CN114023511B - Method for preparing high-temperature electronic paste based on organic phosphorus salt - Google Patents
Method for preparing high-temperature electronic paste based on organic phosphorus salt Download PDFInfo
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- CN114023511B CN114023511B CN202111334245.4A CN202111334245A CN114023511B CN 114023511 B CN114023511 B CN 114023511B CN 202111334245 A CN202111334245 A CN 202111334245A CN 114023511 B CN114023511 B CN 114023511B
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 150000003017 phosphorus Chemical class 0.000 title claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 87
- 239000011521 glass Substances 0.000 claims abstract description 47
- -1 n-hexyl-3-methylimidazole hexafluorophosphate Chemical compound 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 6
- 239000001856 Ethyl cellulose Substances 0.000 claims description 6
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical group CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 229920001249 ethyl cellulose Polymers 0.000 claims description 6
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 6
- 239000011268 mixed slurry Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 6
- 229940116411 terpineol Drugs 0.000 claims description 6
- 239000002562 thickening agent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000002002 slurry Substances 0.000 abstract description 27
- 230000004048 modification Effects 0.000 abstract description 9
- 238000012986 modification Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 239000012071 phase Substances 0.000 description 45
- 238000002360 preparation method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- PSLIMVZEAPALCD-UHFFFAOYSA-N ethanol;ethoxyethane Chemical compound CCO.CCOCC PSLIMVZEAPALCD-UHFFFAOYSA-N 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KQNACZWCHZBAAZ-UHFFFAOYSA-N (sulfonylamino)amine;toluene Chemical compound NN=S(=O)=O.CC1=CC=CC=C1 KQNACZWCHZBAAZ-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- 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
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a method for preparing high-temperature electronic paste based on organic phosphorus salt. The invention improves the dispersibility and the bonding strength of the conductive powder by utilizing n-hexyl-3-methylimidazole hexafluorophosphate (NHIHP) to carry out surface modification on the conductive phase powder; the high-temperature electronic paste comprises the following components in parts by weight: 7-12 parts of novel slurry carrier, 78-90 parts of conductive powder with different particle sizes and 3-5 parts of glass phase. According to the invention, the NHIHP is combined with the surface of the conductive phase, so that the slurry particles are uniformly distributed, the bonding strength among the conductive particles can be enhanced, a compact film is formed, the components are environment-friendly, the conductive effect of the slurry can be enhanced, and the performance of the high-temperature electronic slurry can be improved.
Description
Technical Field
The invention relates to a modification method, in particular to a method for preparing high-temperature electronic paste based on organic phosphorus salt.
Background
The high-temperature electronic paste has wide application in the industrial production of electronic components and integrated circuits, and is generally composed of a conductive phase, a glass phase and an organic solvent, and can be printed to form conductive nanowires; and (3) carrying out high-temperature sintering, wherein an organic phase and a surfactant are pyrolyzed and volatilized, glass powder is fused on a substrate, and the glass powder is adhered with silver powder to form a conductive compact film. In the process, the distribution of the conductive particles and the contact resistance among the particles have a profound effect on the slurry performance, and the formation of a dense conductive film of the slurry and the conductivity thereof are affected. There are many problems to be solved in high temperature electronic paste, such as: the organic solvent has too many pollutants, and is not friendly to the environment; the surface energy of the conductive phase particles is large, the dispersibility is poor, and the conductive phase particles are easy to agglomerate; the problems of large interval gaps, uneven distribution, many gaps of the conductive film, loose connection, unnecessary energy consumption and the like caused by unmodified surface morphology of the conductive phase particles. Various drawbacks have hampered the progress of industrialization of high temperature electronic pastes.
CN108666002A discloses a metal glass-ceramic powder comprising TeO 2 ：10-50wt％，TiO 2 ：15-70wt％，ZnO：2-10wt％，SiO 2 :1-15wt% and Li 2 O:5-20wt% of glass phase has high-temperature viscosity, difficult flow, high surface tension, precise circuit during printing, but poor adhesion effect on conductive phase, easy agglomeration of conductive powder, large connecting gap and poor conductive effect.
