CN102024856A - Environment-friendly crystalline silicon solar-cell back surface field silver-aluminium paste and preparation method thereof - Google Patents
Environment-friendly crystalline silicon solar-cell back surface field silver-aluminium paste and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an environment-friendly crystalline silicon solar-cell back surface field silver-aluminium paste and a preparation method thereof. The silver-aluminium paste comprises the following components in percentage by weight: 15-35% of silver powder, 30-70% of aluminium powder, 10-15% of organic carrier, 1-5% of adhesive, 3.5-13% of solvent and 0.5-2% of dispersant. The organic carrier is prepared by dissolving 10-30% of ethyl cellulose resin in 70-90% of organic solvent. In the paste, environment-friendly glass powder without harmful substances is used as the adhesive, and an environment-friendly organic reagent is used as a solvent and a diluter; and thus, the prepared silver-aluminium paste does not contain six substances (Pb, Cd, Hg, Cr(VI), polybrominated diphenyl PBB and polybrominated diphenyl ether PBDE) inhibited by European Union RoHS Instruction, completely conforms to the Instruction 2005/84/EC on phthalic ester in European Union RoHS, realizes environment friendliness in deed, and is beneficial to the import and export of solar cells made in China and raw materials of the cells.
Description
Technical field
The invention belongs to technical field of electronic materials, particularly a kind of environment-friendly crystal silicon solar battery back electric field silver aluminum slurry and preparation method thereof.
Background technology
The technology of tool meaning became the focus that application is competitively studied in countries in the world during solar photovoltaic technology utilized as solar energy.The nearest 10 years speed increases with every year average 30%, nearest 3 years especially with annual speed rapid growth more than 50%.Solar energy power generating has become renewable energy source domain relaying wind power generation fast, the most maximum industry of industrialized development afterwards.At present, the solar cell in the photovoltaic generation remains based on crystal-silicon solar cell, and the market share reaches 90%, and large tracts of land commercialization efficiency of solar cell can reach 18-19%.Present photovoltaic industry mainly is meant the crystal silicon solar energy battery industry.
Back of the body electric field slurry is the important materials of crystal silicon solar batteries back electrode, and it forms the back electrode grid line of strong adhesion, low ohm contact resistance at the silicon chip back side of crystal silicon solar energy battery by the method for silk screen printing.
It mainly is three kinds of aluminium paste, silver slurry and silver-colored aluminium pastes that present electrode seal burns with electric slurry, and the silver slurry is usually in the battery sensitive surface, and silver-colored aluminium paste and aluminium paste are used in back of the body field plate.
The environmental protection standard of electric slurry industry is followed the RoHS instruction (not containing Pb, Cd, Hg, Cr (VI), Polybrominated biphenyl PBB, Poly Brominated Diphenyl Ethers PBDE) of European Union and the RoHS of the European Union instruction 2005/84/EC about phthalic acid ester, wherein crystal silicon solar battery back electric field silver paste, silver-colored aluminium paste at present at home a year use amount reach more than 150 tons, and along with the growth of photovoltaic industry, existing leaded back electric field silver aluminium paste is increasing to the pollution of environment, and its use will progressively be restricted.
Summary of the invention
Technical problem to be solved by this invention provides a kind of environment-friendly crystal silicon solar battery back electric field silver aluminum slurry and preparation method thereof.
For solving above technical problem, the invention provides a kind of environment-friendly crystal silicon solar battery back electric field silver aluminum slurry, its component and percentage by weight are: silver powder: 15～35%, aluminium powder: 30～70%, organic carrier: 10～15%, binding material: 1～5%, solvent: 3.5～13%, dispersant 0.5～2%, described organic carrier are 10～30% ethyl cellulose resin to be dissolved in 70～90% the organic solvent form.
