Preparation method of silver paste with high adhesive force of front electrode of silicon solar cell
Technical Field
The invention relates to the technical field of front electrodes of solar cells, in particular to a preparation method of silver paste with high adhesive force for the front electrode of a silicon solar cell.
Background
Solar cell is the device of directly converting light energy into electric energy through photoelectric effect or photochemical effect, as long as by the illumination to, just exports voltage and electric current in the twinkling of an eye, and solar cell can divide into according to the difference of used material: the solar cell comprises a silicon solar cell, a multi-component compound thin-film solar cell, a polymer multi-layer modified electrode type solar cell, a nanocrystalline solar cell, an organic solar cell and a plastic solar cell, wherein the silicon solar cell is the most developed at present and is dominant in application, and silver paste is printed on the front side and the back side of the cell and is subjected to high-temperature sintering treatment to enable silver powder to be attached to the surface of the cell to form a positive electrode and a negative electrode.
The prior Chinese patent document (publication number: CN106128554B) discloses an anti-aging crystalline silicon solar cell back electrode silver paste which comprises the following components in percentage by weight: 45-49% of silver-aluminum mixed powder, 4-6% of inorganic glass powder, 0-3% of inorganic anti-aging auxiliary agent and 42-51% of organic binder; the silver-aluminum mixed powder is a mixture of spherical silver powder and spherical aluminum powder, the bonding performance of the silver paste in the document mainly depends on an organic adhesive, the organic adhesive is a conventional raw material, and the bonding force is reduced along with the increase of time, so that the performance of the silver paste is influenced.
The existing Chinese patent document (publication number: CN105895191B) discloses a low-temperature conductive silver paste used for a solar cell and a preparation method thereof, and particularly relates to a low-temperature silver paste based on silver nanofibers and a preparation method thereof. The invention relates to a low-temperature silver paste based on silver nanofibers, which comprises the following components in percentage by weight: 50-70% of silver nanofiber, 10-20% of silver-coated glass powder, 15-25% of organic carrier and 0-5% of inorganic additive.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of silver paste with high adhesion of a front electrode of a silicon solar cell, so as to solve the problems in the background technology.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a preparation method of silver paste with high adhesion of a silicon solar cell front electrode, which comprises the following steps:
step one, weighing the following raw materials in parts by weight: 15-25 parts of silver-loaded modified melamine, 50-60 parts of pretreated silver nanowires, 5-9 parts of modified diamond micro powder, 1-3 parts of curing agent, 0.2-0.8 part of curing accelerator and 10-18 parts of solvent;
step two, adding the silver-loaded modified melamine and the solvent in the step one into a magnetic stirrer, starting the magnetic stirrer, increasing the stirring speed to 550-85 ℃ and stirring for 5-15min, then adding the pretreated silver nanowires and the modified diamond micro powder, decreasing the stirring speed to 350-450r/min and stirring for 15-25min, then adding the curing agent and the curing accelerator, decreasing the stirring speed to 120-160r/min, and continuing stirring for 1-3h to obtain the silver slurry;
the preparation method of the silver-loaded modified melamine comprises the following steps:
step one, preparing modified melamine: mixing melamine and paraformaldehyde according to a ratio of 1:2.5, then feeding into a three-neck flask, adding distilled water and alkali, heating to 70-80 ℃ under stirring, reacting for 30-40min, then adding a modifier, namely terephthalaldehyde, and adjusting the pH value to 7.5 for later use;
step two, pretreating silver nanoparticles: adding silver nanoparticles into absolute ethyl alcohol for mixing, then carrying out ultrasonic dispersion for 10-20min, adding a silane coupling agent KH-560 for hydrothermal treatment for 15-25min, wherein the hydrothermal temperature is 65-75 ℃, then washing with water, centrifuging and drying to obtain the silver nanoparticle composite material;
step three, sequentially feeding the modified melamine prepared in the step one, the pretreated silver nanoparticles prepared in the step two and absolute ethyl alcohol into a high-pressure reaction kettle for reaction, wherein the reaction pressure is 3-4MPa, and the reaction time is 35-45min, so as to obtain silver-loaded modified melamine;
the preparation method of the pretreated silver nanowire comprises the steps of alternately treating the silver nanowire for 4min by combining corona with low-temperature plasma;
adding diamond micro powder and oleic acid into a ball mill for ball milling, wherein the ball milling rotation speed is 300-400r/min, the ball milling is performed for 1-2h, then sending the mixture into a reaction kettle, then adding deionized water for ultrasonic dispersion for 15-25min, then adding concentrated sulfuric acid and concentrated nitric acid into the mixture according to the weight ratio of 2:1, continuously stirring the mixture for 25-35min, and then washing, filtering and drying the mixture to obtain the modified diamond micro powder;
the curing agent is one or a composition of more of methyl ethyl ketone peroxide and benzoyl peroxide;
the curing accelerator is an organic tin curing accelerator;
the solvent is propylene glycol methyl ether acetate.
