CN106887272B - The preparation of chemical reduction method different-grain diameter graphene coated silver powder and the preparation method of slurry - Google Patents
The preparation of chemical reduction method different-grain diameter graphene coated silver powder and the preparation method of slurry Download PDFInfo
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Abstract
The preparation of chemical reduction method different-grain diameter graphene coated silver powder and the preparation method of slurry, the method that it is related to a kind of preparation method of graphene coated silver powder and prepares silver paste using it.The invention aims to solve the problem of that conventional fat acid surfaces chemical agent is modified the dispersibility of silver powder and poor lubricity is unfavorable for solar energy slurry silk-screen printing.Preparation method：One, the graphene oxide of different sizes is prepared；Two, graphene coated silver powder is prepared.The graphene coated silver powder of different-grain diameter is modified unleaded slurry and is prepared in parts by weight by the graphene coated silver powder of 80 parts~92 parts different-grain diameters, 3 parts~15 parts glass powders and 4 parts~10 parts organic carriers；Preparation method：Weighing, mixing, grinding.The graphene coated silver powder that the present invention can get different-grain diameter is modified unleaded slurry.
Description
Technical field
The present invention relates to a kind of preparation method of graphene coated silver powder and the methods for preparing slurry using it.
Background technology
With the development of science and technology, one-component material can no longer meet requirement of the people to material property, by object
The reason two or more Material claddings different from chemical property, due to the synergistic effect between each component so that the property of composite material
It can be better than one-component.Noble silver is widely used in catalysis, conducting resinl, information due to its excellent physics and chemical property
The fields such as storage, electronic material.The excellent mechanics of graphene, optics, electricity and thermal property, make its receive extensive attention with
Using.
Currently, the application percentage of silver powder in solar cells increasingly increases, and in solar energy slurry silver powder dispersibility
And lubricity has the printing of solar energy slurry and significantly affects, traditional solution is selection aliphatic acids surface
Activating agent carries out surface modification, but because the lubricity of the surfactant-modified silver powder of aliphatic acids is poor, is unfavorable for solar energy
Slurry silk-screen printing.
Invention content
The dispersibility and poor lubricity of silver powder are modified the invention aims to solve conventional fat acid surfaces chemical agent, no
The problem of conducive to solar energy slurry silk-screen printing, and a kind of preparation of chemical reduction method different-grain diameter graphene coated silver powder is provided
And the preparation method of slurry.
A method of preparing the graphene coated silver powder of different-grain diameter using chemical reduction method, specifically according to the following steps
It completes：
One, the graphene oxide of different sizes is prepared：
1., graphite powder is added in the sulfuric acid that mass fraction is 98% under conditions of ice-water bath, then low whipping speed
For potassium permanganate powder is added under 150r/min~250r/min, mixed liquor I is obtained；
Step 1 1. described in graphite powder quality and mass fraction be 98% the volume ratio of sulfuric acid be 1g:(10mL
~50mL)；
Step 1 1. described in graphite powder and potassium permanganate powder mass ratio be 1:(2~8)；
2., mixed liquor I is heated to 30 DEG C~40 DEG C, then low whipping speed is to be reacted under 150r/min~250r/min
20min~40min, then low whipping speed are that ultra-pure deionized water is added under 150r/min~250r/min, are then heated to 95
DEG C~100 DEG C, then 10min~20min is kept at being 95 DEG C~100 DEG C in temperature, obtain mixed solution II；
Step 1 2. described in mixed liquor I quality and ultra-pure deionized water volume ratio be 1:(2~4)；
3., ultra-pure deionized water is added into mixed solution II first, then be added mass fraction be 30% hydrogen peroxide,
It is centrifuged again after mixing, obtains solid matter；The hydrochloric acid that use quality score is 5% carries out solid matter clear
It washing, until can't detect sulfate ion in cleaning solution, stopping cleaning, the solid matter after being cleaned, as graphite oxide
Alkene；
Step 1 3. described in the volume ratio of mixed solution II and ultra-pure deionized water be 1:(2~5)；
Step 1 3. described in mixed solution II and mass fraction be 30% the volume ratio of hydrogen peroxide be 1:(0.1~
0.6)；
Step 1 3. described in graphene oxide size be 10 μm~25 μm；
4., graphene oxide is distributed in water, obtain graphene oxide water solution, reuse probe type ultrasonic concussion
Instrument to graphene oxide water solution ultrasonic power be 75W~750W under ultrasound 10min~120min, then temperature be -50 DEG C
It is freeze-dried 10h~12h at~-15 DEG C, obtains the graphene oxide of different sizes；
Step 1 4. described in different sizes graphene oxide D50 sizes be 0.05 μm~2 μm；
Two, graphene coated silver powder is prepared：
1., silver nitrate is dissolved in ultra-pure water, obtain the silver nitrate solution of a concentration of 50g/L~250g/L；
2., glucose, ascorbic acid and hydrazine hydrate be dissolved in ultra-pure water, obtain reducing solution；
Step 2 2. described in reducing solution in glucose a concentration of 75g/L~300g/L；
Step 2 2. described in reducing solution in ascorbic acid a concentration of 75g/L~300g/L；
Step 2 2. described in reducing solution in hydrazine hydrate a concentration of 20g/L~100g/L；
3., surfactant is added in reducing solution, the oxygen of the different sizes obtained in adding step 1 4.
Graphite alkene, stirs evenly, and obtains solution A；
Step 2 3. described in solution A in surfactant quality and reducing solution volume ratio be (10g~50g):
500mL；
Step 2 3. described in different sizes graphene oxide quality and reducing solution volume ratio be (0.1g
~2g):500mL；
4., in the case where temperature is 20 DEG C~45 DEG C and mixing speed is 100r/min~500r/min using dropping funel will be dense
Degree is that the silver nitrate solution of 50g/L~250g/L is slowly dropped in solution A, and time for adding is 20min~80min；Or in temperature
Degree is 20 DEG C~45 DEG C and mixing speed is that will be slowly dropped in solution A using dropping funel under 100r/min~500r/min
In the silver nitrate solution of a concentration of 50g/L~250g/L, time for adding is 20min~80min；A concentration of 50g/L~250g/L
Silver nitrate solution and solution A be thoroughly mixed after again low whipping speed be stirred to react under 100r/min~500r/min 0.5h~
2h, then it is freeze-dried 10h~12h at being -50 DEG C~-15 DEG C in temperature, obtain the graphene coated silver powder of different-grain diameter；
Step 2 4. described in a concentration of 50g/L~250g/L silver nitrate solution and solution A volume ratio be (0.5
~3):1.
The graphene coated silver powder of different-grain diameter is modified unleaded slurry in parts by weight by 80 parts~92 parts different-grain diameters
Graphene coated silver powder, 3 parts~15 parts glass powders and 4 parts~10 parts organic carriers are prepared.