Organic solvent in the described organic carrier is one or more mixtures that mix with arbitrary proportion in butyl carbitol, 1-Methoxy-2-propyl acetate, ethylene glycol ethyl ether, ethylene glycol monomethyl ether acetate, benzinum, turpentine oil, the terpinol;
Described solvent is selected from one or more mixtures that mix with arbitrary proportion in o-phthalic acid dibutyl ester, dibutyl phthalate, adipic acid dibutyl ester or the benzinum;
Described dispersant is selected from one or more mixtures that mix with arbitrary proportion in Tissuemat E, zinc stearate or the microcrystalline wax;
The component of described binding material and mass percent are: Bi
2O
3: 45～55%; B
2O
3: 20～25%; Al
2O
3: 0～4%; SiO
2: 0.5～4%; CaO:0～4%; TiO
2: 0～4%; NiO:0～3%; NiO
2: 0～3%; ZnO:20～30%;
For solving above technical problem, the invention provides a kind of preparation method of environment-friendly crystal silicon solar battery back electric field silver aluminum slurry, may further comprise the steps:
(1) preparation of binding material: raw materials weighing, be passed in the high temperature furnace after mixing, under 900～1200 ℃ condition, be incubated 30～60 minutes, after quenching with deionized water subsequently, ball milling, mistake 200～400 mesh sieves promptly get binding material;
(2) preparation of organic carrier: ethyl cellulose resin 10～30% is joined in 70～90% the organic solvent by weight percentage, place 75～100 ℃ Water Tank with Temp.-controlled then, ethyl cellulose resin is dissolved in the organic solvent fully, after filtering at last, promptly gets organic carrier;
(3) preparation of back electric field silver aluminum slurry: get 15～35% silver powder, 30～70% aluminium powder, the organic carrier of 10～15% steps (2), the binding material of 1～5% step (1), 3.5～13% solvent, 0.5～2% dispersant according to percentage by weight, after mixing, be dispersed to below the 10 μ m, promptly get the environment-friendly crystal silicon solar battery back electric field silver aluminum slurry.
The particle diameter of silver powder is 0.2～1 micron in the described step (3), and the particle diameter of described aluminium powder is 3～6 microns;
Described step (3) is to mix in planetary stirring machine;
Described step (3) is to disperse in three-roller.
Compared with prior art, environment-friendly crystal silicon solar battery back electric field silver aluminum slurry of the present invention and preparation method thereof has the following advantages at least: back electric field silver aluminum slurry of the present invention with the environmental protection glass dust that do not contain hazardous substance as binding agent, the environment-friendly type organic reagent is as solvent and diluent, the silver-colored aluminium paste of preparation does not contain six material (Pb that the RoHS of European Union instruction is forbidden, Cd, Hg, Cr (VI), Polybrominated biphenyl PBB, Poly Brominated Diphenyl Ethers PBDE), meet the instruction 2005/84/EC of the RoHS of European Union fully about phthalic acid ester, accomplish environmental protection truly, helped the import and export of homemade solar cell and raw material thereof.
Embodiment
The component and the mass percent of the present invention's silver aluminum slurry are as shown in table 1 below:
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Silver powder | 15％ | 35 | 25 | 30 | 34 |
| Aluminium powder | 70％ | 30 | 50 | 40 | 50 |
| Organic carrier | 10％ | 15 | 12 | 15 | 10 |
| Binding material | 1％ | 5 | 2.5 | 3 | 2 |
| Solvent | 3.5％ | 13 | 10 | 10 | 3 |
| Dispersant | 0.5％ | 2 | 0.5 | 2 | 1 |
The component and the mass percent of the binding material of the present invention's silver aluminum slurry are as shown in table 2 below:
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Bi 2O 3 | 45％ | 55％ | 50％ | 48％ | 45％ |
| B 2O 3 | 24％ | 22％ | 25％ | 20％ | 19％ |
| Al 2O 3 | 4％ | 0 | 0.5％ | 0 | 0.5 |
| SiO 2 | 4％ | 1％ | 1％ | 0.5％ | 0.5 |
| CaO | 1％ | 0 | 0.5％ | 4％ | 0 |
| TiO 2 | 2％ | 0.5％ | 1％ | 0 | 4 |
| NiO | 0 | 1％ | 0 | 3 | 1 |
| NiO 2 | 0 | 0.5％ | 2％ | 3％ | 0 |
| ZnO | 20％ | 20％ | 20％ | 21.5％ | 30％ |
Embodiment one
(1) preparation of environmental protection glassy bond material
According to component among the embodiment in the table 21 and mass percent raw materials weighing, be passed in the high temperature furnace after mixing, under 1200 ℃ condition, be incubated 60 minutes, after quenching with deionized water subsequently, ball milling to 0.5～2 micron are crossed 200 orders at last and are sieved, and promptly get the binding material that does not contain Pb, Cd, Hg, Cr harmful substances such as (VI);
(2) preparation of organic carrier
Ethyl cellulose resin 10% is joined in 90% the organic solvent by weight percentage, place 75 ℃ Water Tank with Temp.-controlled then, ethyl cellulose resin is dissolved in the organic solvent fully, after filtering at last, promptly get organic carrier; Described organic solvent is that 50% butyl carbitol and percentage by weight are that 50% 1-Methoxy-2-propyl acetate is formed by percentage by weight;
(3) preparation of back electric field silver aluminum slurry
Get the super fine silver powder that particle diameter is the 0.2-1 micron, the aluminium powder that particle diameter is the 3-6 micron, the organic carrier of step (2), the binding material of step (1) according to component listed in the table 1 and mass percent, and solvent and dispersant, with it after mixing in the planetary stirring machine, be dispersed on the three-roller below the 10 μ m, promptly get the environment-friendly crystal silicon solar battery back electric field silver aluminum slurry, described solvent is an o-phthalic acid dibutyl ester, and described dispersant is a Tissuemat E.