CN202011529639.0 discloses that toluene sulfonyl hydrazine is attached to the surface of conductive particles, micro bubbles are generated by hydrolysis to uniformly disperse the conductive particles, the dispersibility of the slurry is improved, but the contact resistance between the conductive particles is improved by the micro bubbles, and the slurry performance is low.
CN20201102070. X discloses a novel glass comprising Bi 2 O 3 ：55～75％、B 2 O 3 ：5～20％、SiO 2 ：5～20％、MgO：1～5％、Al 2 O 3 :1 to 5 percent. The glass and the slurry have better dispersibility, and the dispersibility of the conductive phase is improved, but the addition of auxiliary agents such as toluene, xylene and the like has serious environmental pollution.
Therefore, providing a modification method that is environment-friendly, and enables the conductive phase to have good dispersion performance and the conductive phase powder to adhere tightly is a problem that needs to be solved by those skilled in the art. The patent uses 1-n-hexyl-3-methylimidazole hexafluorophosphate as a surface modification agent to modify the surface of conductive phase powder, improves the dispersibility and the bonding strength, and prepares the environment-friendly high-performance high-temperature electronic paste.
Disclosure of Invention
In view of the above, the present invention aims to solve the problems in the prior art, and provides a method for preparing a high-temperature electronic paste based on an organic phosphorus salt, and in particular provides a modification technical method which is environment-friendly, enables the dispersion performance of a conductive phase to be good and the adhesion of conductive phase powder to be tight, and an application of the modification technical method in the high-temperature electronic paste.
In order to achieve the above object, the technical scheme of the present invention is as follows:
a method for surface modification based on an organic phosphorus salt, comprising the steps of:
uniformly dispersing the conductive powder in a mixed solution of ethanol and diethyl ether, adding organic phosphorus salt into the solution, uniformly stirring for 30min at the constant temperature of 45 ℃, centrifuging and drying in vacuum to obtain a pretreated conductive phase.
The organic phosphorus salt is 1-n-hexyl-3-methylimidazole hexafluorophosphate.
Another object of the present invention is to provide a method for preparing the high temperature electronic paste.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the high-temperature electronic paste specifically comprises the following steps:
(1) Surface pretreatment of conductive phase powder: uniformly dispersing the conductive phase powder in a mixed solution of ethanol and diethyl ether, adding 1-n-hexyl-3-methylimidazole hexafluorophosphate into the solution, adding sodium hypophosphite, uniformly stirring at a constant temperature of 45 ℃ for 30min, centrifuging and drying in vacuum to obtain pretreated conductive powder.
(2) Preparing glass powder: the glass comprises the following components in percentage by mass: bi (Bi) 2 O 3 ：67-78wt％；B 2 O 3 ：5-11wt％；SiO 2 :0-3wt%; znO:8-15wt%; inO:1-7wt%; cuO:0-2wt%; snO:0-2wt%; proportionally placing the glass components into a sintering furnace, heating to 1100 ℃ and sintering for 2 hours at constant temperature, taking out, pouring into deionized water for cold quenching, and ball milling to obtain glass powder with the grain diameter of 5-40 mu m;
(3) Preparing an organic carrier: the mass ratio of the slurry carrier is organic solvent, reducing agent, dispersing agent, coupling agent, thickening agent and 1-n-hexyl-3-methylimidazole hexafluorophosphate in proportion under the condition of 45-65 ℃ and at the rotating speed of 150-250r/min, uniformly stirring for 15-30min, and obtaining the uniformly mixed slurry carrier.
(4) Preparing high-temperature electronic paste: and uniformly stirring and mixing the obtained pretreated conductive powder, glass powder and an organic carrier by using a dispersing machine to obtain the high-temperature electronic paste.
