CN103464779B - Method for adopting sliver-coated nano copper composite particles to prepare conductive ink - Google Patents
Method for adopting sliver-coated nano copper composite particles to prepare conductive ink Download PDFInfo
- Publication number
- CN103464779B CN103464779B CN201310399414.1A CN201310399414A CN103464779B CN 103464779 B CN103464779 B CN 103464779B CN 201310399414 A CN201310399414 A CN 201310399414A CN 103464779 B CN103464779 B CN 103464779B
- Authority
- CN
- China
- Prior art keywords
- nano copper
- solution
- silver
- conductive ink
- copper
- 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.)
- Expired - Fee Related
Links
Abstract
Disclosed is a method for adopting sliver-coated nano copper composite particles to prepare conductive ink. The method includes taking polyvinyl pyrrolidone as a protective agent; utilizing NaH2PO2 H2O to directly reduce a copper sulfate solution into nano copper particles; through a in-situ reduction-oxidation reaction of silver ions with metal copper on the surface of nano copper, directly adding a silver nitrate in a nano copper solution to synthetise sliver-coated nano copper composite particles; mixing the sliver-coated nano copper composite particles and glycerol and glycol reagents according to a certain proportion to obtain conductive ink. The method has the advantages that compared with the prior art, surface cleaning of copper powder is not needed, the ink preparation process is simple, and needed solvent is economical, easy to get and nontoxic; the process from preparation of materials to preparation of the conductive ink and the process of obtaining of a lead by means of writing and inkjet printing are performed in air, and no toxic drug is utilized, so that environmental friendliness is realized and the preparation process can be completed simply and conveniently.
Description
Technical field
The present invention relates to the preparation technology of electrically conductive ink, particularly a kind ofly adopt silver-colored clad nano copper compound particle to prepare the method for electrically conductive ink.
Background technology
Along with the development of science and technology, electronic technology science with industry etc. every field be widely used, can be used as printing conductiving point or conducting wire electrically conductive ink shown great attention to.As conductive filler, silver powder has good electric conductivity and non-oxidizability, but expensive due to it, and cost is too high, is not suitable for industrially promoting.Copper powder also has good electric conductivity, and its low price, be therefore considered to silver powder best substitute, but copper is easily oxidized, which limits its use, and copper powder is made electrically conductive ink and carry out writing, sintering and must carry out in inert gas, this is just unfavorable for its operation.If at the coated one deck silver of Copper Powder Surface, make silver-colored coated copper powder, the oxidation resistance of copper nanoparticle can be improved like this, the good conductive properties of copper nanoparticle can be kept again, not only have both some performance of noble metal, and price is cheaper than single noble metal nano powder, so silver-colored clad nano copper compound particle has wide range of application.Patent of invention [CN1262043A] discloses a kind of method that displacement reaction prepares silver-colored coated copper powder, but it is mainly used in the preparation of antiseptic.Patent of invention [CN201210069139] discloses one L-AA and reduces silver nitrate, be deposited on the preparation method of the silver-colored copper facing powder of Copper Powder Surface, this just needs to activate Copper Powder Surface, clean, sensitization, and step is many, preparation process more complicated.Tang founding father etc., see electronic component and material, Vol.28No.9, adopts with displacement method reduction complexing silver ion, at copper powder particle surface deposition argent, but its complicated process of preparation and only have studied its non-oxidizability, do not study its electric conductivity further.General all with ready-made copper powder direct-reduction silver in the preparation technology of existing silver-colored coated copper powder, this cupric oxide just needing removing Copper Powder Surface to generate, and the silver-colored coated copper powder of synthesis and be prepared into ink process in can use toxic pharmaceuticals, have very major injury to human body and environment.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, thering is provided a kind of adopts silver-colored clad nano copper compound particle to prepare the method for electrically conductive ink, silver-colored clad nano copper compound particle prepared by the method has good antioxygenic property, and the electrically conductive ink that itself and glycerine, ethylene glycol reagent are mixed by a certain percentage is had good electric conductivity.