The graphene coated silver powder of different-grain diameter is modified the preparation method of unleaded slurry, completes according to the following steps：
One, weigh in parts by weight the graphene coated silver powder of 80 parts~92 parts different-grain diameters, 3 parts~15 parts glass powders and
4 parts~10 parts organic carriers；
Two, by the graphene coated silver powder of weighed in step 1 80 parts~92 parts different-grain diameters, 3 parts~15 parts glass powders
It is uniformly mixed, then is ground with 4 parts~10 parts organic carriers, the graphene coated silver powder for obtaining different-grain diameter is modified unleaded slurry
Material；
The fineness that the graphene coated silver powder of different-grain diameter described in step 2 is modified unleaded slurry is less than 5 μm；
Organic carrier described in step 1 is prepared according to the following steps：
1., prepare organic solvent：20 parts~40 parts alcohol esters, 12,27 parts~50 parts adipic acid diformazans are weighed in parts by weight
Ester, 2 parts~5 parts tributyl citrate, 5 parts~10 parts dibutyl phthalates and 0.1 part~2 parts lecithin；By what is weighed
20 parts~40 parts alcohol esters, 12,27 parts~50 parts dimethyl adipates, 2 parts~5 parts tributyl citrate, 5 parts~10 parts adjacent benzene two
Formic acid dibutyl ester and the mixing of 0.1 part~2 parts lecithin, then temperature be 70 DEG C~90 DEG C and mixing speed be 100r/min~
10min~120min is stirred under 500r/min, obtains organic solvent；
2., weigh 1 part~10 parts binders, 2 parts~6 parts modified polyamide waxes, 0.1 part~1 part gas phase in parts by weight
Silica and 1 part~5 parts modified hydrogenated castor oil；Successively by step 2. in weigh 1 part~10 parts binders, 2 parts~6 parts
Modified polyamide wax, 0.1 part~1 part aerosil and 1 part~5 parts modified hydrogenated castor oil are added in step 1 and obtain
Organic solvent in, then in the case where temperature is 70 DEG C~90 DEG C and mixing speed is 100r/min~500r/min stirring 10min~
40min, then low whipping speed are cooled to room temperature under 50r/min~100r/min, obtain organic carrier；
Step 2. described in binder be ethyl cellulose, epoxy resin, alkyd resin, polyurethane resin, melamine
Amine-formaldehyde resins, phenolic resin acrylic resin and one kind in polyvinyl butyral or in which two kinds of mixture；It is described
Ethyl cellulose be N40~N200；
What the glass powder described in step 1 was specifically prepared according to the following steps：
(1), 40 parts~50 parts Bi are weighed in parts by weight2O3, 20 parts~30 parts of SiO2, 20 parts~25 parts of B2O3, 2 parts~13
Part Al2O3, 3 parts~5 parts of TiO2, 1 part~6 parts of BaO, 1 part~7 parts TeO2, 1 part~9 parts of ZrO, 1 part~8 parts Y2O3, 3 parts~5 parts
ZnO and 2 part~5 parts Ag2O；
(2), 40 parts~50 parts Bi that will be weighed in step (1)2O3, 20 parts~30 parts of SiO2, 20 parts~25 parts of B2O3, 2 parts
~13 parts of Al2O3, 3 parts~5 parts of TiO2, 1 part~6 parts of BaO, 1 part~7 parts TeO2, 1 part~9 parts of ZrO, 1 part~8 parts Y2O3, 3 parts
~5 parts of ZnO and 2 part~5 parts Ag2O is uniformly mixed, and obtains mixed-powder；
(3), by mixed-powder temperature be 900 DEG C~1300 DEG C at calcine 0.5h~2h, obtain clear glass precursor solution；
Clear glass precursor solution is taken out from Muffle furnace, then carries out rapid quenching or annealing cooling, obtains crystal type glass；It will crystallization
Type glass obtains glass powder by air-flow crushing；
The grain size of glass powder described in step (3) is 0.7 μm~4.5 μm.
The principle of the present invention and advantage：
One, the present invention restores different sizes GO and silver nitrate simultaneously using chemical reduction method, realizes different-grain diameter
The preparation of RGO coated silvers, this method gained silver powder not only has the advantageous property of conventional precious metal silver, excellent with more graphene
Different mechanics, optics, electricity and thermal property can be used for optics, physics, the fields such as chemistry, biology, electronics and information storage.
Two, the present invention restores different sizes GO and silver nitrate simultaneously using chemical reduction method, realizes different-grain diameter
The preparation of RGO coated silvers, made composite material have excellent performance and are widely applied.
Three, graphene makes it be very suitable for making due to excellent heat conductivility and anti-wear and wear-resistant performance and chemical inertness
For high-performance, the lubricating additive of environmental protection, it is based on this, the present invention realizes different-grain diameter by chemical reduction method using graphene
Graphene coated silver powder preparation, can form Schottky barrier because graphene is contacted with silicon, be effectively promoted electron-hole
Separation, and the graphene coated silver powder of different-grain diameter solve conventional fat acid surfaces chemical agent be modified silver powder lubrication
Property, and then improve solar cell photoelectric transformation efficiency；
Four, the graphene coated silver powder of different-grain diameter prepared by the present invention is modified the conversion ratio of unleaded slurry and reaches 18.4%
(156mm*156mm polycrystal silicon cells), unit consumption is low, by taking 156mm*156mm cell pieces as an example, using the different grains of the invention prepared
The unit consumption that the graphene coated silver powder of diameter is modified the crystal silicon solar batteries that unleaded slurry makes is only 0.101g/pcs, and is used
The unit consumption for the crystal silicon solar batteries that import business slurrying material makes is 0.112g/pcs~0.123g/pcs.
The graphene coated silver powder that the present invention can get different-grain diameter is modified unleaded slurry.
Description of the drawings
Fig. 1 is the SEM figures that the graphene coated silver powder of different-grain diameter prepared by embodiment one amplifies 2000 times.
