CN116062999A - Glass powder combination and preparation method thereof, electronic paste and battery - Google Patents

Abstract

The invention relates to the field of photoelectric materials, in particular to a glass powder combination and a preparation method thereof, electronic paste and a battery. The invention develops a combination of two different glass powder systems, namely a high tellurium glass powder system T, which has a wider contact window and can ensure that the slurry has better contact performance when being applied to batteries with different passivation structures; the high silicon glass powder system G has lower corrosion level, and can ensure that the slurry can not cause excessive corrosion to the silicon wafer under the condition that the passivation film is thinner when the slurry is applied. In addition, the manufacturing process of the glass powder is adjusted, so that the grid line falling problem does not occur after the glass powder is dried when the optimized glass powder is applied to the slurry, and the attractiveness and stability of the battery piece are greatly improved.

Description

Glass powder combination and preparation method thereof, electronic paste and battery

technical field

The invention relates to the field of photoelectric materials, in particular to a glass powder combination and a preparation method thereof, an electronic paste and a battery.

Background technique

Since 2022, the country's photovoltaic installed capacity from January to May this year has accumulated 23.71GW, a year-on-year increase of 139.25%, exceeding the sum of installed capacity from January to August 2021 (22.05GW). Ben's demands never stopped. At present, PERC batteries are the main mass-produced batteries, but the mass production efficiency has approached the theoretical mass production efficiency, and the space for efficiency improvement and cost reduction has been limited. During this process, several high-efficiency crystalline silicon batteries have emerged, such as TOPCon batteries and HJT batteries. , IBC batteries, perovskite batteries, etc. Among them, the metallization process of TOPCon batteries and IBC batteries requires the use of high-temperature silver paste, and the metallization of HJT batteries requires the use of low-temperature silver paste.

The improvement of the efficiency of TOPCon batteries, IBC batteries and the current mainstream PERC batteries largely depends on the optimization of the passivation technology on the front surface and the back surface. In recent years, the aluminum oxide passivation film grown by atomic layer deposition technology has been proved to be a A better passivation material, compared with commonly used passivation materials such as silicon oxide, silicon nitride, silicon oxynitride, etc., the fixed negative charge concentration in the aluminum oxide film can reach a higher concentration, which can provide a very good field effect The passivation effect reduces the J0, metal of the metal composite and improves the efficiency, but at the same time the passivation effect is good, it brings difficulties to the slurry contact. The metallization slurry needs to have good contact performance and anti-corrosion performance If it is too large, it will cause burn-through and reduce efficiency.

The mainstream slurry is mainly suitable for commonly used passivation structures such as silicon oxide and silicon nitride. When the passivation structure of aluminum oxide is used, serious EL clouds will appear, with low efficiency and poor stability. After printing with conventional paste, the powder is often scraped off during the drying process, resulting in a large number of EL broken grids after sintering, which affects the efficiency and appearance. Therefore, it is imperative to develop metallization pastes suitable for alumina passivation structures.

Contents of the invention

In view of this, the invention provides a glass frit combination, a preparation method thereof, an electronic paste and a battery.

In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:

In a first aspect, the present invention provides a glass frit combination, including a glass frit system T and a glass frit system G;

The oxides of the glass frit system T include: tellurium oxide and lead oxide;

The oxides of the glass frit system G include: silicon oxide and tungsten oxide;

The mass ratio (1.5-4) of the glass powder system T to the glass powder system G:1.

Preferably, in parts by mass, the oxides of the glass frit system T include: 30-50 parts of tellurium oxide and 30-45 parts of lead oxide;

In parts by mass, the oxides of the glass frit system G include: 10-30 parts of silicon oxide and 8-15 parts of tungsten oxide.

Preferably, the glass frit system T includes: bismuth oxide, tungsten oxide, tellurium oxide, lead oxide and alkali metal oxides;

The glass frit system G includes: bismuth oxide, tungsten oxide, tellurium oxide, lead oxide, silicon oxide, alkaline earth metal oxide and boron oxide.