Embodiment two
(1) preparation of environmental protection glassy bond material
According to component among the embodiment in the table 22 and mass percent raw materials weighing, be passed in the high temperature furnace after mixing, under 900 ℃ condition, be incubated 60 minutes, after quenching with deionized water subsequently, ball milling to 0.5～2 micron are crossed 400 orders at last and are sieved, and promptly get the binding material that does not contain Pb, Cd, Hg, Cr harmful substances such as (VI);
(2) preparation of organic carrier
Ethyl cellulose resin 30% is joined in 70% the organic solvent by weight percentage, place 100 ℃ Water Tank with Temp.-controlled then, ethyl cellulose resin is dissolved in the organic solvent fully, after filtering at last, promptly get organic carrier; Described organic solvent is that 10% 1-Methoxy-2-propyl acetate, percentage by weight are that 50% ethylene glycol ethyl ether, percentage by weight are that 30% ethylene glycol monomethyl ether acetate, percentage by weight are 5% benzinum by percentage by weight, and percentage by weight is that 5% terpinol is formed;
(3) preparation of back electric field silver aluminum slurry
Component and mass percent according to table 1 are got the super fine silver powder that particle diameter is the 0.2-1 micron, the aluminium powder that particle diameter is the 3-6 micron, the organic carrier of step (2), binding material and the solvent and the dispersant of step (1), with it after mixing in the planetary stirring machine, be dispersed on the three-roller below the 10 μ m, promptly get the environment-friendly crystal silicon solar battery back electric field silver aluminum slurry, the component of described solvent and percentage by weight are: o-phthalic acid dibutyl ester: 13%; Dibutyl phthalate (DBP): 20%; Dioctyl adipate: 50%; Benzinum: 17%; The component of described dispersant and percentage by weight are: Tissuemat E: 30%; Zinc stearate: 50%; Microcrystalline wax: 20%.
Embodiment three
(1) preparation of environmental protection glassy bond material
According to component among the embodiment in the table 13 and mass percent raw materials weighing, be passed in the high temperature furnace after mixing, under 1000 ℃ condition, be incubated 50 minutes, after quenching with deionized water subsequently, ball milling to 0.5～2 micron are crossed 300 orders at last and are sieved, and promptly get the binding material that does not contain Pb, Cd, Hg, Cr harmful substances such as (VI);
(2) preparation of organic carrier
Ethyl cellulose resin 20% is joined in 80% the organic solvent by weight percentage, place 95 ℃ Water Tank with Temp.-controlled then, ethyl cellulose resin is dissolved in the organic solvent fully, after filtering at last, promptly get organic carrier; Described organic solvent is an ethylene glycol monomethyl ether acetate;
(3) preparation of back electric field silver aluminum slurry
Get the super fine silver powder that particle diameter is the 0.2-1 micron, the aluminium powder that particle diameter is the 3-6 micron, the organic carrier of step (2), binding material and the solvent and the dispersant of step (1) according to component and mass percent that table 1 is listed, with it after mixing in the planetary stirring machine, be dispersed on the three-roller below the 10 μ m, promptly get the environment-friendly crystal silicon solar battery back electric field silver aluminum slurry, described solvent is that 55% dioctyl adipate and percentage by weight are that 45% benzinum is formed by percentage by weight, and described dispersant is a zinc stearate.