Specific implementation mode
Specific implementation mode one：Present embodiment is a kind of graphene coated preparing different-grain diameter using chemical reduction method
The method of silver powder, is specifically realized by the following steps：
One, the graphene oxide of different sizes is prepared：
1., graphite powder is added in the sulfuric acid that mass fraction is 98% under conditions of ice-water bath, then low whipping speed
For potassium permanganate powder is added under 150r/min~250r/min, mixed liquor I is obtained；
Step 1 1. described in graphite powder quality and mass fraction be 98% the volume ratio of sulfuric acid be 1g:(10mL
~50mL)；
Step 1 1. described in graphite powder and potassium permanganate powder mass ratio be 1:(2~8)；
2., mixed liquor I is heated to 30 DEG C~40 DEG C, then low whipping speed is to be reacted under 150r/min~250r/min
20min~40min, then low whipping speed are that ultra-pure deionized water is added under 150r/min~250r/min, are then heated to 95
DEG C~100 DEG C, then 10min~20min is kept at being 95 DEG C~100 DEG C in temperature, obtain mixed solution II；
Step 1 2. described in mixed liquor I quality and ultra-pure deionized water volume ratio be 1:(2~4)；
3., ultra-pure deionized water is added into mixed solution II first, then be added mass fraction be 30% hydrogen peroxide,
It is centrifuged again after mixing, obtains solid matter；The hydrochloric acid that use quality score is 5% carries out solid matter clear
It washing, until can't detect sulfate ion in cleaning solution, stopping cleaning, the solid matter after being cleaned, as graphite oxide
Alkene；
Step 1 3. described in the volume ratio of mixed solution II and ultra-pure deionized water be 1:(2~5)；
Step 1 3. described in mixed solution II and mass fraction be 30% the volume ratio of hydrogen peroxide be 1:(0.1~
0.6)；
Step 1 3. described in graphene oxide size be 10 μm~25 μm；
4., graphene oxide is distributed in water, obtain graphene oxide water solution, reuse probe type ultrasonic concussion
Instrument to graphene oxide water solution ultrasonic power be 75W~750W under ultrasound 10min~120min, then temperature be -50 DEG C
It is freeze-dried 10h~12h at~-15 DEG C, obtains the graphene oxide of different sizes；
Step 1 4. described in different sizes graphene oxide D50 sizes be 0.05 μm~2 μm；
Two, graphene coated silver powder is prepared：
1., silver nitrate is dissolved in ultra-pure water, obtain the silver nitrate solution of a concentration of 50g/L~250g/L；
2., glucose, ascorbic acid and hydrazine hydrate be dissolved in ultra-pure water, obtain reducing solution；
Step 2 2. described in reducing solution in glucose a concentration of 75g/L~300g/L；
Step 2 2. described in reducing solution in ascorbic acid a concentration of 75g/L~300g/L；
Step 2 2. described in reducing solution in hydrazine hydrate a concentration of 20g/L~100g/L；
3., surfactant is added in reducing solution, the oxygen of the different sizes obtained in adding step 1 4.
Graphite alkene, stirs evenly, and obtains solution A；
Step 2 3. described in solution A in surfactant quality and reducing solution volume ratio be (10g~50g):
500mL；
Step 2 3. described in different sizes graphene oxide quality and reducing solution volume ratio be (0.1g
~2g):500mL；
4., in the case where temperature is 20 DEG C~45 DEG C and mixing speed is 100r/min~500r/min using dropping funel will be dense
Degree is that the silver nitrate solution of 50g/L~250g/L is slowly dropped in solution A, and time for adding is 20min~80min；Or in temperature
Degree is 20 DEG C~45 DEG C and mixing speed is that will be slowly dropped in solution A using dropping funel under 100r/min~500r/min
In the silver nitrate solution of a concentration of 50g/L~250g/L, time for adding is 20min~80min；A concentration of 50g/L~250g/L
Silver nitrate solution and solution A be thoroughly mixed after again low whipping speed be stirred to react under 100r/min~500r/min 0.5h~
2h, then it is freeze-dried 10h~12h at being -50 DEG C~-15 DEG C in temperature, obtain the graphene coated silver powder of different-grain diameter；
Step 2 4. described in a concentration of 50g/L~250g/L silver nitrate solution and solution A volume ratio be (0.5
~3):1.
Specific implementation mode two：The difference of present embodiment and specific implementation mode one is：Step 2 3. described in
Surfactant is one kind or in which several mixtures in CTAB, CTAC, OA and OM.Other and one phase of specific implementation mode
Together.
Specific implementation mode three：The difference of present embodiment and specific implementation mode one or two is：Step 2 4. in institute
The grain size of the graphene coated silver powder for the different-grain diameter stated is 0.1 μm~4.5 μm.Other and specific implementation mode one or two-phase
Together.
Specific implementation mode four：Present embodiment is that the graphene coated silver powder of different-grain diameter is modified unleaded slurry by weight
Number by 80 parts~92 parts different-grain diameters graphene coated silver powder, 3 parts~15 parts glass powders and 4 parts~10 parts organic carrier systems
It is standby to form.
Specific implementation mode five：The difference of present embodiment and specific implementation mode four is：The graphene of different-grain diameter
Coated silver is modified unleaded slurry in parts by weight by the graphene coated silver powder of 80 parts~85 parts different-grain diameters, 3 parts~8 parts glass
Glass powder and 4 parts~7 parts organic carriers are prepared.Other are identical as specific implementation mode four.
Specific implementation mode six：The difference of present embodiment and specific implementation mode four or five is：The stone of different-grain diameter
Black alkene coated silver be modified unleaded slurry in parts by weight by the graphene coated silver powder of 85 parts~92 parts different-grain diameters, 8 parts~
15 parts of glass powders and 7 parts~10 parts organic carriers are prepared.Other are identical as specific implementation mode four or five.
Specific implementation mode seven：The difference of present embodiment and specific implementation mode four to six is：The stone of different-grain diameter
Black alkene coated silver is modified unleaded slurry in parts by weight by the graphene coated silver powder of 86 parts of different-grain diameters, 9 parts of glass powders and 8
Part organic carrier is prepared.Other are identical as specific implementation mode four to six.
Specific implementation mode eight：The difference of present embodiment and specific implementation mode four to seven is：Described having is airborne
Body is prepared according to the following steps：
One, organic solvent is prepared：20 parts~40 parts alcohol esters, 12,27 parts~50 parts adipic acid diformazans are weighed in parts by weight
Ester, 2 parts~5 parts tributyl citrate, 5 parts~10 parts dibutyl phthalates and 0.1 part~2 parts lecithin；By what is weighed
20 parts~40 parts alcohol esters, 12,27 parts~50 parts dimethyl adipates, 2 parts~5 parts tributyl citrate, 5 parts~10 parts adjacent benzene two
Formic acid dibutyl ester and the mixing of 0.1 part~2 parts lecithin, then temperature be 70 DEG C~90 DEG C and mixing speed be 100r/min~
10min~120min is stirred under 500r/min, obtains organic solvent；
Two, 1 part~10 parts binders, 2 parts~6 parts modified polyamide waxes, 0.1 part~1 part gas phase are weighed in parts by weight
Silica and 1 part~5 parts modified hydrogenated castor oil；Successively by weighed in step 21 part~10 parts binders, 2 parts~6 parts
Modified polyamide wax, 0.1 part~1 part aerosil and 1 part~5 parts modified hydrogenated castor oil are added in step 1 and obtain
Organic solvent in, then in the case where temperature is 70 DEG C~90 DEG C and mixing speed is 100r/min~500r/min stirring 10min~
40min, then low whipping speed are cooled to room temperature under 50r/min~100r/min, obtain organic carrier；
Binder described in step 2 is ethyl cellulose, epoxy resin, alkyd resin, polyurethane resin, melamine
Amine-formaldehyde resins, phenolic resin acrylic resin and one kind in polyvinyl butyral or in which two kinds of mixture；It is described
Ethyl cellulose be N40~N200.Other are identical as specific implementation mode four to seven.