Preferably, glass frit system T and glass frit system G are included;

In parts by mass, the oxides of the glass frit system T include the following components:

In parts by mass, the oxides of the glass frit system G include the following components:

    

Preferably, in the glass frit system T, the mass ratio of the tellurium oxide to the lead oxide is 40:25.

Preferably, in the oxides of the glass powder system T, the mass ratio of the bismuth oxide, the tungsten oxide, the tellurium oxide, the lead oxide to the alkali metal oxide is 18:7:40: 25:10.

Preferably, in the glass frit system G, the mass ratio of silicon oxide to tungsten oxide is 20:10.

Preferably, among the oxides of the glass frit system G, the bismuth oxide, the tungsten oxide, the tellurium oxide, the lead oxide, the silicon oxide, the alkaline earth metal oxide and the boron oxide The mass ratio is 20:10:15:25:20:4:6.

Preferably, the mass ratio of the glass frit system T to the glass frit system G is 70:30.

In the second aspect, the present invention also provides a preparation method comprising any one of the glass powder combinations, which is: after mixing, melting and drying the raw materials of the glass powder system T and the glass powder system G, respectively The glass powder combination is obtained through water milling, jet milling, drying and crushing.

Preferably, the water mill adopts four kinds of zirconium balls, the mass ratio of circular zirconium balls with a diameter of 7mm, cylindrical zirconium balls with a diameter of 7mm, circular zirconium balls with a diameter of 5mm, and cylindrical zirconium balls with a diameter of 5mm is 2:2:1:1;

Preferably, the grinding air pressure of the jet mill is 0.65Mpa, and the rotating speed of the classifying wheel is 100Hz.

In the third aspect, the present invention also provides the use of the glass frit combination described in any one of the above, or the glass frit combination prepared by the preparation method described in any one of the above in the preparation of electronic paste or battery.

In the fourth aspect, the present invention also provides electronic paste, including the glass powder combination described in any one of the above, or the glass powder combination prepared by any of the above preparation methods, as well as silver powder and organic binder .

Preferably, in terms of parts by mass, the following components are included:

75-92 parts of silver powder

6-14 parts of organic binder.

Preferably, the silver powder includes one or more of spherical and microcrystalline powders, and the average particle size of the silver powder is 1.0 μm˜3.0 μm.

Preferably, the organic adhesive includes one or a combination of two or more of solvents, thickeners, plasticizers or thixotropic agents.

Preferably, the solvent includes one or more of DOP, DBE, terpineol, butyl carbitol, butyl carbitol acetate, benzyl alcohol, ethylene glycol monomethyl ether or diethylene glycol diethyl ether A combination of two or more.

Preferably, the thickener includes one or a combination of ethyl cellulose, cellulose acetate, solid acrylic resin or ABS resin.

Preferably, the preparation method of the organic binder includes: mixing raw materials, stirring and melting at 70-100° C. to obtain a uniform organic binder.

Preferably, the preparation method of the electronic paste includes: mixing the silver powder, the glass powder and the organic binder in proportion, after wetting, grinding and dispersing for 1-4 hours, and filtering to obtain the electronic paste material.

In the fifth aspect, the present invention also provides the use of the electronic paste described in any one of the above items in the preparation of batteries.

In the sixth aspect, the present invention also provides a battery, including: the glass frit combination described in any one of the above or the glass frit combination prepared by any one of the above preparation methods, or the electronic paste described in any one of the above materials, and other acceptable excipients

The present invention has developed two different glass powder systems, the high tellurium glass powder system T, which has a wider contact window and can ensure that the slurry has better contact performance when applied to batteries with different passivation structures; Silica glass powder system G, this system has a low corrosion level, which can ensure that the slurry will not cause excessive corrosion to the silicon wafer when the passivation film is thin. In addition, the present invention adjusts the manufacturing process of the glass powder, and when the optimized glass powder is applied to the slurry, there is no grid line falling off problem after drying, which greatly improves the aesthetics and stability of the battery sheet.