Preferably, in the step (1), the conductive phase powder is at least one of silver powder and silver-coated copper powder, and the conductive phase powder and the 1-n-hexyl-3-methylimidazole hexafluorophosphate are mixed according to the mass ratio (28-32) of 1.
Further, the proportioned conductive phase powder is silver powder or silver-coated copper powder subjected to surface pretreatment, wherein the small-particle-size powder is granular powder with the average particle size of 0.5-1 mu m, and the large-particle-size powder is flaky powder with the average particle size of 7-10 mu m; wherein the average particle diameter of the granular conductive phase powder is 0.5 μm,0.7 μm,0.9 μm or 1 μm, and the average particle diameter of the flaky conductive phase powder is 7 μm,8 μm,9 μm or 10 μm; the mass ratio of the small-particle-size powder to the large-particle-size powder is M Small size ：M Big size = (0.6-1): 2, wherein the mass ratio may be 0.6:2,0.7:2,0.8:2,0.9:2,1:2.
Further, the mass ratio of the ethanol to the diethyl ether in the ethanol and diethyl ether mixed solution is (3-5): 1, the centrifugal speed is 6000-10000rpm, and the time is 5-10min.
Preferably, in the step (2), the glass phase powder is a Bi-B-Zn based glass powder.
Preferably, in the step (3), the organic solvent is high temperature resistant resin or terpineol, the reducing agent is at least one of citric acid, ascorbic acid and formic acid, the dispersing agent is polyvinyl alcohol, the coupling agent is silane coupling agent, and the thickening agent is ethylcellulose.
Further, the mass ratio of the organic solvent, the reducing agent, the dispersing agent, the coupling agent, the thickening agent and the 1-n-hexyl-3-methylimidazole hexafluorophosphate in the slurry carrier is (65-85): 5-15): 1-8): 3-10): 2-10): 0-2.
Preferably, in the step (4), the mass ratio of the slurry carrier, the conductive phase powder and the glass phase powder in the high-temperature electronic slurry is (7-12): 78-90): 3-5.
Further, the rotational speed of the disperser in the stirring step is 9000-15000rpm, and the treatment time is 15-30min.
Compared with the prior art, the method for preparing the high-temperature electronic paste based on the organic phosphorus salt has the following excellent effects:
the invention improves the dispersibility and the bonding strength of the conductive powder by utilizing the 1-n-hexyl-3-methylimidazole hexafluorophosphate to carry out surface modification on the conductive phase powder; the high-temperature electronic paste comprises the following components in parts by weight: 7-12 parts of slurry carrier, 78-90 parts of conductive powder with different particle sizes and 3-5 parts of glass phase. According to the invention, the 1-n-hexyl-3-methylimidazole hexafluorophosphate is combined with the surface of the conductive phase, so that the slurry particles are uniformly distributed, the bonding strength among the conductive particles can be enhanced, a compact film is formed, the components are environment-friendly, the conductive effect of the slurry can be enhanced, and the performance of the high-temperature electronic slurry can be improved.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical aspects of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiment of the invention discloses a method for preparing high-temperature electronic paste based on 1-n-hexyl-3-methylimidazole hexafluorophosphate, and particularly discloses a method for preparing high-temperature electronic paste.
The present invention will be further specifically illustrated by the following examples, which are not to be construed as limiting the invention, but rather as falling within the scope of the present invention, for some non-essential modifications and adaptations of the invention that are apparent to those skilled in the art based on the foregoing disclosure.
The technical scheme of the invention will be further described below with reference to specific embodiments.