Modified hydrogenated castor oil described in present embodiment step 2 is bought from Changxing consonance limited public affairs of high molecular material
Department, model RC-HST；
Modified polyamide wax described in present embodiment step 2 is bought from Changxing consonance high molecular material Co., Ltd,
Model MAW-6600.
Specific implementation mode nine：The difference of present embodiment and specific implementation mode four to eight is：The glass powder
Specifically prepare according to the following steps：
One, 40 parts~50 parts Bi are weighed in parts by weight2O3, 20 parts~30 parts of SiO2, 20 parts~25 parts of B2O3, 2 parts~13
Part Al2O3, 3 parts~5 parts of TiO2, 1 part~6 parts of BaO, 1 part~7 parts TeO2, 1 part~9 parts of ZrO, 1 part~8 parts Y2O3, 3 parts~5 parts
ZnO and 2 part~5 parts Ag2O；
Two, by weighed in step 1 40 parts~50 parts Bi2O3, 20 parts~30 parts of SiO2, 20 parts~25 parts of B2O3, 2 parts~
13 parts of Al2O3, 3 parts~5 parts of TiO2, 1 part~6 parts of BaO, 1 part~7 parts TeO2, 1 part~9 parts of ZrO, 1 part~8 parts Y2O3, 3 parts~5
ZnO and 2 part~5 parts Ag of part2O is uniformly mixed, and obtains mixed-powder；
Three, by mixed-powder temperature be 900 DEG C~1300 DEG C at calcine 0.5h~2h, obtain clear glass precursor solution；
Clear glass precursor solution is taken out from Muffle furnace, then carries out rapid quenching or annealing cooling, obtains crystal type glass；It will crystallization
Type glass obtains glass powder by air-flow crushing；
The grain size of glass powder described in step 3 is 0.7 μm~4.5 μm.Other and four to eight phase of specific implementation mode
Together.
Specific implementation mode ten：Present embodiment is that the graphene coated silver powder of different-grain diameter is modified the preparation of unleaded slurry
Method is completed according to the following steps：
One, weigh in parts by weight the graphene coated silver powder of 80 parts~92 parts different-grain diameters, 3 parts~15 parts glass powders and
4 parts~10 parts organic carriers；
Two, by the graphene coated silver powder of weighed in step 1 80 parts~92 parts different-grain diameters, 3 parts~15 parts glass powders
It is uniformly mixed, then is ground with 4 parts~10 parts organic carriers, the graphene coated silver powder for obtaining different-grain diameter is modified unleaded slurry
Material；
The fineness that the graphene coated silver powder of different-grain diameter described in step 2 is modified unleaded slurry is less than 5 μm；
Organic carrier described in step 1 is prepared according to the following steps：
1., prepare organic solvent：20 parts~40 parts alcohol esters, 12,27 parts~50 parts adipic acid diformazans are weighed in parts by weight
Ester, 2 parts~5 parts tributyl citrate, 5 parts~10 parts dibutyl phthalates and 0.1 part~2 parts lecithin；By what is weighed
20 parts~40 parts alcohol esters, 12,27 parts~50 parts dimethyl adipates, 2 parts~5 parts tributyl citrate, 5 parts~10 parts adjacent benzene two
Formic acid dibutyl ester and the mixing of 0.1 part~2 parts lecithin, then temperature be 70 DEG C~90 DEG C and mixing speed be 100r/min~
10min~120min is stirred under 500r/min, obtains organic solvent；
2., weigh 1 part~10 parts binders, 2 parts~6 parts modified polyamide waxes, 0.1 part~1 part gas phase in parts by weight
Silica and 1 part~5 parts modified hydrogenated castor oil；Successively by step 2. in weigh 1 part~10 parts binders, 2 parts~6 parts
Modified polyamide wax, 0.1 part~1 part aerosil and 1 part~5 parts modified hydrogenated castor oil are added in step 1 and obtain
Organic solvent in, then in the case where temperature is 70 DEG C~90 DEG C and mixing speed is 100r/min~500r/min stirring 10min~
40min, then low whipping speed are cooled to room temperature under 50r/min~100r/min, obtain organic carrier；
Step 2. described in binder be ethyl cellulose, epoxy resin, alkyd resin, polyurethane resin, melamine
Amine-formaldehyde resins, phenolic resin acrylic resin and one kind in polyvinyl butyral or in which two kinds of mixture；It is described
Ethyl cellulose be N40~N200；
What the glass powder described in step 1 was specifically prepared according to the following steps：
(1), 40 parts~50 parts Bi are weighed in parts by weight2O3, 20 parts~30 parts of SiO2, 20 parts~25 parts of B2O3, 2 parts~13
Part Al2O3, 3 parts~5 parts of TiO2, 1 part~6 parts of BaO, 1 part~7 parts TeO2, 1 part~9 parts of ZrO, 1 part~8 parts Y2O3, 3 parts~5 parts
ZnO and 2 part~5 parts Ag2O；
(2), 40 parts~50 parts Bi that will be weighed in step (1)2O3, 20 parts~30 parts of SiO2, 20 parts~25 parts of B2O3, 2 parts
~13 parts of Al2O3, 3 parts~5 parts of TiO2, 1 part~6 parts of BaO, 1 part~7 parts TeO2, 1 part~9 parts of ZrO, 1 part~8 parts Y2O3, 3 parts
~5 parts of ZnO and 2 part~5 parts Ag2O is uniformly mixed, and obtains mixed-powder；
(3), by mixed-powder temperature be 900 DEG C~1300 DEG C at calcine 0.5h~2h, obtain clear glass precursor solution；
Clear glass precursor solution is taken out from Muffle furnace, then carries out rapid quenching or annealing cooling, obtains crystal type glass；It will crystallization
Type glass obtains glass powder by air-flow crushing；
The grain size of glass powder described in step (3) is 0.7 μm~4.5 μm.
Present embodiment step 2. described in modified hydrogenated castor oil purchase from Changxing coordinate the limited public affairs of high molecular material
Department, model RC-HST；
Present embodiment step 2. described in the purchase of modified polyamide wax from Changxing consonance high molecular material Co., Ltd,
Model MAW-6600.
The principle and advantage of present embodiment：
One, present embodiment restores different sizes graphene oxide and silver nitrate simultaneously using chemical reduction method, real
The preparation of different-grain diameter redox graphene coated silver is showed, silver powder is not only with conventional precious metal silver obtained by this method
Advantageous property can be used for optics, physics, chemistry, life with more mechanics, optics, electricity and the thermal property that graphene is excellent
The fields such as object, electronics and information storage.
Two, present embodiment restores different sizes graphene oxide and silver nitrate simultaneously using chemical reduction method, real
The preparation of different-grain diameter redox graphene coated silver is showed, made composite material has excellent performance and widely answers
With.