Description of drawings

The above and other objects, features and advantages of exemplary embodiments of the present disclosure will become readily understood by reading the following detailed description with reference to the accompanying drawings. In the drawings, several embodiments of the present disclosure are shown by way of illustration and not limitation, and the same or corresponding reference numerals indicate the same or corresponding parts, wherein:

Fig. 1 shows the metal composite performance of optimization group A on different passivation structures;

Fig. 2 shows the contact performance of optimization group A on different passivation structures;

Fig. 3 shows the metal composite performance of optimized group B on different passivation structures;

Fig. 4 shows the contact performance of optimized group B on different passivation structures;

Figure 5 shows the metal composite performance of optimized group C on different passivation structures;

Fig. 6 shows the contact performance of optimized group C on different passivation structures;

Fig. 7 shows the glass powder contact performance comparison of different ball milling processes;

Figure 8 shows the glass powder metal composite comparison of different ball milling processes;

Fig. 9 shows the glass frit contact performance comparison after improving the ball milling process;

Figure 10 shows the performance comparison of metal composites after the improved ball milling process.

Detailed ways

The invention discloses a glass powder combination and a preparation method thereof, an electronic paste and a battery, and those skilled in the art can learn from the content of this article and appropriately improve the process parameters to realize it. In particular, it should be pointed out that all similar replacements and modifications are obvious to those skilled in the art, and they are all considered to be included in the present invention. The method and application of the present invention have been described through preferred embodiments, and the relevant personnel can obviously make changes or appropriate changes and combinations to the method and application described herein without departing from the content, spirit and scope of the present invention to realize and Apply the technology of the present invention.

In the glass powder combination and the preparation method thereof, the electronic paste and the battery provided by the present invention, the raw materials and reagents used can be purchased from the market.

Below in conjunction with embodiment, further set forth the present invention:

Exploration of the proportioning ratio of different oxides in the glass frit system T of embodiment 1

The contact resistivity test uses the TLM method, that is, the rectangular transmission line method. The printed and sintered solar cells are cut into strips of a certain width (the width is set to W), and the constant current source of the instrument is used to measure the distance between the grid lines at different distances. According to the formula RL(Ln)=2Rc×(Rs/W)*Ln (the resistance measured by RL, Rc is the total contact resistance , Rs is the semiconductor sheet resistance, W is the width of the cut strip, and Ln is the distance between different gate lines), after obtaining Rc and Rs, the contact resistivity ρc is obtained according to the formula ρc=(Rc2·W2)/Rs.

The metal composite test is to use a metal composite screen for the paste (there are seven regional patterns with different line widths on the screen, representing different degrees of metallization levels, respectively 2.52%, 3.02%, 3.95%, 4.61%, 10.54%, 14.37%, 18.41%, the corresponding line widths are 30μm, 45μm, 60μm, 80μm, 180μm, 280μm, 380μm) printed on the silicon wafer, each area is tested with a sunsVoc tester, and J01 is obtained; take The metallized area is the x-axis, the measured J01 is the y-axis, and a straight line is fitted, and the slope k in the obtained equation is the metal composite value.

Table 1 The composition comparison of glass frit T after adjustment

Sample serial number Tellurium oxide content/% Lead oxide content/% preferred group A 40 25 Experimental group A1 45 20 Experimental group A2 35 30

It can be seen from Table 1 that the optimized group A after adjusting the ratio has the best comprehensive performance on the two passivation structures; at the same time, we can see that the high tellurium glass powder system T has better performance on different passivation structures. Excellent contact performance, but because of the greater damage to the silicon wafer, the metal compound is better, and when used alone, the opening pressure will be lower. When using it, it is necessary to make a design to prevent excessive corrosion in the formula.