Technical scheme of the present invention:
Adopt silver-colored clad nano copper compound particle to prepare a method for electrically conductive ink, using polyvinylpyrrolidone (PVP) as protective agent, utilize NaH
2pO
2h
2copper-bath is directly reduced into nano copper particle by O, by the in-situ oxidation reduction reaction of the metallic copper on silver ion and Nanometer Copper surface, in Nanometer Copper solution, directly add liquor argenti nitratis ophthalmicus synthesize silver-colored clad nano copper compound particle, described silver-colored clad nano copper compound particle and glycerine, ethylene glycol reagent are mixed and made into electrically conductive ink by a certain percentage, specifically comprise the following steps:
1) by polyvinylpyrrolidone and NaH
2pO
2h
2o joins deionized water for stirring and dissolves wiring solution-forming A, by CuSO
45H
2o joins deionized water and joins middle stirring and dissolving and obtain copper-bath, in copper-bath, drip concentration be ammoniacal liquor to the pH value of 25wt% is 10 wiring solution-forming B, solution B is added in solution A and adds thermal agitation, redox reaction is carried out after 2 hours at temperature is 100-140 DEG C, mixed solution becomes rufous, can obtain nano copper particle solution;
2) above-mentioned obtained nano copper particle solution being carried out ultrasonic agitation makes it be uniformly dispersed, be that the liquor argenti nitratis ophthalmicus of 0.0068-0.0136g/ml to be added dropwise in nano copper particle solution stirring reaction half an hour by concentration, now solution colour becomes taupe, be separated synthetic and use ethanol eccentric cleaning 2-4 time, obtain silver-colored clad nano copper compound particle after drying, the silver-colored clad nano copper compound particle of preparation has good antioxygenic property;
3) add above-mentioned silver-colored clad nano copper compound particle after being mixed with glycerine by ethanol to carry out ultrasonic agitation and make it dissolve completely, obtained electrically conductive ink;
4) above-mentioned electrically conductive ink will be made to load in the neutral shaft of a writing brush, photo papers will be drawn as wire, then sinter at 150-180 DEG C of temperature, can target product be obtained.
Polyvinylpyrrolidone (PVP), NaH in described solution A
2pO
2h
2the amount ratio of O and deionized water is 1g:2g:100ml; CuSO in solution B
45H
2the amount ratio of O, deionized water and ammoniacal liquor is 1g:20ml:1ml; The mass ratio of solution A and solution B is 1:3.2-4.
The volume ratio of described ethanol and glycerine is 1:3, and in electrically conductive ink, the mass percent of silver-colored clad nano copper compound particle is 30-40%.
Advantage of the present invention is: compared with prior art, and the present invention does not need to carry out surface clean to copper powder, and preparation ink process is simple, and required solvent economy is easy to get and nontoxic; The present invention is prepared into preparation electrically conductive ink from material, and by writing, to obtain wire be all carry out in atmosphere for the mode of inkjet printing, and without the use of toxic pharmaceuticals, environmental friendliness, can complete preparation technology simply and easily.
Detailed description of the invention
Embodiment 1:
Silver-colored clad nano copper compound particle is adopted to prepare a method for electrically conductive ink, using polyvinylpyrrolidone (PVP) as protective agent, the NaH of utilization
2pO
2h
2copper-bath is directly reduced into nano copper particle by O, by the in-situ oxidation reduction reaction of the metallic copper on silver ion and Nanometer Copper surface, in Nanometer Copper solution, directly add liquor argenti nitratis ophthalmicus synthesize silver-colored clad nano copper compound particle, described silver-colored clad nano copper compound particle and glycerine, ethylene glycol reagent are mixed and made into electrically conductive ink by a certain percentage, specifically comprise the following steps:
1) by 0.4g polyvinylpyrrolidone and 0.8gNaH
2pO
2h
2o joins 40ml deionized water for stirring and dissolves wiring solution-forming A, by 0.5gCuSO
45H
2o adds 10ml deionized water and is mixed with copper-bath, in copper-bath, drip concentration be ammoniacal liquor to the pH value of 25wt% is 10 wiring solution-forming B, solution B is added in solution A and adds thermal agitation, react 2 hours at temperature is 100 DEG C, solution becomes rufous, can obtain nano copper particle solution;
2) above-mentioned obtained nano copper particle solution being carried out ultrasonic agitation makes it be uniformly dispersed, be that the liquor argenti nitratis ophthalmicus of 0.0068g/ml to be added dropwise in nano copper particle solution stirring reaction half an hour by concentration, now solution colour becomes taupe, be separated synthetic and use ethanol eccentric cleaning 3 times, after drying, obtaining silver-colored clad nano copper compound particle;
3) add above-mentioned silver-colored clad nano copper compound particle after being mixed with volume ratio 1:3 with glycerine by ethanol to carry out ultrasonic agitation and make it dissolve completely, in electrically conductive ink, the mass percent of silver-colored clad nano copper compound particle is 40% obtained electrically conductive ink;
4) above-mentioned electrically conductive ink will be made to load in the neutral shaft of a writing brush, photo papers will be drawn as wire, then sinter at 160 DEG C of temperature, can target product be obtained.