Three, graphene makes it be very suitable for making due to excellent heat conductivility and anti-wear and wear-resistant performance and chemical inertness
For high-performance, the lubricating additive of environmental protection, it is based on this, present embodiment realizes difference by chemical reduction method using graphene
The preparation of the graphene coated silver powder of grain size can form Schottky barrier because graphene is contacted with silicon, be effectively promoted electronics-
The separation in hole, and the graphene coated silver powder of different-grain diameter solves the profit that conventional fat acid surfaces chemical agent is modified silver powder
Slip, and then improve solar cell photoelectric transformation efficiency；
Four, the graphene coated silver powder of different-grain diameter prepared by present embodiment is modified the conversion ratio of unleaded slurry and reaches
18.4% (156mm*156mm polycrystal silicon cells), unit consumption is low, by taking 156mm*156mm cell pieces as an example, using present embodiment system
The unit consumption that the graphene coated silver powder of standby different-grain diameter is modified the crystal silicon solar batteries that unleaded slurry makes is only 0.101g/
Pcs, and use the unit consumption of the crystal silicon solar batteries of import business slurrying material making for 0.112g/pcs~0.123g/pcs.
The graphene coated silver powder that present embodiment can get different-grain diameter is modified unleaded slurry.
Embodiment one：A method of preparing the graphene coated silver powder of different-grain diameter using chemical reduction method, specifically
It completes according to the following steps：
One, the graphene oxide of different sizes is prepared：
1., graphite powder is added in the sulfuric acid that mass fraction is 98% under conditions of ice-water bath, then low whipping speed
For potassium permanganate powder is added under 200r/min, mixed liquor I is obtained；
Step 1 1. described in graphite powder quality and mass fraction be 98% the volume ratio of sulfuric acid be 1g:30mL；
Step 1 1. described in graphite powder and potassium permanganate powder mass ratio be 1:5；
2., mixed liquor I is heated to 35 DEG C, then low whipping speed is to react 30min, then low whipping speed under 200r/min
For ultra-pure deionized water is added under 200r/min, 98 DEG C is then heated to, then 15min is kept at being 98 DEG C in temperature, is mixed
Close solution II；
Step 1 2. described in mixed liquor I quality and ultra-pure deionized water volume ratio be 1:3；
3., ultra-pure deionized water is added into mixed solution II first, then be added mass fraction be 30% hydrogen peroxide,
It is centrifuged again after mixing, obtains solid matter；The hydrochloric acid that use quality score is 5% carries out solid matter clear
It washing, until can't detect sulfate ion in cleaning solution, stopping cleaning, the solid matter after being cleaned, as graphite oxide
Alkene；
Step 1 3. described in the volume ratio of mixed solution II and ultra-pure deionized water be 1:3；
Step 1 3. described in mixed solution II and mass fraction be 30% the volume ratio of hydrogen peroxide be 1:0.35；
Step 1 3. described in graphene oxide size be 10 μm~25 μm；
4., graphene oxide is distributed in water, obtain graphene oxide water solution, reuse probe type ultrasonic concussion
Instrument ultrasound 60min in the case where ultrasonic power is 200W to graphene oxide water solution, then it is freeze-dried 10h at being -30 DEG C in temperature,
Obtain the graphene oxide of different sizes；
Step 1 4. described in different sizes graphene oxide D50 sizes be 0.05 μm~2 μm；
Two, graphene coated silver powder is prepared：
1., silver nitrate is dissolved in ultra-pure water, obtain the silver nitrate solution of a concentration of 150g/L；
2., glucose, ascorbic acid and hydrazine hydrate be dissolved in ultra-pure water, obtain reducing solution；
Step 2 2. described in reducing solution in glucose a concentration of 150g/L；
Step 2 2. described in reducing solution in ascorbic acid a concentration of 150g/L；
Step 2 2. described in reducing solution in hydrazine hydrate a concentration of 60g/L；
3., surfactant is added in reducing solution, the oxygen of the different sizes obtained in adding step 1 4.
Graphite alkene, stirs evenly, and obtains solution A；
Step 2 3. described in surfactant be CTAB；
Step 2 3. described in solution A in surfactant quality and reducing solution volume ratio be 30g:500mL；
Step 2 3. described in different sizes graphene oxide quality and reducing solution volume ratio be 1g:
500mL；
4., in the case where temperature is 30 DEG C and mixing speed is 300r/min using dropping funel by the nitric acid of a concentration of 150g/L
Silver-colored solution is slowly dropped in solution A, time for adding 50min；Or in the case where temperature is 35 DEG C and mixing speed is 300r/min
It will be slowly dropped in solution A in the silver nitrate solution of a concentration of 150g/L using dropping funel, time for adding 50min；It is dense
Degree be 150g/L silver nitrate solution and solution A be thoroughly mixed after again low whipping speed 1h is stirred to react under being 300r/min, then
It is freeze-dried 10h at being -30 DEG C in temperature, obtains the graphene coated silver powder of different-grain diameter；
Step 2 4. described in a concentration of 150g/L silver nitrate solution and solution A volume ratio be 1.5:1.
Step 2 4. described in different-grain diameter graphene coated silver powder grain size be 2.5 μm~3.5 μm.
Fig. 1 is the SEM figures that the graphene coated silver powder of different-grain diameter prepared by embodiment one amplifies 2000 times.
The dispersion of graphene coated silver powder is more uniform as can be seen from Figure 1, does not occur significantly to reunite.