Preferably, the particle size of the silver nanoparticles in the second preparation step of the silver-loaded modified melamine is 4-10 nm.
Preferably, the corona combined with low-temperature plasma alternating treatment specifically comprises: the silver nanowires were placed in a glass container of aqueous solution and placed between upper and lower electrodes at a voltage of 6kV for 15s followed by corona treatment for 45s with a treatment power of 5 kW.
Preferably, the silver nanowire has a length of 40-80 μm and a diameter of 30-50nm
The silver-loaded modified melamine is prepared by mixing modified melamine and silver nanoparticles, the modified melamine is prepared by performing polycondensation reaction on melamine and formaldehyde, a large amount of imino and hydroxyl exist in the space, a space net structure is formed under the action of a curing agent, the adhesive force of the material is improved, and the silver nanoparticles are arranged in the space net structureThe method comprises the following steps of sub-aggregation, combination of silver nanowires and silver-loaded modified melamine in a hydrogen bond mode, insertion of the silver nanowires in a spatial network structure, cooperative combination with silver nanoparticles in the network structure, and enhancement of conductivity, wherein the silver nanowires are subjected to corona combined low-temperature plasma treatment to enhance the surface activity of the silver nanowires, and meanwhile, the bonding strength of the silver nanowires and the silver-loaded modified melamine is improved, the specific surface area of diamond micro powder is increased after modification, the contact tightness between raw materials is improved, the surface is modified by mixed acid with strong oxidizing property and is combined with the silver-loaded modified melamine to form a cross network structure, the system is more stable, and the adhesion and the conductivity are obviously improved2O3、La2O3The additive has the obvious advantages that the diamond micro powder has high hardness and good mechanical property, the specific surface area is improved after the modification, the surface is modified, the enhancement is combined with the silver-loaded modified melamine to form a stable system, and the effects of adhesive force and the like can be obviously enhanced.
Compared with the prior art, the invention has the following beneficial effects:
the silver paste disclosed by the invention is good in conductivity and strong in adhesive force, is superior to a comparative example in acid-base resistance and washing resistance under the condition of ensuring good conductivity compared with the prior art, is applied to the front of a silicon solar cell as an electrode material, and has good application value.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1.
The preparation method of the silver paste with high adhesion for the front electrode of the silicon solar cell comprises the following steps:
step one, weighing the following raw materials in parts by weight: 15 parts of silver-loaded modified melamine, 50 parts of pretreated silver nanowires, 5 parts of modified diamond micro powder, 1 part of curing agent, 0.2 part of curing accelerator and 10 parts of solvent;
and step two, adding the silver-loaded modified melamine and the solvent in the step one into a magnetic stirrer, starting the magnetic stirrer, increasing the stirring speed to 550r/min, stirring at 75 ℃ for 5min, then adding the silver nanowires and the modified diamond micro powder, reducing the stirring speed to 350r/min, stirring for 15min, then adding the curing agent and the curing accelerator, reducing the stirring speed to 120r/min, and continuing stirring for 1h to obtain the silver paste.
The preparation method of the silver-loaded modified melamine comprises the following steps:
step one, preparing modified melamine: mixing melamine and paraformaldehyde according to a ratio of 1:2.5, then feeding into a three-neck flask, adding distilled water and alkali, heating to 70 ℃ under the condition of stirring, reacting for 30min, then adding a modifier of terephthalaldehyde, and adjusting the pH value to 7.5 for later use;
step two, pretreating silver nanoparticles: adding silver nanoparticles (with particle size of 4nm) into absolute ethyl alcohol, mixing, performing ultrasonic dispersion for 10min, adding silane coupling agent KH-560, performing hydrothermal treatment for 15min at the hydrothermal temperature of 65 ℃, then washing with water, centrifuging, and drying to obtain the product;
and step three, sequentially feeding the modified melamine prepared in the step one, the pretreated silver nanoparticles prepared in the step two and absolute ethyl alcohol into a high-pressure reaction kettle for reaction, wherein the reaction pressure is 3MPa, and the reaction time is 35min, so as to obtain the silver-loaded modified melamine.
The method for pretreating the silver nanowires is implemented by alternately treating the silver nanowires for 4min through corona and low-temperature plasma.
The corona combined low-temperature plasma treatment method of the embodiment is to place the silver nanowires in a glass container of an aqueous solution, place the silver nanowires between an upper electrode and a lower electrode, treat the silver nanowires for 15s under the voltage of 6kV, and then carry out corona treatment for 45s under the treatment power of 5 kW.
The silver nanowires of this example were 40 μm in length and 30nm in diameter.