Detection shows: obtained electrically conductive ink has good electric conductivity.
Embodiment 2:
Adopt silver-colored clad nano copper compound particle to prepare a method for electrically conductive ink, specifically comprise the following steps:
1) by 0.4g polyvinylpyrrolidone and 0.8gNaH
2pO
2h
2o joins 40ml deionized water for stirring and dissolves wiring solution-forming A, by 0.5gCuSO
45H
2o adds 10ml deionized water and is mixed with copper-bath, in copper-bath, drip concentration be ammoniacal liquor to the pH value of 25wt% is 10 wiring solution-forming B, solution B is added in solution A and adds thermal agitation, react 2 hours at temperature is 120 DEG C, solution becomes rufous, can obtain nano copper particle solution;
2) above-mentioned obtained nano copper particle solution being carried out ultrasonic agitation makes it be uniformly dispersed, be that the liquor argenti nitratis ophthalmicus of 0.0136g/ml to be added dropwise in nano copper particle solution stirring reaction half an hour by concentration, now solution colour becomes taupe, be separated synthetic and use ethanol eccentric cleaning 3 times, after drying, obtaining silver-colored clad nano copper compound particle;
3) add above-mentioned silver-colored clad nano copper compound particle after being mixed with volume ratio 1:3 with glycerine by ethanol to carry out ultrasonic agitation and make it dissolve completely, in electrically conductive ink, the mass percent of silver-colored clad nano copper compound particle is 30% obtained electrically conductive ink;
4) above-mentioned electrically conductive ink will be made to load in the neutral shaft of a writing brush, photo papers will be drawn as wire, then sinter at 170 DEG C of temperature, can target product be obtained.
Detection shows: obtained electrically conductive ink has good electric conductivity.
Claims (3)
1. adopt silver-colored clad nano copper compound particle to prepare a method for electrically conductive ink, it is characterized in that: using polyvinylpyrrolidone as protective agent, utilize NaH
2pO
2h
2copper-bath is directly reduced into nano copper particle by O, by the in-situ oxidation reduction reaction of the metallic copper on silver ion and Nanometer Copper surface, in Nanometer Copper solution, directly add liquor argenti nitratis ophthalmicus synthesize silver-colored clad nano copper compound particle, described silver-colored clad nano copper compound particle and glycerine, ethylene glycol reagent are mixed and made into electrically conductive ink by a certain percentage, specifically comprise the following steps:
1) by polyvinylpyrrolidone and NaH
2pO
2h
2o joins deionized water for stirring and dissolves wiring solution-forming A, by CuSO
45H
2o joins deionized water for stirring dissolving and obtains copper-bath, in copper-bath, drip concentration be ammoniacal liquor to the pH value of 25wt% is 10 wiring solution-forming B, solution B is added in solution A and adds thermal agitation, redox reaction is carried out after 2 hours at temperature is 100-140 DEG C, mixed solution becomes rufous, can obtain nano copper particle solution;
2) above-mentioned obtained nano copper particle solution being carried out ultrasonic agitation makes it be uniformly dispersed, be that the liquor argenti nitratis ophthalmicus of 0.0068-0.0136g/ml to be added dropwise in nano copper particle solution stirring reaction half an hour by concentration, now solution colour becomes taupe, be separated synthetic and use ethanol eccentric cleaning 2-4 time, obtain silver-colored clad nano copper compound particle after drying, the silver-colored clad nano copper compound particle of preparation has good antioxygenic property;
3) add above-mentioned silver-colored clad nano copper compound particle after being mixed with glycerine by ethanol to carry out ultrasonic agitation and make it dissolve completely, obtained electrically conductive ink;
4) above-mentioned electrically conductive ink is loaded in the neutral shaft of a writing brush, photo papers is drawn as wire, then sinter at 150-180 DEG C of temperature, can target product be obtained.