By adjusting the ratio of different oxides in the glass powder system T, the following optimal ratio is obtained, bismuth oxide: tungsten oxide: tellurium oxide: lead oxide: alkali metal, when the mass ratio of these oxides is 18: At 7:40:25:10, the prepared glass powder has a wider contact window, but the corrosion is greater, and another glass powder system needs to be used when using it.

The proportioning of different oxides in the glass frit system G of embodiment 2

The contact resistivity test uses the TLM method, that is, the rectangular transmission line method. The printed and sintered solar cells are cut into strips of a certain width (the width is set to W), and the constant current source of the instrument is used to measure the distance between the grid lines at different distances. According to the formula RL(Ln)=2Rc×(Rs/W)*Ln (the resistance measured by RL, Rc is the total contact resistance , Rs is the semiconductor sheet resistance, W is the width of the cut strip, and Ln is the distance between different gate lines), after obtaining Rc and Rs, the contact resistivity ρc is obtained according to the formula ρc=(Rc2·W2)/Rs.

The metal composite test is to use a metal composite screen for the paste (there are seven regional patterns with different line widths on the screen, representing different degrees of metallization levels, respectively 2.52%, 3.02%, 3.95%, 4.61%, 10.54%, 14.37%, 18.41%, the corresponding line widths are 30μm, 45μm, 60μm, 80μm, 180μm, 280μm, 380μm) printed on the silicon wafer, each area is tested with a sunsVoc tester, and J01 is obtained; take The metallized area is the x-axis, the measured J01 is the y-axis, and a straight line is fitted, and the slope k in the obtained equation is the metal composite value.

Table 2 The composition comparison of glass frit G after adjustment

Sample serial number Silicon oxide content/% Tungsten oxide content/% preferred group B 20 10 Experimental group B1 15 15 Experimental group B2 10 20

It can be seen from Table 2 that the optimized group B after adjusting the ratio has the best performance on the two passivation structures. At the same time, we can see that the high-silica glass powder system G has lower metal recombination in different passivation structures, but because it has less damage to the silicon wafer, the contact performance is average, and the opening pressure will be lower when used alone. Higher, but the window is narrow, and there may be clouds and fog. When using it, it is necessary to make a design in the formula to improve the contact performance.

By adjusting the ratio of different oxides in the glass powder system G, the following optimal ratios are obtained, bismuth oxide: tungsten oxide: tellurium oxide: lead oxide: silicon oxide: alkaline earth metal: boron oxide, when these oxides When the mass ratio is 20:10:15:25:20:4:6, the prepared glass frit can control the corrosion performance better, but the contact performance is deviated, so it needs to be used with the glass frit system T.

Example 3

From the results of Example 1 and Example 2, it can be seen that the high-tellurium glass powder system T has good contact performance, but the corrosion is too large, which easily causes excessive corrosion to the silicon wafer; the high-silicon glass powder system G has a lower metal Composite, but the contact performance is relatively general, and it is prone to poor contact; in summary, the two glass powder systems are used in combination, and the ratio of the two is adjusted to achieve the best performance.

Table 3 Proportion of glass frit T and glass frit G in the adjusted slurry

model T ratio of glass frit system % of glass frit system G preferred group C 70 30 Experimental group C1 85 15 Experimental group C2 55 45

From the experimental data in Table 3, it can be seen that when the proportion of glass frit system T is 70%, and the content of glass frit system G is 30%, the comprehensiveness of the slurry is the best, especially on the alumina passivation layer. good performance.

Example 4 Comparison of particle size data when D50 produced by different ball milling processes is around 1.5 μm

The production process of the water mill method is batching→mixing→smelting (1100°C heat preservation for 80min)→drying (150°C)→ball milling tank water milling (10h)→filtering and standing→drying (150°C)→crushing→finished glass powder. Among them, the ball milling process adopts a 4L ball mill tank, and four kinds of zirconium balls are used, which are circular zirconium balls with a diameter of 7 mm: cylindrical zirconium balls with a diameter of 7 mm: circular zirconium balls with a diameter of 5 mm: 5 mm cylindrical zirconium balls = 2:2:1:1, the total mass of zirconium balls is 4Kg.

