hz ultrasonic disperse 0.5-2h in mesh and the filtering of 325 mesh;
B, black holesization is carried out using graphene oxide conductive paste to be directly electroplated
B1 it) cleans: electroplate being placed in 3-5min in 60 DEG C -70 DEG C of cleaning solution, is cleaned after taking-up with deionized water;
B2) whole hole: the electroplate after cleaning is placed in 3-5min in 60 DEG C -70 DEG C of conditioner, uses cold air drying after taking-up;
B3 it) coats: the electroplate behind whole hole being immersed in graphene oxide conductive paste taken out after 3-5min at room temperature, heated-air drying
After be again dipped into 3-5min in graphene oxide conductive paste, heated-air drying again after taking-up;
B4) microetch: immersing 2min in micro-corrosion liquid for the electroplate after coating at room temperature, cleaned up after taking-up with deionized water,
It air-dries;
B5) electro-coppering: carrying out copper facing operation for the plating plate surface after microetch, and graphene oxide conductive paste black holesization electricity is made
Plate plate.
2. application of the graphene oxide conductive paste according to claim 1 in black holesization is directly electroplated, which is characterized in that
Step A3) diisocyanate is MDI or HDI.
3. application of the graphene oxide conductive paste according to claim 1 in black holesization is directly electroplated, which is characterized in that
Step A3) organic amine is tetraethylenepentamine, triethylene tetramine or triethanolamine, the concentration of aqueous solution of the organic amine is
5wt%-15wt%.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113207243A (en) * | 2021-05-08 | 2021-08-03 | 电子科技大学中山学院 | Preparation and application method of black hole liquid |
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CN114845480A (en) * | 2022-03-31 | 2022-08-02 | 厦门大学 | Flexible copper-clad plate graphene oxide hole metallization method |
CN114988401A (en) * | 2022-05-16 | 2022-09-02 | 南通赛可特电子有限公司 | Method for directly blackening PCB modified graphene oxide |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1562738A (en) * | 2004-04-15 | 2005-01-12 | 上海交通大学 | Functional nano carbon tubes possessing isocyanate radical on its surface and preparation method |
CN101394712A (en) * | 2007-09-21 | 2009-03-25 | 清华大学 | Hole blackening solution and preparation thereof |
CN102424381A (en) * | 2011-09-09 | 2012-04-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene oxide reducing method |
CN103491727A (en) * | 2013-09-29 | 2014-01-01 | 哈尔滨工业大学 | Method using printed circuit board graphite oxide reduction method to carry out hole conductivity |
CN103608288A (en) * | 2011-11-30 | 2014-02-26 | 积水化学工业株式会社 | Functional-group-modified carbon material, and method for producing same |
CN103839605A (en) * | 2014-02-26 | 2014-06-04 | 华中科技大学 | Electrocondution slurry and preparation method and application of electrocondution slurry |
KR20170098341A (en) * | 2016-02-19 | 2017-08-30 | 전자부품연구원 | Heating composition having graphene oxide and heater using the same |
CN108323036A (en) * | 2018-02-10 | 2018-07-24 | 深圳市祥盛兴科技有限公司 | A kind of blank hole liquid and black holes chemical industry skill |
CN108962425A (en) * | 2018-08-02 | 2018-12-07 | 佛山腾鲤新能源科技有限公司 | A kind of preparation method of graphene conductive slurry |
CN108963255A (en) * | 2018-06-01 | 2018-12-07 | 湖南国盛石墨科技有限公司 | A kind of preparation method of the conduction liquid of containing graphene |
CN109243671A (en) * | 2018-11-29 | 2019-01-18 | 圣盟(廊坊)新材料研究院有限公司 | A kind of preparation method of graphene composite conductive slurry |
-
2019
- 2019-03-28 CN CN201910244507.4A patent/CN109811382B/en active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1562738A (en) * | 2004-04-15 | 2005-01-12 | 上海交通大学 | Functional nano carbon tubes possessing isocyanate radical on its surface and preparation method |
CN101394712A (en) * | 2007-09-21 | 2009-03-25 | 清华大学 | Hole blackening solution and preparation thereof |
CN102424381A (en) * | 2011-09-09 | 2012-04-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene oxide reducing method |
CN103608288A (en) * | 2011-11-30 | 2014-02-26 | 积水化学工业株式会社 | Functional-group-modified carbon material, and method for producing same |
CN103491727A (en) * | 2013-09-29 | 2014-01-01 | 哈尔滨工业大学 | Method using printed circuit board graphite oxide reduction method to carry out hole conductivity |
CN103839605A (en) * | 2014-02-26 | 2014-06-04 | 华中科技大学 | Electrocondution slurry and preparation method and application of electrocondution slurry |
KR20170098341A (en) * | 2016-02-19 | 2017-08-30 | 전자부품연구원 | Heating composition having graphene oxide and heater using the same |
CN108323036A (en) * | 2018-02-10 | 2018-07-24 | 深圳市祥盛兴科技有限公司 | A kind of blank hole liquid and black holes chemical industry skill |
CN108963255A (en) * | 2018-06-01 | 2018-12-07 | 湖南国盛石墨科技有限公司 | A kind of preparation method of the conduction liquid of containing graphene |
CN108962425A (en) * | 2018-08-02 | 2018-12-07 | 佛山腾鲤新能源科技有限公司 | A kind of preparation method of graphene conductive slurry |
CN109243671A (en) * | 2018-11-29 | 2019-01-18 | 圣盟(廊坊)新材料研究院有限公司 | A kind of preparation method of graphene composite conductive slurry |
Non-Patent Citations (3)
Title |
---|
UTTAM SAHA ET AL: "Diisocyanate modified graphene oxide network structure: steric effect of diisocyanates on bimolecular cross-linking degree", 《J NANOPART RES》 * |
付长璟: "《石墨烯的制备、结构及应用》", 30 June 2017, 哈尔滨工业大学出版社 * |
李晓萱 等: "甲苯二异氰酸酯插层改性氧化石墨烯", 《化工新型材料》 * |
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