2. adopt silver-colored clad nano copper compound particle to prepare the method for electrically conductive ink according to claim 1, it is characterized in that: polyvinylpyrrolidone, NaH in described solution A
2pO
2h
2the amount ratio of O and deionized water is 1g:2g:100ml; CuSO in solution B
45H
2the amount ratio of O, deionized water and ammoniacal liquor is 1g:20ml:1ml; The mass ratio of solution A and solution B is 1:3.2-4.
3. adopt silver-colored clad nano copper compound particle to prepare the method for electrically conductive ink according to claim 1, it is characterized in that: the volume ratio of described ethanol and glycerine is 1:3, in electrically conductive ink, the mass percent of silver-colored clad nano copper compound particle is 30-40%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310399414.1A CN103464779B (en) | 2013-09-05 | 2013-09-05 | Method for adopting sliver-coated nano copper composite particles to prepare conductive ink |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310399414.1A CN103464779B (en) | 2013-09-05 | 2013-09-05 | Method for adopting sliver-coated nano copper composite particles to prepare conductive ink |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103464779A CN103464779A (en) | 2013-12-25 |
| CN103464779B true CN103464779B (en) | 2015-06-03 |
Family
ID=49789944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310399414.1A Expired - Fee Related CN103464779B (en) | 2013-09-05 | 2013-09-05 | Method for adopting sliver-coated nano copper composite particles to prepare conductive ink |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103464779B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6404614B2 (en) * | 2014-06-25 | 2018-10-10 | 古河機械金属株式会社 | Manufacturing method of core-shell type metal fine particles, core-shell type metal fine particles, conductive ink and substrate |
| CN104754875B (en) * | 2015-03-08 | 2018-01-23 | 北京化工大学 | The preparation method of copper@silver metal conducting films and its application on a printed circuit board |
| CN104946022B (en) * | 2015-07-10 | 2018-03-16 | 东北大学 | A kind of high stability agranular type silver base conductive ink and preparation method thereof |
| CN105598468B (en) * | 2016-03-17 | 2018-05-15 | 中国科学院深圳先进技术研究院 | A kind of preparation method of wicker copper nano particle available for electrically conductive ink |
| CN105903980A (en) * | 2016-05-16 | 2016-08-31 | 深圳市微纳集成电路与***应用研究院 | Copper nanometer powder and preparation method thereof as well as silver-coated copper powder and preparation method thereof |
| KR101789213B1 (en) * | 2016-06-03 | 2017-10-26 | (주)바이오니아 | Method of Manufacturing Silver-Coated Copper Nano Wire Having Core-Shell Structure by Chemical Reduction Method |
| CN107983970A (en) * | 2017-11-24 | 2018-05-04 | 电子科技大学 | A kind of preparation method of Cu-Ag Nanoalloys |
| CN108084799A (en) * | 2017-11-30 | 2018-05-29 | 哈尔滨工业大学深圳研究生院 | A kind of material for radio frequency discrimination RFID antenna conductive patterns |
| CN108176849B (en) * | 2017-12-12 | 2020-01-17 | 南京邮电大学 | Silver-coated copper nano powder and preparation method and application thereof |
| CN112608638A (en) * | 2021-01-14 | 2021-04-06 | 成都萃匀离环保科技有限公司 | Preparation method of high-stability modified polyepoxy resin composite conductive coating |
| CN114799195A (en) * | 2022-03-10 | 2022-07-29 | 昆明理工大学 | Preparation method of self-assembled micro-nano structure Cu-Ag nano particles |
| CN116285493A (en) * | 2023-04-27 | 2023-06-23 | 英科卡乐油墨(湖北)有限公司 | Universal water-based silver ink for PE film paper |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100438408B1 (en) * | 2001-08-16 | 2004-07-02 | 한국과학기술원 | Method for Synthesis of Core-Shell type and Solid Solution type Metallic Alloy Nanoparticles via Transmetalation Reactions and Their Applications |
| CN101244459A (en) * | 2008-03-25 | 2008-08-20 | 合肥工业大学 | Chemical plating silver copper powder, chemical plating liquid and chemical plating method |
| CN101306468A (en) * | 2007-05-19 | 2008-11-19 | 浙江师范大学 | Preparation method of conductive silver composite nano particles coated by polypyrrole |
