Disclosure of Invention
The invention aims to overcome the defects of poor conductivity and low battery efficiency of conductive glass powder in the prior art, and provides glass powder and a preparation method thereof.
In order to achieve the above object, a first aspect of the present invention provides a glass frit, which comprises the following raw materials: 10-20wt% of Bi2O342-74wt% of ZnO, 10-20wt% of WO32-5wt% of TeO21-4wt% of Li2O, 1-4wt% of V2O51-3wt% of TiCoO21-2wt% of PbO.
Preferably, the raw materials of the glass powder comprise: 10-15wt% of Bi2O354.7-74wt% of ZnO, 10-17wt% of WO32-4wt% of TeO21-3wt% of Li2O, 1-3wt% of V2O51-2wt% of TiCoO21-1.3wt% of PbO.
Preferably, said WO3And TiCoO2The mass ratio of (1): 1 to 1.5 of said Bi2O3And said V2O5The mass ratio of (1): 1.2-1.6.
Preferably, said WO3And TiCoO2The mass ratio of (1): 1 to 1.3 of said Bi2O3And said V2O5The mass ratio of (1):1.2-1.3。
in a second aspect, the present invention provides a method for preparing the glass frit, which comprises:
(1) adding Bi2O3、ZnO、TeO2、Li2O、V2O5Mixing the PbO and the raw materials to obtain a first material;
(2) mixing WO3And TiCoO2Mixing to obtain a second material;
(3) mixing the first material and the second material, pretreating, performing first smelting and water quenching, performing second smelting and water quenching, drying and ball milling;
wherein the temperature of the second smelting is higher than the temperature of the first smelting by 100-200 ℃.
Preferably, the temperature of the second melting is 130-150 ℃ higher than that of the first melting.
Preferably, the temperature of the second smelting is 1200-1250 ℃, and the temperature of the first smelting is 1000-1100 ℃.
Preferably, the time of the second smelting is 0.5-1h, and the time of the first smelting is 1-2 h.
Preferably, the conditions of the pretreatment are: the temperature is 500 ℃ and 800 ℃, and the time is 0.5-2 h.
Preferably, the drying conditions are: the temperature is 100 ℃ and 250 ℃, and the time is 1-2 h.
The inventors have found that by adding a specific amount of WO to the glass oxide3、TiCoO2、Bi2O3、V2O5、TeO2And the glass powder is matched with other components, has a synergistic effect, can effectively improve various performances of the glass powder, and is extremely low in lead content, green and environment-friendly. Moreover, the dosage of each component is reasonably distributed, and the cost is low. The glass powder prepared by the specific method has good conductivity and high battery efficiency. Further, the specific WO of the present invention is adopted3And TiCoO2Mass ratio of Bi2O3And V2O5The mass ratio of (A) to (B) is preferably such that each component can fully exert its ownSo that the conductivity is better and the battery efficiency is higher.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a glass frit, which comprises the following raw materials: 10-20wt% of Bi2O342-74wt% of ZnO, 10-20wt% of WO32-5wt% of TeO21-4wt% of Li2O, 1-4wt% of V2O51-3wt% of TiCoO21-2wt% of PbO.
In the present invention, each raw material is commercially available.
According to the present invention, preferably, the raw materials of the glass frit include: 10-15wt% of Bi2O354.7-74wt% of ZnO, 10-17wt% of WO32-4wt% of TeO21-3wt% of Li2O, 1-3wt% of V2O51-2wt% of TiCoO21-1.3wt% of PbO.
According to the invention, preferably, said WO3And TiCoO2The mass ratio of (1): 1 to 1.5 of said Bi2O3And said V2O5The mass ratio of (1): 1.2-1.6. By adopting the preferred technical scheme, the components can fully play respective roles, so that the conductivity is better and the battery efficiency is higher.
According to the invention, preferably, said WO3And TiCoO2The mass ratio of (1): 1 to 1.3 of said Bi2O3And said V2O5The mass ratio of (1): 1.2-1.3.
According to a preferred embodiment of the invention, the glass isThe raw materials of the powder comprise: 10-20wt% of Bi2O342-74wt% of ZnO, 10-20wt% of WO32-5wt% of TeO21-4wt% of Li2O, 1-4wt% of V2O51-3wt% of TiCoO21-2% by weight of WO3. Said WO3And TiCoO2The mass ratio of (1): 1 to 1.5 of said Bi2O3And said V2O5The mass ratio of (1): 1.2-1.6. Under the preferred scheme, the synergistic effect of the components can be optimized.
As described above, the second aspect of the present invention provides the method for producing a glass frit, which comprises:
(1) adding Bi2O3、ZnO、TeO2、Li2O、V2O5Mixing the PbO and the raw materials to obtain a first material;
(2) mixing WO3And TiCoO2Mixing to obtain a second material;
(3) mixing the first material and the second material, pretreating, performing first smelting and water quenching, performing second smelting and water quenching, drying and ball milling;
wherein the temperature of the second smelting is higher than the temperature of the first smelting by 100-200 ℃.
The inventor researches and discovers that the glass powder prepared by adopting the specific method, particularly performing pretreatment, then performing first smelting and water quenching, and then performing second smelting and water quenching, wherein the temperature of the second smelting is 100-200 ℃ higher than that of the first smelting, has excellent conductive performance and good battery efficiency.
According to the invention, the temperature of the second melting is preferably 130-150 ℃ higher than the temperature of the first melting.