Embodiment four
(1) preparation of environmental protection glassy bond material
According to component among the embodiment in the table 24 and mass percent raw materials weighing, be passed in the high temperature furnace after mixing, under 1100 ℃ condition, be incubated 60 minutes, after quenching with deionized water subsequently, ball milling to 0.5～2 micron are crossed 300 orders at last and are sieved, and promptly get the binding material that does not contain Pb, Cd, Hg, Cr harmful substances such as (VI);
(2) preparation of organic carrier
Ethyl cellulose resin 25% is joined in 75% the organic solvent by weight percentage, place 95 ℃ Water Tank with Temp.-controlled then, ethyl cellulose resin is dissolved in the organic solvent fully, after filtering at last, promptly get organic carrier; Described organic solvent is an ethylene glycol monomethyl ether acetate;
(3) preparation of back electric field silver aluminum slurry
Component and mass percent according to embodiment in the table 14 are got the super fine silver powder that particle diameter is the 0.2-1 micron, particle diameter is the aluminium powder of 3-6 micron, the organic carrier of step (2), the binding material of step (1), and solvent and dispersant, with it after mixing in the planetary stirring machine, be dispersed on the three-roller below the 10 μ m, promptly get the environment-friendly crystal silicon solar battery back electric field silver aluminum slurry, described solvent is that 50% o-phthalic acid dibutyl ester and percentage by weight are that 50% benzinum is formed by percentage by weight, and described dispersant is that 50% zinc stearate and 50% Tissuemat E are formed by percentage by weight.
Embodiment five
(1) preparation of environmental protection glassy bond material
According to component among the embodiment in the table 25 and mass percent raw materials weighing, be passed in the high temperature furnace after mixing, under 1200 ℃ condition, be incubated 55 minutes, after quenching with deionized water subsequently, ball milling to 0.5～2 micron are crossed 400 orders at last and are sieved, and promptly get the binding material that does not contain Pb, Cd, Hg, Cr harmful substances such as (VI);
(2) preparation of organic carrier
Ethyl cellulose resin 28% is joined in 72% the organic solvent by weight percentage, place 90 ℃ Water Tank with Temp.-controlled then, ethyl cellulose resin is dissolved in the organic solvent fully, after filtering at last, promptly get organic carrier; Described organic solvent is that 20% benzinum, percentage by weight are that 30% turpentine oil and 50% terpinol are formed by percentage by weight;
(3) preparation of back electric field silver aluminum slurry
Get the super fine silver powder that particle diameter is the 0.2-1 micron according to component among the embodiment in the table 15 and mass percent, particle diameter is the aluminium powder of 3-6 micron, the organic carrier of step (2), the binding material of step (1), and solvent and dispersant, with it after mixing in the planetary stirring machine, be dispersed on the three-roller below the 10 μ m, promptly get the environment-friendly crystal silicon solar battery back electric field silver aluminum slurry, described solvent is that 50% o-phthalic acid dibutyl ester and percentage by weight are that 35% dibutyl phthalate and percentage by weight are that 15% adipic acid dibutyl ester is formed by percentage by weight; Described dispersant is a microcrystalline wax.
The performance of the environment-friendly crystal silicon solar battery back electric field silver aluminum slurry that the present invention is prepared is as follows:
The maximum fineness of slurry≤15 microns, average fineness≤10 micron, solids content 45-85%, viscosity 150-300kcps (BROOKFIELD DV-II viscosimeter+14# rotor, 10RPM), sintering temperature 550-760 ℃.Use this back electric field silver aluminum slurry printing, the silicon solar cell after burning till has higher electricity conversion.
The above only is one embodiment of the present invention, it or not whole or unique execution mode, the conversion of any equivalence that those of ordinary skills take technical solution of the present invention by reading specification of the present invention is claim of the present invention and contains.
Claims (9)
1. environment-friendly crystal silicon solar battery back electric field silver aluminum slurry, its component and percentage by weight are: silver powder: 15～35%, aluminium powder: 30～70%, organic carrier: 10～15%, binding material: 1～5%, solvent: 3.5～13%, dispersant 0.5～2%, described organic carrier are 10～30% ethyl cellulose resin to be dissolved in 70～90% the organic solvent form.