Example 1:
a method for preparing high-temperature electronic paste based on organic phosphorus salt specifically comprises the following steps:
step one: surface pretreatment of conductive phase powder: dispersing 85g of proportioned conductive phase powder into 510mL of ethanol diethyl ether mixed solution, adding 1g of 1-n-hexyl-3-methylimidazole hexafluorophosphate into the solution, adding 4g of sodium hypophosphite, uniformly stirring at a constant temperature of 45 ℃ for 30min, centrifuging at 10000rpm for 15min, and vacuum drying to obtain pretreated conductive phase powder;
step two: preparing glass powder: taking out each glass component according to a proportion, putting the glass component into a sintering heat preservation furnace for firing, and carrying out cold quenching by using deionized water, so that the obtained glass is ball-milled to obtain glass powder;
step three: preparation of the organic carrier: the mass ratio of terpineol, citric acid, polyvinyl alcohol, a silane coupling agent, ethyl cellulose and 1-n-hexyl-3-methylimidazole hexafluorophosphate in the slurry carrier is uniformly stirred for 20min at the rotating speed of 150rpm under the condition of 50 ℃ according to the mass ratio of 76:8:6:5:5:0, so that the uniformly mixed slurry carrier is obtained;
step four: preparation of the slurry: and dispersing the obtained pretreated conductive powder, glass phase powder and organic carrier at a mass ratio of 85:5:10 for 20min by using a dispersing machine at a rotating speed of 8000rpm to obtain uniform and environment-friendly high-temperature electronic paste.
Example 2:
a method for preparing high-temperature electronic paste based on organic phosphorus salt specifically comprises the following steps:
step one: surface pretreatment of conductive phase powder: dispersing 85g of proportioned conductive phase powder into 510mL of ethanol diethyl ether mixed solution, adding 3g of 1-n-hexyl-3-methylimidazole hexafluorophosphate into the solution, adding 4g of sodium hypophosphite, uniformly stirring at a constant temperature of 45 ℃ for 30min, centrifuging at 10000rpm for 15min, and vacuum drying to obtain pretreated conductive phase powder;
step two: preparing glass powder: taking out each glass component according to a proportion, putting the glass component into a sintering heat preservation furnace for firing, and carrying out cold quenching by using deionized water, so that the obtained glass is ball-milled to obtain glass powder;
step three: preparation of the organic carrier: the slurry carrier is prepared by uniformly stirring terpineol, citric acid, polyvinyl alcohol, a silane coupling agent, ethyl cellulose and 1-n-hexyl-3-methylimidazole hexafluorophosphate at a mass ratio of 76:8:6:5:5:0 at a rotating speed of 150rpm for 20min under the condition of 50 ℃ to obtain the uniformly mixed slurry carrier.
Step four: preparation of the slurry: and dispersing the obtained pretreated conductive powder, glass phase powder and organic carrier at a mass ratio of 85:5:10 for 20min by using a dispersing machine at a rotating speed of 10000rpm to obtain uniform and environment-friendly high-temperature electronic paste.
Example 3:
a method for preparing high-temperature electronic paste based on organic phosphorus salt specifically comprises the following steps:
step one: surface pretreatment of conductive phase powder: dispersing 85g of proportioned conductive phase powder into 510mL of ethanol diethyl ether mixed solution, adding 5g of 1-n-hexyl-3-methylimidazole hexafluorophosphate into the solution, adding 4g of sodium hypophosphite, uniformly stirring at a constant temperature of 45 ℃ for 30min, centrifuging at 10000rpm for 15min, and vacuum drying to obtain pretreated conductive phase powder;
step two: preparing glass powder: taking out each glass component according to a proportion, putting the glass component into a sintering heat preservation furnace for firing, and carrying out cold quenching by using deionized water, so that the obtained glass is ball-milled to obtain glass powder;
step three: preparation of the organic carrier: the mass ratio of terpineol, citric acid, polyvinyl alcohol, a silane coupling agent, ethyl cellulose and 1-n-hexyl-3-methylimidazole hexafluorophosphate in the slurry carrier is uniformly stirred for 20min at the rotating speed of 150rpm under the condition of 50 ℃ according to the mass ratio of 76:8:6:5:5:0, so that the uniformly mixed slurry carrier is obtained;
step four: preparation of the slurry: and dispersing the obtained pretreated conductive powder, glass phase powder and organic carrier at a mass ratio of 85:5:10 for 20min by using a dispersing machine at a rotating speed of 10000rpm to obtain uniform and environment-friendly high-temperature electronic paste.