According to the invention, the temperature of the second smelting is preferably 1200-1250 ℃, and the temperature of the first smelting is preferably 1000-1100 ℃.
According to the invention, preferably, the time of the second smelting is 0.5-1h, and the time of the first smelting is 1-2 h.
According to the present invention, preferably, the conditions of the pretreatment are: the temperature is 500 ℃ and 800 ℃, and the time is 0.5-2 h.
According to the present invention, preferably, the drying conditions are: the temperature is 100 ℃ and 250 ℃, and the time is 1-2 h.
In the present invention, the above water quenching is a conventional method in the art, and for example, the water quenching process may be: quickly pouring the glass into deionized water for water quenching to enable the glass to become a glass block, and then drying the glass block at the temperature of 200-400 ℃ and then repeating the water quenching.
According to a preferred embodiment of the present invention, a method for preparing glass frit comprises:
(1) adding Bi2O3、ZnO、TeO2、Li2O、V2O5Mixing the PbO and the raw materials to obtain a first material;
(2) mixing WO3And TiCoO2Mixing to obtain a second material;
(3) mixing the first material and the second material, pretreating, performing first smelting and water quenching, performing second smelting and water quenching, drying and ball milling;
wherein the temperature of the second smelting is higher than the temperature of the first smelting by 100-200 ℃. The temperature of the second smelting is 1200-1250 ℃, and the temperature of the first smelting is 1000-1100 ℃. The time of the second smelting is 0.5-1h, and the time of the first smelting is 1-2 h. The pretreatment conditions are as follows: the temperature is 500 ℃ and 800 ℃, and the time is 0.5-2 h. The drying conditions are as follows: the temperature is 100 ℃ and 250 ℃, and the time is 1-2 h.
The present invention will be described in detail below by way of examples. In the following examples, the starting materials were all commercially available products unless otherwise specified.
Example 1
(1) Adding Bi2O3、ZnO、TeO2、Li2O、V2O5Mixing the PbO and the raw materials to obtain a first material;
(2) mixing WO3And TiCoO2Mixing to obtain a second material;
(3) and mixing the first material and the second material, pretreating, performing first smelting and water quenching, performing second smelting and water quenching, drying and ball milling. The water quenching process comprises the following steps: and quickly pouring the mixture into deionized water for water quenching to enable the glass to become a glass block, drying the glass block at 260 ℃ for 1h, and then repeatedly performing water quenching to obtain the glass powder. The amounts of the above-mentioned raw materials and the process parameters are shown in table 1.
The positive electrode silver paste and the solar cell piece (sintering temperature is 790 ℃) are prepared by adopting glass powder according to the method of embodiment 1 in CN103295661A, and the height-width ratio of the main grid line, the series resistance, the filling factor and the photoelectric conversion efficiency are measured. The results are shown in Table 2.
Examples 2 to 3
The procedure is as in example 1, except that the amounts of the starting materials and the process parameters indicated in Table 1 are used.
Examples 4 to 5
The procedure is as in example 1, except that the amounts of the starting materials and the process parameters indicated in Table 1 are used.
Example 6
The procedure is as in example 1, except that the WO3And TiCoO2The mass ratio of (1): 1.5 of said Bi2O3And said V2O5The mass ratio of (1): 1.6.
example 7
The procedure is as in example 1, except that the WO3And TiCoO2The mass ratio of (1): 1, said Bi2O3And said V2O5The mass ratio of (1): 1.
example 8
The process of example 1 was followed except that the temperature of the second melting was 200 ℃ higher than that of the first melting and the temperature of the first melting was 1050 ℃.
Example 9
The procedure is as in example 1, except that the temperature of the pretreatment is 300 ℃.
Comparative example 1
The procedure is as in example 1, except that WO is not introduced3And TiCoO2。
Comparative example 2
The procedure is as in example 1, except that no TiCoO is introduced2And V2O5。
Comparative example 3
The procedure of example 1 was followed except that the temperature of the second melting was equal to that of the first melting and was 1050 ℃.
TABLE 1
Wherein, the amount of ZnO used in each embodiment is the balance which meets the 100 percent of the total amount of the corresponding raw materials.
TABLE 2
Example numbering
|
Height-width ratio of main grid line
|
Series resistance omega
|
Filling factor%
|
Photoelectric conversion efficiency,%
|
Example 1
|
0.278340
|
0.002238
|
83.52
|
25.86
|
Example 2
|
0.272675
|
0.002163
|
83.69
|
25.97
|
Example 3
|
0.275326
|
0.002137
|
83.85
|
26.42
|
Example 4
|
0.263247
|
0.002357
|
82.63
|
24.47
|
Example 5
|
0.261579
|
0.002396
|
82.80
|
24.68
|
Example 6
|
0.261093
|
0.002458
|
82.92
|
24.52
|
Example 7
|
0.257053
|
0.002413
|
82.27
|
23.97
|
Example 8
|
0.258045
|
0.002382
|
82.48
|
23.89
|
Example 9
|
0.254752
|
0.002369
|
82.59
|
23.57
|
Comparative example 1
|
0.232548
|
0.003461
|
77.36
|
20.32
|
Comparative example 2
|
0.241683
|
0.003527
|
77.83
|
20.47
|
Comparative example 3
|
0.239603
|
0.003385
|
77.52
|
20.26 |
As can be seen from the results of table 2, the examples according to the present invention have significantly better effects.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.