The preparation method of the modified diamond micro powder comprises the steps of adding the diamond micro powder and oleic acid into a ball mill for ball milling at the ball milling rotation speed of 300r/min for 1h, then sending the mixture into a reaction kettle, adding deionized water for ultrasonic dispersion for 15min, then adding concentrated sulfuric acid and concentrated nitric acid according to the weight ratio of 2:1, continuing stirring for 25min, and then washing, leaching and drying.
The curing agent of this example was methyl ethyl ketone peroxide.
The curing accelerator in this example was an organotin curing accelerator.
The solvent of this example was propylene glycol methyl ether acetate.
Example 2.
The preparation method of the silver paste with high adhesion for the front electrode of the silicon solar cell comprises the following steps:
step one, weighing the following raw materials in parts by weight: 25 parts of silver-loaded modified melamine, 60 parts of pretreated silver nanowires, 9 parts of modified diamond micro powder, 3 parts of curing agent, 0.8 part of curing accelerator and 18 parts of solvent;
and step two, adding the silver-loaded modified melamine and the solvent in the step one into a magnetic stirrer, starting the magnetic stirrer, increasing the stirring speed to 650r/min, stirring at 85 ℃ for 15min, then adding the silver nanowires and the modified diamond micro powder, reducing the stirring speed to 450r/min, stirring for 25min, then adding the curing agent and the curing accelerator, reducing the stirring speed to 160r/min, and continuing stirring for 3h to obtain the silver paste.
The preparation method of the silver-loaded modified melamine comprises the following steps:
step one, preparing modified melamine: mixing melamine and paraformaldehyde according to a ratio of 1:2.5, then feeding into a three-neck flask, adding distilled water and alkali, heating to 80 ℃ under the condition of stirring, reacting for 40min, then adding a modifier of terephthalaldehyde, and adjusting the pH value to 7.5 for later use;
step two, pretreating silver nanoparticles: adding silver nanoparticles (with particle size of 4-10nm) into absolute ethyl alcohol, mixing, performing ultrasonic dispersion for 20min, adding silane coupling agent KH-560, performing hydrothermal treatment for 25min at 75 deg.C, washing with water, centrifuging, and drying;
and step three, sequentially feeding the modified melamine prepared in the step one, the pretreated silver nanoparticles prepared in the step two and absolute ethyl alcohol into a high-pressure reaction kettle for reaction, wherein the reaction pressure is 4MPa, and the reaction time is 45min, so as to obtain the silver-loaded modified melamine.
The method for pretreating the silver nanowires is implemented by alternately treating the silver nanowires for 4min through corona and low-temperature plasma.
The corona combined low-temperature plasma treatment method of the embodiment is to place the silver nanowires in a glass container of an aqueous solution, place the silver nanowires between an upper electrode and a lower electrode, treat the silver nanowires for 15s at a voltage of 6KV, and then perform corona treatment for 45s at a treatment power of 5 Kw.
The silver nanowires of this example were 80um in length and 50nm in diameter.
The preparation method of the modified diamond micro powder comprises the steps of adding the diamond micro powder and oleic acid into a ball mill for ball milling at the ball milling rotation speed of 400r/min for 2h, then sending the mixture into a reaction kettle, adding deionized water for ultrasonic dispersion for 25min, then adding concentrated sulfuric acid and concentrated nitric acid according to the weight ratio of 2:1, continuing stirring for 35min, and then washing, leaching and drying.
The curing agent of this example was benzoyl peroxide.
The curing accelerator in this example was an organotin curing accelerator.
The solvent of this example was propylene glycol methyl ether acetate.
Example 3.
The preparation method of the silver paste with high adhesion for the front electrode of the silicon solar cell comprises the following steps:
step one, weighing the following raw materials in parts by weight: 20 parts of silver-loaded modified melamine, 55 parts of pretreated silver nanowires, 7 parts of modified diamond micro powder, 2 parts of curing agent, 0.5 part of curing accelerator and 14 parts of solvent;
and step two, adding the silver-loaded modified melamine and the solvent in the step one into a magnetic stirrer, starting the magnetic stirrer, increasing the stirring speed to 600r/min, stirring at the stirring temperature of 80 ℃, stirring for 10min, then adding the silver nanowires and the modified diamond micro powder, reducing the stirring speed to 400r/min, stirring for 20min, then adding the curing agent and the curing accelerator, reducing the stirring speed to 140r/min, and continuously stirring for 2h to obtain the silver paste.