2. environment-friendly crystal silicon solar battery back electric field silver aluminum slurry as claimed in claim 1 is characterized in that: the organic solvent in the described organic carrier is one or more mixtures that mix with arbitrary proportion in butyl carbitol, 1-Methoxy-2-propyl acetate, ethylene glycol ethyl ether, ethylene glycol monomethyl ether acetate, benzinum, turpentine oil, the terpinol.
3. environment-friendly crystal silicon solar battery back electric field silver aluminum slurry as claimed in claim 1 is characterized in that: described solvent is selected from one or more mixtures that mix with arbitrary proportion in o-phthalic acid dibutyl ester, dibutyl phthalate, adipic acid dibutyl ester and the benzinum.
4. environment-friendly crystal silicon solar battery back electric field silver aluminum slurry as claimed in claim 1 is characterized in that: described dispersant is selected from one or more mixtures that mix with arbitrary proportion in Tissuemat E, zinc stearate and the microcrystalline wax.
5. environment-friendly crystal silicon solar battery back electric field silver aluminum slurry as claimed in claim 1 is characterized in that: the component of described binding material and mass percent are: Bi
2O
3: 45～55%; B
2O
3: 20～25%; Al
2O
3: 0～4%; SiO
2: 0.5～4%; CaO:0～4%; TiO
2: 0～4%; NiO:0～3%; NiO
2: 0～3%; ZnO:20～30%.
6. the preparation method of the described environment-friendly crystal silicon solar battery back electric field silver aluminum slurry of claim 5 is characterized in that: may further comprise the steps:
(1) preparation of binding material: raw materials weighing, be passed in the high temperature furnace after mixing, under 900～1200 ℃ condition, be incubated 30～60 minutes, after quenching with deionized water subsequently, ball milling, mistake 200～400 mesh sieves promptly get binding material;
(2) preparation of organic carrier: ethyl cellulose resin 10～30% is joined in 70～90% the organic solvent by weight percentage, place 75～100 ℃ Water Tank with Temp.-controlled then, ethyl cellulose resin is dissolved in the organic solvent fully, after filtering at last, promptly gets organic carrier;
(3) preparation of back electric field silver aluminum slurry: get 15～35% silver powder, 30～70% aluminium powder, the organic carrier of 10～15% steps (2), the binding material of 1～5% step (1), 3.5～13% solvent, 0.5～2% dispersant according to percentage by weight, after it is mixed, be dispersed to below the 10 μ m, promptly get the environment-friendly crystal silicon solar battery back electric field silver aluminum slurry.
7. the preparation method of environment-friendly crystal silicon solar battery back electric field silver aluminum slurry as claimed in claim 6 is characterized in that: the particle diameter of silver powder is 0.2～1 micron in the described step (3), and the particle diameter of described aluminium powder is 3～6 microns.
8. the preparation method of environment-friendly crystal silicon solar battery back electric field silver aluminum slurry as claimed in claim 6 is characterized in that: in the described step (3), mix in planetary stirring machine.
9. the preparation method of environment-friendly crystal silicon solar battery back electric field silver aluminum slurry as claimed in claim 6 is characterized in that: in the described step (3), disperse in three-roller.
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| CN103871541B (en) * | 2012-05-03 | 2017-04-12 | 苏州晶银新材料股份有限公司 | Electrocondution slurry for back electrode of solar battery |
| CN102831954A (en) * | 2012-08-24 | 2012-12-19 | 合肥中南光电有限公司 | Silver paste on back of crystalline silicon solar cell and preparation method of silver paste |
| CN105047250A (en) * | 2015-02-05 | 2015-11-11 | 长兴材料工业股份有限公司 | Aluminium paste composition and solar cell module using the composition |
| CN106328250A (en) * | 2015-06-29 | 2017-01-11 | 江苏正能电子科技有限公司 | Back-passivation solar cell aluminium paste |
| CN104966546A (en) * | 2015-07-09 | 2015-10-07 | 福州阳光福斯新能源科技有限公司 | Back-surface silver paste for crystal silicon solar cell |
| CN113394310A (en) * | 2021-06-02 | 2021-09-14 | 浙江爱旭太阳能科技有限公司 | Manufacturing method of solar cell for preventing back circuit from falling off at lap joint and cell |
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Application publication date: 20110420 |