| CN102120265A (en) * | 2010-01-07 | 2011-07-13 | 中国科学院化学研究所 | Preparation method of colloid of mono-dispersed silver nano particles and nano silver powder and conductive ink thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100781586B1 (en) * | 2006-02-24 | 2007-12-05 | 삼성전기주식회사 | Core-shell structure metall nanoparticles and its manufacturing method |
-
2013
- 2013-09-05 CN CN201310399414.1A patent/CN103464779B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100438408B1 (en) * | 2001-08-16 | 2004-07-02 | 한국과학기술원 | Method for Synthesis of Core-Shell type and Solid Solution type Metallic Alloy Nanoparticles via Transmetalation Reactions and Their Applications |
| CN101306468A (en) * | 2007-05-19 | 2008-11-19 | 浙江师范大学 | Preparation method of conductive silver composite nano particles coated by polypyrrole |
| CN101244459A (en) * | 2008-03-25 | 2008-08-20 | 合肥工业大学 | Chemical plating silver copper powder, chemical plating liquid and chemical plating method |
| CN102120265A (en) * | 2010-01-07 | 2011-07-13 | 中国科学院化学研究所 | Preparation method of colloid of mono-dispersed silver nano particles and nano silver powder and conductive ink thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103464779A (en) | 2013-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103464779B (en) | Method for adopting sliver-coated nano copper composite particles to prepare conductive ink | |
| Dai et al. | Room temperature sintering of Cu-Ag core-shell nanoparticles conductive inks for printed electronics | |
| CN103128308B (en) | Method for preparing compact silver-coated copper powder by using one pot method | |
| JP5080731B2 (en) | Fine silver particle-attached silver-copper composite powder and method for producing the fine silver particle-attached silver-copper composite powder | |
| CN106583712B (en) | A kind of preparation method of wicker copper nano particle | |
| CN103008679A (en) | Method for preparing nano-silver particle and nano-silver wire mixed conductive ink | |
| CN101214547A (en) | Micrometer silver-copper granule containing nano level surface structure and preparation and application thereof | |
| Zhang et al. | PVP-mediated galvanic replacement synthesis of smart elliptic Cu–Ag nanoflakes for electrically conductive pastes | |
| KR101807919B1 (en) | Carrier-nano particles complex, method for fabricating the same and catalyst comprising the same | |
| KR20150145892A (en) | Silver Coated Copper Nano Wire and Method for Manufacturing Thereof | |
| Shang et al. | Synthesis of Cu@ Ag core–shell nanoparticles for characterization of thermal stability and electric resistivity | |
| Li et al. | Synthesis and characterization of silver–copper colloidal ink and its performance against electrical migration | |
| CN102161104A (en) | Preparation method of copper-silver composite powder | |
| CN102220045A (en) | Low-temperature-sintered solvent-based nano-silver electroconductive ink and preparation process thereof | |
| JP2013541640A (en) | Silver particles and method for producing the same | |
| CN110170650B (en) | Method for preparing high-compactness and completely-coated silver-coated copper powder | |
| KR20130004064A (en) | Silver powder for sintered conductive paste | |
| CN105903980A (en) | Copper nanometer powder and preparation method thereof as well as silver-coated copper powder and preparation method thereof | |
| CN106086837A (en) | A kind of preparation method of antioxidation silver-plated copper powder | |
| CN104801709A (en) | Nickel-coated copper clad metal powder and preparation method and application thereof | |
| JP2012167337A (en) | Method of manufacturing silver coated flake copper powder | |
| CN103691965A (en) | Preparation method for copper/silver heterojunction nano-particles | |
| JP4666663B2 (en) | Silver compound-coated copper powder, method for producing the silver compound-coated copper powder, storage method for the silver compound-coated copper powder, and conductive paste using the silver compound-coated copper powder | |
| JP5576319B2 (en) | Copper particles | |
| JP2014091842A (en) | Method of manufacturing silver coating copper alloy powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150603 Termination date: 20160905 |