The preparation method of the silver-loaded modified melamine comprises the following steps:
step one, preparing modified melamine: mixing melamine and paraformaldehyde according to a ratio of 1:2.5, then feeding into a three-neck flask, adding distilled water and alkali, heating to 75 ℃ under the condition of stirring, reacting for 35min, then adding a modifier of terephthalaldehyde, and adjusting the pH value to 7.5 for later use;
step two, pretreating silver nanoparticles: adding silver nanoparticles (with particle diameter of 7nm) into absolute ethyl alcohol, mixing, performing ultrasonic dispersion for 15min, adding silane coupling agent KH-560, performing hydrothermal treatment for 20min at 70 deg.C, washing with water, centrifuging, and drying;
and step three, sequentially feeding the modified melamine prepared in the step one, the pretreated silver nanoparticles prepared in the step two and absolute ethyl alcohol into a high-pressure reaction kettle for reaction, wherein the reaction pressure is 3.5MPa, and the reaction time is 40min, so as to obtain the silver-loaded modified melamine.
The method for pretreating the silver nanowires is implemented by alternately treating the silver nanowires for 4min through corona and low-temperature plasma.
The corona combined low-temperature plasma treatment method of the embodiment is to place the silver nanowires in a glass container of an aqueous solution, place the silver nanowires between an upper electrode and a lower electrode, treat the silver nanowires for 15s at a voltage of 6KV, and then perform corona treatment for 45s at a treatment power of 5 Kw.
The silver nanowires of this example were 60um in length and 40nm in diameter.
The preparation method of the modified diamond micro powder comprises the steps of adding the diamond micro powder and oleic acid into a ball mill for ball milling at the ball milling rotation speed of 350r/min for 1.5h, then sending into a reaction kettle, adding deionized water for ultrasonic dispersion for 20min, then adding concentrated sulfuric acid and concentrated nitric acid according to the weight ratio of 2:1, continuing stirring for 30min, and then washing, filtering and drying.
The curing agent of this example was benzoyl peroxide.
The curing accelerator in this example was an organotin curing accelerator.
The solvent of this example was propylene glycol methyl ether acetate.
Comparative example 1.
The materials and preparation process were substantially the same as those of example 3, except that the modified melamine was not used.
Comparative example 2.
The material and preparation process are basically the same as those of example 3, except that the modified diamond micropowder is not added.
Comparative example 3.
The material and preparation process are basically the same as those of example 3, except that the modified diamond micropowder is changed into Al2O3。
Comparative example 4
Chinese patent literature (publication number: CN105895191B) discloses a low-temperature conductive silver paste used for a solar cell and a raw material and a preparation method of example 3 in the preparation method of the low-temperature conductive silver paste.
The silver pastes prepared in examples 1 to 3 and comparative examples 1 to 4 were printed on the front surface of the solar cell, and then calcined at a temperature of 320 ℃ for 1 hour to form a silver layer, and then protected at a temperature of 35 ℃ for 12 hours to perform a scrub resistance test; the scrub-resistant testing method is to place the silver layer on the front side of the solar cell on a linear scrubbing machine for scrubbing until the silver layer is cracked to obtain scrubbing times.
Preparing silver layers from the silver pastes in the examples 1 to 3 and the comparative examples 1 to 4 by adopting a method in a scrub resistance test, and then carrying out an acid and alkali resistance test; soaking with 10% sodium hydroxide solution and 10% acetic acid solution, respectively, and measuring soaking passage time.
The results of adhesion property test of examples 1 to 3 and comparative examples 1 to 4 are as follows
As shown in examples 1 to 3 and comparative examples 1 to 4, the acid and alkali resistance, the washing resistance and the peel strength of examples 1 to 3 of the present invention are superior to those of comparative examples 1 to 4, and the number of times of washing resistance is increased by 75 times to 52.45% compared to comparative example 4 of example 3 of the present invention, and further, the acid and alkali resistance of examples 1 to 3 of the present invention is passed at 96 hours, while the acid and alkali resistance of comparative example 4 is not passed at 48 hours and the acid resistance is not passed at 96 hours, so that the adhesion of the present invention is remarkably improved.
After the adhesive force of the silver paste is measured, the conductivity of the silver paste is further measured, the relationship between the adhesive force and the conductivity is explored, corresponding adjustment is made, and then the conductivity and the adhesive force are coordinated, so that the performance of the prepared silver paste is more perfect.
Measuring electrical performance using a silicon solar cell efficiency measurement device
|
Series resistance (omega)
|
Conversion efficiency (%)
|
Example 1
|
0.00185
|
18.06
|
Example 2
|
0.00186
|
18.05
|
Example 3
|
0.00183
|
18.08
|
Comparative example 1
|
0.00198
|
17.84
|
Comparative example 2
|
0.00194
|
17.92
|
Comparative example 3
|
0.00191
|
17.95
|
Comparative example 4
|
0.00182
|
18.10 |
From the efficiency of the silicon solar cell, the conversion efficiency of the examples 1 to 3 of the invention is slightly lower than that of the comparative example 4, but the difference is smaller, so that the conversion efficiency is ensured while the adhesive force of the silver paste is improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.