The production process of the sand mill method is batching→mixing→smelting (1100°C for 80min)→drying (150°C)→primary crushing with a pulverizer→sand mill ball milling→filtering and standing→drying (150°C)→crushing → Finished glass powder. Among them, the main adjustment parameter of the sand mill is the rotational speed, which is set to 1000r/min, and the number of times is twice.

The production process of the jet mill is batching, mixing, melting (1100°C heat preservation for 80 minutes), drying (150°C), preliminary crushing with a pulverizer, jet mill ball milling, drying (150°C), crushing, and finished glass powder. Among them, the main adjustment parameters of the jet milling process are the grinding air pressure, which is set to 0.65Mpa, and the speed of the classification wheel is adjusted, which is set to 100Hz.

The traditional ball milling method mostly uses a drum-type water mill to process the smelted glass powder to the required particle size, but the glass powder produced by this ball milling method has a large particle size span, a large difference in the internal size of the particle size, and Dmax is biased. When it is applied in the paste, it is easy to increase the printing broken grid, and the grid line will fall off after drying, that is, the printing performance is poor, and the drying window is narrow, but the glass powder D10 processed by the water mill is small, that is, it has a higher performance in sintering. Reactivity, the glass powder produced by this method has a better contact window; the glass powder produced by the sand milling process has a certain decrease in the particle size span, but there will still be a certain amount of powder removal during 3M tearing. The proportion of broken grids in the slurry is also reduced, and the electrical performance is slightly worse than that of the water mill; the glass frit made by the jet mill has the smallest span, and there is almost no broken grid in continuous printing, and 3M tearing has no powder removal, but the electrical performance It is also slightly worse than the water grinding method.

Table 4 The particle size distribution of glass powders of different ball milling processes

craft D10/μm D50/μm D90/μm D100/μm K water mill 0.451 1.532 7.946 18.453 4.89 sanding 0.645 1.513 5.89 9.543 3.47 jet mill 0.845 1.495 4.103 6.432 2.18

Table 5 Performance comparison of glass powders with different ball milling processes

craft EL performance Broken grid ratio/% 3M tear off water mill No clouds and fog, a lot of broken grids 15.3 severe powdering sanding No clouds, a few broken grids 8.7 Slight powder removal jet mill No clouds, almost no breaks 0.3 No powder removal

It can be seen from Table 5 that the glass powder produced by the single water grinding method has a large D100 and a large particle size span, and a large number of grids are broken when it is applied to the slurry, and the 3M tearing is seriously de-powdered after drying; the single-use sand The glass powder made by grinding method has significantly less broken grid ratio, and the 3M tearing is slightly de-powdered; the glass powder made by single-jet mill has almost no broken grid when applied to the slurry, and the 3M tearing does not de-powder. The glass powder EL and 3M made by this process perform better in tearing.

From the performance comparison results in Figure 7 and Figure 8, it can be seen that the contact performance of the glass frit made by a single water mill is the best, and it can form a good contact with the passivation structure of silicon nitride and aluminum oxide. The glass frit contact performance needs to be improved.

It can be seen from the results that the three ball milling methods have their own characteristics, so they can be combined for ball milling to optimize the best ball milling process. Therefore, the smelted glass powder is firstly ball-milled with a water mill until the D50 is about 20 μm, and then processed by sand milling and jet milling respectively to compare the changes in performance.

Example 5

Three kinds of ball milling ways in embodiment 4 are carried out combined ball milling, thus preferably go out best ball milling process. Therefore, the smelted glass powder is firstly ball-milled with a water mill until the D50 is about 20 μm, and then processed by sand milling and jet milling respectively to compare the changes in performance.