Embodiment two：The graphene coated silver powder of different-grain diameter prepared by embodiment one is prepared to the graphene of different-grain diameter
The method that coated silver is modified unleaded slurry, is specifically realized by the following steps：
One, the graphene coated silver powder, 9 parts of glass powders and 8 parts of organic carriers of 86 parts of different-grain diameters are weighed in parts by weight；
Two, the graphene coated silver powder of weighed in step 1 86 parts of different-grain diameters, 9 parts of glass powders and 8 parts are had airborne
Body is uniformly mixed, then is ground, and the graphene coated silver powder for obtaining different-grain diameter is modified unleaded slurry；
The fineness that the graphene coated silver powder of different-grain diameter described in step 2 is modified unleaded slurry is less than 5 μm；
Organic carrier described in step 1 is prepared according to the following steps：
1., prepare organic solvent：30 parts of alcohol esters, 12,35 parts of dimethyl adipates, 3 parts of citric acids three are weighed in parts by weight
Butyl ester, 7 parts of dibutyl phthalates and 1 part of lecithin；By 12,35 parts of dimethyl adipates of weigh 30 parts of alcohol esters, 3 parts of lemons
Lemon acid tributyl, 7 parts of dibutyl phthalates and the mixing of 1 part of lecithin, then be 80 DEG C in temperature and mixing speed is 300r/
60min is stirred under min, obtains organic solvent；
2., weigh 5 parts of binders, 3 parts of modified polyamide waxes, 0.5 part of aerosil and 3 parts of modifications in parts by weight
Rilanit special；Successively by step 2. in the 5 parts of binders, 3 parts of modified polyamide waxes, the 0.5 part of aerosil and 3 that weigh
The modified hydrogenated castor oil of part is added in the organic solvent obtained in step 1, then is 80 DEG C in temperature and is with mixing speed
25min is stirred under 300r/min, then low whipping speed is cooled to room temperature under 50r/min, obtains organic carrier；
Step 2. described in binder be polyvinyl butyral；
What the glass powder described in step 1 was specifically prepared according to the following steps：
(1), 45 parts of Bi are weighed in parts by weight2O3, 25 parts of SiO2, 20 parts of B2O3, 7 parts of Al2O3, 4 parts of TiO2, 3 parts of BaO, 4
Part TeO2, 5 parts of ZrO, 4 parts of Y2O3, 4 parts of ZnO and 3 part of Ag2O；
(2), the 45 parts of Bi that will be weighed in step (1)2O3, 25 parts of SiO2, 20 parts of B2O3, 7 parts of Al2O3, 4 parts of TiO2, 3 parts
BaO, 4 parts of TeO2, 5 parts of ZrO, 4 parts of Y2O3, 4 parts of ZnO and 3 part of Ag2O is uniformly mixed, and obtains mixed-powder；
(3), by mixed-powder temperature be 1200 DEG C at calcine 1h, obtain clear glass precursor solution；By clear glass
Liquid takes out from Muffle furnace, then carries out rapid quenching or annealing cooling, obtains crystal type glass；Crystal type glass is passed through into gas
Stream crushes, and obtains glass powder；
The grain size of glass powder described in step (3) is 0.7 μm~4.5 μm.
The present embodiment step 2. described in the purchase of modified hydrogenated castor oil from Changxing consonance high molecular material Co., Ltd,
Model RC-HST；
The present embodiment step 2. described in the purchase of modified polyamide wax from Changxing consonance high molecular material Co., Ltd, type
Number be MAW-6600.
Comparative example：The present embodiment and the difference of embodiment two are：One, weigh in parts by weight 86 parts of silver powder, 9 parts
Glass powder and 8 parts of organic carriers；Two, weighed in step 1 86 parts of silver powder, 9 parts of glass powders and 8 parts of organic carriers are mixed equal
It is even, then be ground, it obtains silver powder and is modified unleaded slurry.Other steps and parameter are identical as embodiment two.
The graphene coated silver powder of different-grain diameter prepared by embodiment two is modified unleaded slurry and prepared by comparative example
Silver powder be modified unleaded slurry and be respectively printed at length of side 156*156mm, 190 ± 10 μm of thickness, the polysilicon of 70~90 Ω of sheet resistance
Solar battery sheet front, measures the unit for electrical property parameters of solar cell, as shown in Table 1 and Table 2 after drying, sintering；
The silk screen print method halftone parameter that prints electrode on polysilicon solar battery slice front is：Aluminium outer frame diameter 320mm*
320mm, 400 mesh of screen cloth mesh number, 20 μm of linear diameter, 20 μm of film thickness, tension 22N；Printed thin grid width be generally 70 μm~
90 μm, 23 μm or so of height.
Table 1 is that the unleaded slurry of silver powder modification prepared by comparative example is printed on length of side 156*156mm, 190 ± 10 μ of thickness
The electrical property ginseng of solar cell is measured after the polysilicon solar battery slice front drying of m, 70~90 Ω of sheet resistance, sintering
Number.
Table 2 is that the unleaded slurry of graphene coated silver powder modification of different-grain diameter prepared by embodiment two is printed on length of side 156*
156mm, 190 ± 10 μm of thickness measure the sun after the polysilicon solar battery slice front drying of 70~90 Ω of sheet resistance, sintering
The unit for electrical property parameters of energy battery.
Table 1
Table 2
From Tables 1 and 2 it is found that the graphene coated silver powder of different-grain diameter prepared by embodiment one, which is raw material, prepares difference
The graphene coated silver powder of grain size is modified unleaded slurry and is applied in solar cell positive silver paste, and the unit for electrical property parameters of battery is bright
It is that Eff photoelectric conversion efficiencies are high to show and be applied to corresponding battery parameter in solar cell positive silver paste than fine silver powder.
The conversion ratio that the graphene coated silver powder of different-grain diameter prepared by embodiment one is modified unleaded slurry reaches 18.4%
(156mm*156mm polycrystal silicon cells), unit consumption is low, by taking 156mm*156mm cell pieces as an example, using the difference of the preparation of embodiment one
The unit consumption that the graphene coated silver powder of grain size is modified the crystal silicon solar batteries that unleaded slurry makes is only 0.101g/pcs, and is adopted
The unit consumption of the crystal silicon solar batteries made of import business slurrying material is 0.112g/pcs~0.123g/pcs.
Claims (10)
1. a kind of method for the graphene coated silver powder preparing different-grain diameter using chemical reduction method, it is characterised in that this method has
Body is completed according to the following steps：
One, the graphene oxide of different sizes is prepared：
1., graphite powder is added in the sulfuric acid that mass fraction is 98% under conditions of ice-water bath, then low whipping speed is
Potassium permanganate powder is added under 150r/min~250r/min, obtains mixed liquor I；
Step 1 1. described in graphite powder quality and mass fraction be 98% the volume ratio of sulfuric acid be 1g:(10mL~
50mL)；
Step 1 1. described in graphite powder and potassium permanganate powder mass ratio be 1:(2~8)；
2., mixed liquor I is heated to 30 DEG C~40 DEG C, then low whipping speed is to react 20min under 150r/min~250r/min
~40min, then low whipping speed be 150r/min~250r/min under ultra-pure deionized water is added, be then heated to 95 DEG C~
100 DEG C, then 10min~20min is kept at being 95 DEG C~100 DEG C in temperature, obtain mixed solution II；
Step 1 2. described in mixed liquor I quality and ultra-pure deionized water volume ratio be 1g:(2~4) mL；
3., ultra-pure deionized water is added into mixed solution II first, then be added mass fraction be 30% hydrogen peroxide, mixing
It is centrifuged again after uniformly, obtains solid matter；The hydrochloric acid that use quality score is 5% cleans solid matter,
Until can't detect sulfate ion in cleaning solution, stop cleaning, the solid matter after being cleaned, as graphene oxide；
Step 1 3. described in the volume ratio of mixed solution II and ultra-pure deionized water be 1:(2~5)；
Step 1 3. described in mixed solution II and mass fraction be 30% the volume ratio of hydrogen peroxide be 1:(0.1~0.6)；
Step 1 3. described in graphene oxide size be 10 μm~25 μm；
4., graphene oxide is distributed in water, obtain graphene oxide water solution, reuse probe type ultrasonic concussion instrument pair
Graphene oxide water solution ultrasonic power be 75W~750W under ultrasound 10min~120min, then temperature be -50 DEG C~-15
It is freeze-dried 10h~12h at DEG C, obtains the graphene oxide of different sizes；
Step 1 4. described in different sizes graphene oxide D50 sizes be 0.05 μm~2 μm；
Two, graphene coated silver powder is prepared：
1., silver nitrate is dissolved in ultra-pure water, obtain the silver nitrate solution of a concentration of 50g/L~450g/L；
2., glucose, ascorbic acid and hydrazine hydrate be dissolved in ultra-pure water, obtain reducing solution；
Step 2 2. described in reducing solution in glucose a concentration of 75g/L~300g/L；
Step 2 2. described in reducing solution in ascorbic acid a concentration of 75g/L~300g/L；
Step 2 2. described in reducing solution in hydrazine hydrate a concentration of 20g/L~100g/L；
3., surfactant is added in reducing solution, the oxidation stone of the different sizes obtained in adding step 1 4.