Example 4:
a method for preparing high-temperature electronic paste based on organic phosphorus salt specifically comprises the following steps:
step one: surface pretreatment of conductive phase powder: dispersing 85g of proportioned conductive phase powder into 510mL of ethanol diethyl ether mixed solution, adding 3g of 1-n-hexyl-3-methylimidazole hexafluorophosphate into the solution, adding 4g of sodium hypophosphite, uniformly stirring at a constant temperature of 45 ℃ for 30min, centrifuging at 10000rpm for 15min, and vacuum drying to obtain pretreated conductive phase powder; step two: preparing glass powder: taking out each glass component according to a proportion, putting the glass component into a sintering heat preservation furnace for firing, and carrying out cold quenching by using deionized water, so that the obtained glass is ball-milled to obtain glass powder;
step three: preparation of the organic carrier: the slurry carrier is prepared by uniformly stirring terpineol, citric acid, polyvinyl alcohol, a silane coupling agent, ethyl cellulose and 1-n-hexyl-3-methylimidazole hexafluorophosphate at a mass ratio of 76:8:6:5:5:2 at a rotating speed of 150rpm for 20min under the condition of 50 ℃ to obtain the uniformly mixed slurry carrier.
Step four: preparation of the slurry: and dispersing the obtained pretreated conductive powder, glass phase powder and organic carrier at a mass ratio of 85:5:10 for 20min by using a dispersing machine at a rotating speed of 10000rpm to obtain uniform and environment-friendly high-temperature electronic paste.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The present invention is not limited to the above embodiments, but one or a combination of several embodiments can achieve the object of the present invention as well.
To further verify the excellent effects of the present invention, the inventors have also conducted the following experiments:
comparative example 1:
this comparative example provides a high temperature electronic paste in accordance with example 2 except that 1-n-hexyl-3-methylimidazole hexafluorophosphate was not added in the surface pretreatment of the conductive phase powder of step one.
Comparative example 2:
this comparative example provides a high temperature electronic paste in accordance with example 4 except that 1-n-hexyl-3-methylimidazole hexafluorophosphate was not added in the surface pretreatment of the conductive phase powder of step one.
Comparative example 3
High temperature electronic paste is common in certain markets.
Performance test:
the electroconductive pastes provided in examples 1 to 4 and comparative examples 1 to 3 were subjected to film formation:
and (3) adopting a semi-automatic precise printer, carrying out 325 meshes on a screen, curing the screen at 400 ℃ for 10min after printing, and curing the screen at 700 ℃ for 20min to carry out resistance test and adhesive strength test, wherein the thickness of the adhesive film is 30 um.
And printing the slurry on a flexible substrate, curing for 10min, starting 200 times of bending, and testing the resistivity after bending.
The results were as follows:
the results show that the product provided by the invention has better electric conductivity; comparing examples 1-4 with comparative examples 1-3, it can be found that the invention uses the surface modification technique of 1-n-hexyl-3-methylimidazole hexafluorophosphate to make the conductive powder disperse better, the conductive film is denser, the reducibility of the conductive film makes the gap in the conductive film smaller, and the performance of the slurry is improved.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for preparing high-temperature electronic paste based on organic phosphorus salt, which is characterized by comprising the following steps:
(1) Surface pretreatment of conductive phase powder: uniformly dispersing conductive phase powder in a mixed solution of ethanol and diethyl ether, adding 1-n-hexyl-3-methylimidazole hexafluorophosphate into the solution, adding sodium hypophosphite, uniformly stirring at a constant temperature of 45 ℃ for 30min, centrifuging and drying in vacuum to obtain pretreated conductive powder;
(2) Preparing glass powder: the glass components are put into a sintering furnace for firing, then deionized water is used for cold quenching, and glass powder is obtained through ball milling;
(3) Preparing an organic carrier: uniformly stirring an organic solvent, a reducing agent, a dispersing agent, a coupling agent, a thickening agent and 1-n-hexyl-3-methylimidazole hexafluorophosphate at a temperature of 45-65 ℃ at a rotating speed of 150-250r/min for 15-30min to obtain a uniformly mixed slurry carrier;
(4) Preparing high-temperature electronic paste: and uniformly stirring and mixing the obtained pretreated conductive powder, glass powder and an organic carrier by using a dispersing machine to obtain the high-temperature electronic paste.