The production process of the water mill + sand mill method is batching → mixing → smelting (insulation at 1100°C for 80 minutes) → drying (150°C) → ball milling tank water milling (4h) → sand mill ball milling → filtering and standing → drying (150°C )→crushing→finished glass powder. Among them, the ball milling process adopts a 4L ball mill tank, and four kinds of zirconium balls are used, which are circular zirconium balls with a diameter of 7 mm: cylindrical zirconium balls with a diameter of 7 mm: circular zirconium balls with a diameter of 5 mm: 5 mm cylindrical zirconium balls = 2:2:1:1, the total mass of zirconium balls is 4Kg. Among them, the main adjustment parameter of the sand mill is the rotational speed, which is set to 1000r/min, and the number of times is twice.

The production process of water mill + jet mill is batching→mixing→smelting (1100°C heat preservation for 80min)→drying (150°C)→ball mill tank water milling (4h)→jet mill processing→drying (150°C)→crushing→finished product glass powder. Among them, the ball milling process adopts a 4L ball mill tank, and four kinds of zirconium balls are used, which are circular zirconium balls with a diameter of 7 mm: cylindrical zirconium balls with a diameter of 7 mm: circular zirconium balls with a diameter of 5 mm: 5 mm cylindrical zirconium balls = 2:2:1:1, the total mass of zirconium balls is 4Kg. Among them, the main adjustment parameters of the jet milling process are the grinding air pressure, which is set to 0.65Mpa, and the speed of the classification wheel is adjusted, which is set to 100Hz.

The particle size distribution of the glass powder of the improved ball milling process after table 6

craft D10/μm D50/μm D90/μm D100/μm K water mill 0.451 1.532 7.946 18.453 4.89 Water grinding + sanding 0.503 1.497 6.545 13.274 4.04 water mill + jet mill 0.552 1.516 4.504 7.07 2.61

From the results in Table 6, it can be seen that the D10 of the glass frits produced by combined ball milling has decreased to a certain extent, and the D100 has increased to a certain extent, and the span has also slightly increased.

Table 7 Performance comparison of glass powder after improved ball milling process

craft EL performance Broken grid ratio/% 3M tear off water mill No clouds and fog, a lot of broken grids 15.3 severe powdering Water grinding + sanding No clouds and fog, a lot of broken grids 10.45 Slight powder removal water mill + jet mill No clouds, almost no breaks 0.41 No powder removal

From the results in Table 7, it can be seen that when the glass powder produced by water mill + sand mill is applied to the slurry, there will still be a large number of broken grids, and the 3M tearing will cause slight powder removal; the glass powder produced by water mill + jet mill is applied to the slurry There is almost no broken grid when tearing, and the 3M tearing has no powder removal, which is a good performance.

From the results in Figure 9 and Figure 10, it can be seen that the glass powder made by water mill + jet mill has the best performance in contact performance and metal composite performance.

Based on the above results, it can be seen that after the improved ball milling process, the performance of the glass powder made by water mill + jet mill is better.

The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (23)

1. A glass frit combination, characterized by comprising a glass frit system T and a glass frit system G;

the oxides of the glass frit system T include: tellurium oxide and lead oxide;

the oxide of the glass frit system G includes: silicon oxide and tungsten oxide;

the mass ratio of the glass powder system T to the glass powder system G is (1.5-4): 1.

2. the glass frit combination according to claim 1, wherein the oxide of the glass frit system T comprises, in parts by mass: 30-50 parts of tellurium oxide and 30-45 parts of lead oxide;

the oxide of the glass powder system G comprises the following components in parts by mass: 10-30 parts of silicon oxide and 8-15 parts of tungsten oxide.

3. The glass frit combination according to claim 1 or 2, wherein the glass frit system T comprises: bismuth oxide, tungsten oxide, tellurium oxide, lead oxide, and alkali metal oxide;

the glass frit system G includes: bismuth oxide, tungsten oxide, tellurium oxide, lead oxide, silicon oxide, alkaline earth metal oxide, and boron oxide.