Black alkene, stirs evenly, and obtains solution A；
Step 2 3. described in solution A in surfactant quality and reducing solution volume ratio be (10g~50g):
500mL；
Step 2 3. described in different sizes graphene oxide quality and reducing solution volume ratio be (0.1g~
2g):500mL；
4., be 20 DEG C~45 DEG C in temperature and mixing speed is that 100r/min~500r/min is 20 DEG C~45 DEG C in temperature and stirs
It is that a concentration of 50g/L~250g/ will be slowly dropped in solution A using dropping funel under 100r/min~500r/min to mix speed
In the silver nitrate solution of L, time for adding is 20min~80min；The silver nitrate solution and solution A of a concentration of 50g/L~250g/L
Low whipping speed is to be stirred to react 0.5h~2h under 100r/min~500r/min again after being thoroughly mixed, then in temperature is -50 DEG C
It is freeze-dried 10h~12h at~-15 DEG C, obtains the graphene coated silver powder of different-grain diameter；
Step 2 4. described in a concentration of 50g/L~250g/L silver nitrate solution and solution A volume ratio be (0.5~3):
1。
2. a kind of side of graphene coated silver powder preparing different-grain diameter using chemical reduction method according to claim 1
Method, it is characterised in that step 2 3. described in surfactant be one kind in CTAB, CTAC and OM or in which several mixed
Close object.
3. a kind of side of graphene coated silver powder preparing different-grain diameter using chemical reduction method according to claim 1
Method, it is characterised in that step 2 4. described in different-grain diameter graphene coated silver powder grain size be 0.1 μm~4.5 μm.
4. the graphene coated silver powder using different-grain diameter as described in claim 1 is the graphite of different-grain diameter prepared by raw material
Alkene coated silver is modified unleaded slurry, it is characterised in that the graphene coated silver powder of different-grain diameter is modified unleaded slurry by weight
Number is prepared by the graphene coated silver powder of 80 parts~92 parts different-grain diameters, 3 parts~15 parts glass powders and 4 parts~10 parts organic carriers
It forms.
5. the graphene coated silver powder of different-grain diameter according to claim 4 is modified unleaded slurry, it is characterised in that different
The graphene coated silver powder of grain size is modified unleaded slurry in parts by weight by the graphene coated silver of 80 parts~85 parts different-grain diameters
Powder, 3 parts~8 parts glass powders and 4 parts~7 parts organic carriers are prepared.
6. the graphene coated silver powder of different-grain diameter according to claim 4 is modified unleaded slurry, it is characterised in that different
The graphene coated silver powder of grain size is modified unleaded slurry in parts by weight by the graphene coated silver of 85 parts~92 parts different-grain diameters
Powder, 8 parts~15 parts glass powders and 7 parts~10 parts organic carriers are prepared.
7. the graphene coated silver powder of different-grain diameter according to claim 4 is modified unleaded slurry, it is characterised in that different
The graphene coated silver powder of grain size be modified unleaded slurry in parts by weight by the graphene coated silver powder of 86 parts of different-grain diameters, 9 parts
Glass powder and 8 parts of organic carriers are prepared.
8. the graphene coated silver powder of different-grain diameter according to claim 4 is modified unleaded slurry, it is characterised in that described
Organic carrier prepare according to the following steps：
One, organic solvent is prepared：Weigh in parts by weight 20 parts~40 parts alcohol esters, 12,27 parts~50 parts dimethyl adipates, 2 parts
~5 parts of tributyl citrate, 5 parts~10 parts dibutyl phthalates and 0.1 part~2 parts lecithin；By weigh 20 parts~
40 parts of alcohol esters, 12,27 parts~50 parts dimethyl adipates, 2 parts~5 parts tributyl citrate, 5 parts~10 parts phthalic acids two
Butyl ester and the mixing of 0.1 part~2 parts lecithin, then be 70 DEG C~90 DEG C in temperature and mixing speed is 100r/min~500r/min
Lower stirring 10min~120min, obtains organic solvent；
Two, 1 part~10 parts binders, 2 parts~6 parts modified polyamide waxes, 0.1 part~1 part gas phase dioxy are weighed in parts by weight
SiClx and 1 part~5 parts modified hydrogenated castor oil；Successively by weighed in step 21 part~10 parts binders, 2 parts~6 parts modifications
Polyamide wax, 0.1 part~1 part aerosil and 1 part~5 parts modified hydrogenated castor oil are added to having of being obtained in step 1
In solvent, then in the case where temperature is 70 DEG C~90 DEG C and mixing speed is 100r/min~500r/min stirring 10min~
40min, then low whipping speed are cooled to room temperature under 50r/min~100r/min, obtain organic carrier；
Binder described in step 2 is ethyl cellulose, epoxy resin, alkyd resin, polyurethane resin, melamine first
Urea formaldehyde, phenolic resin acrylic resin and one kind in polyvinyl butyral or in which two kinds of mixture；The second
Base cellulose is N40~N200.
9. the graphene coated silver powder of different-grain diameter according to claim 4 is modified unleaded slurry, it is characterised in that described
Glass powder specifically prepare according to the following steps：
One, 40 parts~50 parts Bi are weighed in parts by weight2O3, 20 parts~30 parts of SiO2, 20 parts~25 parts of B2O3, 2 parts~13 parts
Al2O3, 3 parts~5 parts of TiO2, 1 part~6 parts of BaO, 1 part~7 parts TeO2, 1 part~9 parts of ZrO, 1 part~8 parts Y2O3, 3 parts~5 parts
ZnO and 2 part~5 parts Ag2O；
Two, by weighed in step 1 40 parts~50 parts Bi2O3, 20 parts~30 parts of SiO2, 20 parts~25 parts of B2O3, 2 parts~13 parts
Al2O3, 3 parts~5 parts of TiO2, 1 part~6 parts of BaO, 1 part~7 parts TeO2, 1 part~9 parts of ZrO, 1 part~8 parts Y2O3, 3 parts~5 parts
ZnO and 2 part~5 parts Ag2O is uniformly mixed, and obtains mixed-powder；
Three, by mixed-powder temperature be 900 DEG C~1300 DEG C at calcine 0.5h~2h, obtain clear glass precursor solution；It will be clear
Clear glass precursor solution takes out from Muffle furnace, then carries out rapid quenching or annealing cooling, obtains crystal type glass；By crystal type glass
Glass obtains glass powder by air-flow crushing；
The grain size of glass powder described in step 3 is 0.7 μm~4.5 μm.