2. The method for preparing high-temperature electronic paste based on organic phosphorus salt according to claim 1, wherein in the step (1), the conductive phase powder is at least one of silver powder and silver-coated copper powder, and the conductive phase powder and 1-n-hexyl-3-methylimidazole hexafluorophosphate are mixed according to a mass ratio (28-32): 1.
3. The method for preparing a high-temperature electronic paste based on an organic phosphorus salt according to claim 1 or 2, wherein said conductive phase powder is silver powder or silver-coated copper powder after surface pretreatment, the small particle size powder thereof is granular powder having an average particle size of 0.5 to 1 μm, and the large particle size powder thereof is flake powder having an average particle size of 7 to 10 μm; wherein the average particle diameter of the granular conductive phase powder is 0.5 μm,0.7 μm,0.9 μm or 1 μm, and the sheet-like conductive phase powderThe average particle diameter of (2) is 7 μm,8 μm,9 μm or 10 μm; the mass ratio of the small-particle-size powder to the large-particle-size powder is M Small size ：M Big size =（0.6-1）:2。
4. The method for preparing high-temperature electronic paste based on organic phosphorus salt according to claim 3, wherein the mass ratio of ethanol to diethyl ether in the mixed solution of ethanol and diethyl ether is (3-5): 1, and the centrifugal speed is 6000-10000rpm, and the time is 5-10min.
5. The method for preparing high-temperature electronic paste based on organic phosphorus salt according to claim 1, wherein in the step (2), the glass component comprises, in mass percent:
Bi 2 O 3 ：67-78 wt%；B 2 O 3 ：5-11 wt%；SiO 2 :0-3wt%; znO:8-15wt%; inO:1-7wt%; cuO:0-2wt%; snO: 0-2-wt% and the glass powder is prepared by using Bi-B-Zn as a base.
6. The method for preparing high-temperature electronic paste based on organic phosphorus salt according to claim 1 or 5, wherein the sintering temperature in the step (2) is 1100 ℃, and the constant-temperature sintering time is 2h.
7. The method for preparing high-temperature electronic paste based on organic phosphorus salt according to claim 1, wherein in the step (3), the organic solvent is high-temperature resistant resin or terpineol, the reducing agent is at least one of citric acid, ascorbic acid and formic acid, the dispersing agent is polyvinyl alcohol, the coupling agent is silane coupling agent, and the thickening agent is ethylcellulose.
8. The method for preparing high-temperature electronic paste based on organic phosphorus salt according to claim 6, wherein the mass ratio of organic solvent, reducing agent, dispersing agent, coupling agent, thickening agent and 1-n-hexyl-3-methylimidazolium hexafluorophosphate in the paste carrier is (65-85): 5-15): 1-8): 3-10): 2-10): 0-2.
9. The method for preparing high-temperature electronic paste based on organic phosphorus salt according to claim 1, wherein in the step (4), the mass ratio of the paste carrier, the conductive phase powder and the glass phase powder in the high-temperature electronic paste is (7-12): 78-90): 3-5.
10. The method for preparing high-temperature electronic paste based on organic phosphorus salt according to claim 1 or 8, wherein the rotation speed of the disperser is 9000-15000rpm and the treatment time is 15-30min.
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