4. A glass frit combination according to any one of claims 1 to 3, comprising a glass frit system T and a glass frit system G;

the oxide of the glass powder system T comprises the following components in parts by mass:

the oxide of the glass powder system G comprises the following components in parts by mass:

5. the glass frit combination according to claim 4, wherein the mass ratio of tellurium oxide to lead oxide in the glass frit system T comprises 40:25.

6. The glass frit combination according to claim 4, wherein the mass ratio of bismuth oxide, tungsten oxide, tellurium oxide, lead oxide to alkali metal oxide in the oxide of the glass frit system T is 18:7:40:25:10.

7. the glass frit combination according to claim 4, wherein the mass ratio of the silicon oxide to the tungsten oxide in the glass frit system G comprises 20:10.

8. The glass frit combination according to claim 4, wherein the mass ratio of the bismuth oxide, the tungsten oxide, the tellurium oxide, the lead oxide, the silicon oxide, the alkaline earth metal oxide and the boron oxide in the oxide of the glass frit system G is 20:10:15:25:20:4:6.

9. the glass frit combination according to claim 1, wherein the mass ratio of the glass frit system T to the glass frit system G is 70:30.

10. The method of preparing a glass frit composition according to any one of claims 1 to 9, wherein the method of preparing is: and mixing, smelting and drying the raw materials of the glass powder system T and the glass powder system G, and respectively carrying out water grinding, air flow grinding, drying and crushing to obtain the glass powder combination.

11. The preparation method according to claim 10, wherein the water mill adopts four kinds of zirconium balls, namely round zirconium balls with the diameter of 7mm, cylindrical zirconium balls with the diameter of 7mm, round zirconium balls with the diameter of 5mm and cylindrical zirconium balls with the diameter of 5mm, and the mass ratio of the round zirconium balls to the cylindrical zirconium balls is 2:2:1:1.

12. The method of claim 10, wherein the jet mill has a grinding pressure of 0.65Mpa and a classifying wheel rotation of 100Hz.

13. Use of a glass frit combination according to any one of claims 1 to 9 or a glass frit combination produced by a production method according to any one of claims 10 to 12 for producing an electronic paste or a battery.

14. An electronic paste comprising the glass frit combination according to any one of claims 1 to 9 or the glass frit combination produced by the production method according to any one of claims 10 to 12, and silver powder and an organic binder.

15. The electronic paste according to claim 14, comprising the following components in parts by mass:

16. the electronic paste according to claim 14 or 15, wherein the silver powder comprises one or more of a spheroid-like powder and a microcrystalline powder, and the average particle size of the silver powder is 1.0 μm to 3.0 μm.

17. The electronic paste of claim 14 or 15, wherein the organic binder comprises a composition of one or more of a solvent, a thickener, a plasticizer, or a thixotropic agent.

18. The electronic paste of claim 14 or 15, wherein the solvent comprises one or more of DOP, DBE, terpineol, butyl carbitol acetate, benzyl alcohol, ethylene glycol monomethyl ether, or diethylene glycol diethyl ether.

19. The electronic paste of claim 14 or 15, wherein the thickener comprises a composition of one or more of ethylcellulose, cellulose acetate, solid acrylic resin, or ABS resin.

20. The electronic paste according to claim 14 or 15, wherein the organic binder is prepared by a method comprising: mixing the raw materials, stirring and melting at 70-100 ℃ to obtain the uniform organic adhesive.

21. The electronic paste according to claim 14 or 15, wherein the electronic paste is prepared by a method comprising: mixing the silver powder, the glass powder and the organic adhesive in proportion, wetting, grinding and dispersing for 1-4 h, and filtering to obtain the electronic paste.

22. Use of an electronic paste according to any of claims 14 to 21 for the preparation of a battery.

23. A battery comprising a glass frit combination according to any one of claims 1 to 9 or a glass frit combination produced according to the production method of any one of claims 10 to 12, or an electronic paste according to any one of claims 14 to 21, and acceptable other auxiliary materials.

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