10. the graphene coated silver powder of different-grain diameter as claimed in claim 4 is modified unleaded slurry, it is characterised in that different grains
The preparation method that the graphene coated silver powder of diameter is modified unleaded slurry is completed according to the following steps：
One, the graphene coated silver powder of 80 parts~92 parts different-grain diameters, 3 parts~15 parts glass powders and 4 parts are weighed in parts by weight
~10 parts of organic carriers；
Two, by the graphene coated silver powder of weighed in step 1 80 parts~92 parts different-grain diameters, 3 parts~15 parts glass powders and 4
Part~10 parts of organic carriers are uniformly mixed, then are ground, and the graphene coated silver powder for obtaining different-grain diameter is modified unleaded slurry；
The fineness that the graphene coated silver powder of different-grain diameter described in step 2 is modified unleaded slurry is less than 5 μm；
Organic carrier described in step 1 is prepared according to the following steps：
1., prepare organic solvent：Weigh in parts by weight 20 parts~40 parts alcohol esters, 12,27 parts~50 parts dimethyl adipates, 2 parts
~5 parts of tributyl citrate, 5 parts~10 parts dibutyl phthalates and 0.1 part~2 parts lecithin；By weigh 20 parts~
40 parts of alcohol esters, 12,27 parts~50 parts dimethyl adipates, 2 parts~5 parts tributyl citrate, 5 parts~10 parts phthalic acids two
Butyl ester and the mixing of 0.1 part~2 parts lecithin, then be 70 DEG C~90 DEG C in temperature and mixing speed is 100r/min~500r/min
Lower stirring 10min~120min, obtains organic solvent；
2., weigh 1 part~10 parts binders, 2 parts~6 parts modified polyamide waxes, 0.1 part~1 part gas phase dioxy in parts by weight
SiClx and 1 part~5 parts modified hydrogenated castor oil；Successively by step 2. in weigh 1 part~10 parts binders, 2 parts~6 parts modifications
Polyamide wax, 0.1 part~1 part aerosil and 1 part~5 parts modified hydrogenated castor oil are added to having of being obtained in step 1
In solvent, then in the case where temperature is 70 DEG C~90 DEG C and mixing speed is 100r/min~500r/min stirring 10min~
40min, then low whipping speed are cooled to room temperature under 50r/min~100r/min, obtain organic carrier；
Step 2. described in binder be ethyl cellulose, epoxy resin, alkyd resin, polyurethane resin, melamine first
Urea formaldehyde, phenolic resin acrylic resin and one kind in polyvinyl butyral or in which two kinds of mixture；The second
Base cellulose is N40~N200；
What the glass powder described in step 1 was specifically prepared according to the following steps：
(1), 40 parts~50 parts Bi are weighed in parts by weight2O3, 20 parts~30 parts of SiO2, 20 parts~25 parts of B2O3, 2 parts~13 parts
Al2O3, 3 parts~5 parts of TiO2, 1 part~6 parts of BaO, 1 part~7 parts TeO2, 1 part~9 parts of ZrO, 1 part~8 parts Y2O3, 3 parts~5 parts
ZnO and 2 part~5 parts Ag2O；
(2), 40 parts~50 parts Bi that will be weighed in step (1)2O3, 20 parts~30 parts of SiO2, 20 parts~25 parts of B2O3, 2 parts~13
Part Al2O3, 3 parts~5 parts of TiO2, 1 part~6 parts of BaO, 1 part~7 parts TeO2, 1 part~9 parts of ZrO, 1 part~8 parts Y2O3, 3 parts~5 parts
ZnO and 2 part~5 parts Ag2O is uniformly mixed, and obtains mixed-powder；
(3), by mixed-powder temperature be 900 DEG C~1300 DEG C at calcine 0.5h~2h, obtain clear glass precursor solution；It will be clear
Clear glass precursor solution takes out from Muffle furnace, then carries out rapid quenching or annealing cooling, obtains crystal type glass；By crystal type glass
Glass obtains glass powder by air-flow crushing；
The grain size of glass powder described in step (3) is 0.7 μm~4.5 μm.
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| CN110089524A (en) * | 2018-01-31 | 2019-08-06 | 皇杰新能源科技(上海)有限公司 | Graphene coated nano silver antibacterial material and preparation method thereof |
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| CN114260460A (en) * | 2021-12-24 | 2022-04-01 | 陕西煤业化工技术研究院有限责任公司 | Submicron graphene silver powder suitable for 5G field and preparation method and application thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103811130A (en) * | 2014-03-05 | 2014-05-21 | 电子科技大学 | Preparation method of graphene compound silver paste and graphene compound silver paste |
| CN104217783A (en) * | 2014-09-19 | 2014-12-17 | 无锡光富光伏材料有限公司 | Reduced graphene oxide nano-silver paste and preparation method and application thereof |
| CN105772739A (en) * | 2016-03-12 | 2016-07-20 | 常州大学 | Preparation method for graphene/nano-silver composite antibacterial material |
| CN105845198A (en) * | 2016-05-16 | 2016-08-10 | 南通天盛新能源股份有限公司 | Solar cell front side silver slurry doped with modified graphene and manufacture method therefor |
| CN105976893A (en) * | 2016-06-22 | 2016-09-28 | 中国科学院宁波材料技术与工程研究所 | Lead-free graphene/nano-silver composite electronic silver paste and preparation method thereof |
Family Cites Families (1)
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|---|---|---|---|---|
| KR101225497B1 (en) * | 2009-11-05 | 2013-01-23 | (주)덕산테코피아 | Conductive paste and the manufacturing method thereof and the electric device comprising thereof |
-
2017
- 2017-03-16 CN CN201710158797.1A patent/CN106887272B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103811130A (en) * | 2014-03-05 | 2014-05-21 | 电子科技大学 | Preparation method of graphene compound silver paste and graphene compound silver paste |
| CN104217783A (en) * | 2014-09-19 | 2014-12-17 | 无锡光富光伏材料有限公司 | Reduced graphene oxide nano-silver paste and preparation method and application thereof |
| CN105772739A (en) * | 2016-03-12 | 2016-07-20 | 常州大学 | Preparation method for graphene/nano-silver composite antibacterial material |
| CN105845198A (en) * | 2016-05-16 | 2016-08-10 | 南通天盛新能源股份有限公司 | Solar cell front side silver slurry doped with modified graphene and manufacture method therefor |
| CN105976893A (en) * | 2016-06-22 | 2016-09-28 | 中国科学院宁波材料技术与工程研究所 | Lead-free graphene/nano-silver composite electronic silver paste and preparation method thereof |
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