CN115780824A - Preparation method and application of silver powder with high sintering activity - Google Patents
Preparation method and application of silver powder with high sintering activity Download PDFInfo
- Publication number
- CN115780824A CN115780824A CN202310043190.4A CN202310043190A CN115780824A CN 115780824 A CN115780824 A CN 115780824A CN 202310043190 A CN202310043190 A CN 202310043190A CN 115780824 A CN115780824 A CN 115780824A
- Authority
- CN
- China
- Prior art keywords
- solution
- silver
- silver powder
- acid
- deionized water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The application relates to the technical field of metal powder preparation, in particular to a preparation method and application of silver powder with high sintering activity, which comprises the following steps: adding a stabilizer into the reducing agent solution, and then adding a silver nitrate solution to obtain a nano silver solution; weighing silver nitrate and water, and mixing to obtain a solution A; weighing a reducing agent, mixing with water, and adding a nano silver solution to obtain a solution B; weighing a dispersing agent and mixing with water to obtain a solution C; quickly adding the solution A into the solution B, adding the solution A at an interval of 1-30s, and adding the solution C to obtain a reaction solution; adding a modifier into the reaction solution, performing surface treatment and curing to obtain a product; and washing the product with deionized water, separating and drying to obtain the product. According to the method, the dispersing agent is not added in the reaction process, and the dispersing agent is added after the reaction, so that fine silver crystal grains instantly generated in the reaction grow in situ, and the silver powder particles combined by the method are good in overall dispersibility, small in average particle size, small in crystal grain size and high in sintering activity.
Description
Technical Field
The application relates to the technical field of metal powder preparation, in particular to a preparation method and application of silver powder with high sintering activity.
Background
At present, the crystalline silicon solar cell is generally prepared by adopting a high-speed screen printing technology and a high-temperature short-time sintering process, and electrons are collected and led out through silver grid lines printed on the front surface and the back surface of a silicon wafer. The development of the technology promotes the efficiency of the crystalline silicon solar cell to break through continuously, the quality of the front silver paste determines the photoelectric conversion efficiency of the crystalline silicon solar cell, and the requirement on sintering of the front silver paste of the crystalline silicon solar cell is higher and higher. The open-circuit voltage is an important parameter influencing the photoelectric conversion efficiency, and the silver powder is used as the main body of the front silver paste, and the sintering activity of the silver powder directly determines the open-circuit voltage. Therefore, the development of silver powders having high sintering activity is one of the mainstream technical development directions in the field of silver powders at present.
Generally, the sintering activity of a silver powder is related to the average particle diameter of the silver powder and the size of crystal grains constituting the silver powder, and the smaller the average particle diameter of the silver powder is, the smaller the crystal grains are, the higher the sintering activity of the silver powder is. In order to reduce the particle size of the silver powder and prevent particle agglomeration, a large amount of dispersing agent is often added in the reaction process, which inevitably affects the nucleation growth process of the silver powder particles and causes the coarse grain size of the silver powder particles, however, the problems of agglomeration of the silver powder particles, poor integral dispersibility, large average particle size and the like are caused without adding the dispersing agent, and the finally formed silver powder particles have low activity.
Therefore, the preparation of the silver powder with the average particle size and the grain size meeting the requirement of high sintering activity simultaneously has important significance for the development of the crystalline silicon solar cell.
Disclosure of Invention
In order to prepare silver powder with high sintering activity and average grain diameter and grain size, the application provides a preparation method and application of silver powder with high sintering activity.
In a first aspect, the present application provides a method for preparing silver powder with high sintering activity, which adopts the following technical scheme:
a preparation method of silver powder with high sintering activity comprises the following steps:
s1, nano-silver solution: adding a stabilizer into the reducing agent solution, uniformly stirring, adding a silver nitrate solution, stirring for reaction, standing and curing to obtain a nano silver solution;
s2, preparing a reaction solution: weighing silver nitrate and deionized water, and stirring until the silver nitrate and the deionized water are completely dissolved to obtain a solution A; weighing a reducing agent and deionized water, stirring until the reducing agent and the deionized water are completely dissolved, adding an acid liquor to adjust the pH value to 1-2, adding the nano-silver solution, and stirring uniformly to obtain a solution B; weighing a dispersing agent and deionized water, and stirring until the dispersing agent and the deionized water are completely dissolved to obtain a solution C; controlling the solution A, the solution B and the solution C at the same temperature;
s3: high sinterability silver powder: under the condition of stirring, quickly adding the solution A into the solution B for 1-60s of feeding time, after the addition is finished, adding the solution C at an interval of 1-30s, and then adding the solution C to obtain a reaction solution; adding alkali liquor into the reaction solution, adjusting the pH to 5-8, adding a modifier, performing surface treatment and curing to obtain a product; and washing the product with deionized water, separating and drying to obtain the silver powder with high sintering activity.
By adopting the technical scheme, the preparation method adopted by the application does not add a dispersing agent in the silver powder reaction process, has short feeding time and high reaction speed, generates tiny crystal grains instantly and grows up without being interfered by the dispersing agent, directly combines the fine grains into silver powder particles, avoids agglomeration of the silver powder particles by a process of adding the dispersing agent after the reaction, has good integral dispersibility, and prepares the silver powder with high sintering activity, wherein the average grain diameter of the silver powder is between 1.4 and 2.0 mu m, the grain size is between 55 and 112nm, the average grain diameter is small, the grain size is small, the activity is high, the open-circuit voltage is high after sintering the prepared front silver paste, the photoelectric conversion efficiency is high, and the preparation method has wide application prospect in the field of electronic paste such as the front silver paste of the crystalline silicon solar cell.
Preferably, in the S1, the concentration of the silver nitrate solution is 0.01-1mmol/L; the mass ratio of the stabilizer to the silver nitrate is (0.5-50): 1.7; the molar ratio of the reducing agent to the silver nitrate is (0.1-5): 1; the curing time is 5-30min.
Preferably, in S1, the reducing agent is one or more of glucose, ascorbic acid, hydrazine hydrate, sodium borohydride, hydroxylamine, and formaldehyde, and is further preferably formaldehyde; the stabilizer is one or more of adipic acid, terephthalic acid, citric acid, malic acid, maleic acid, sodium citrate and sodium dodecyl sulfate, and is further preferably a mixture of adipic acid and sodium dodecyl sulfate.
By adopting the technical scheme, formaldehyde is used as a reducing agent to reduce silver ions, and the formaldehyde reduction method has a high reduction rate and uniformly dispersed generated nano-particles, so that the effect of selecting formaldehyde is better when preparing nano-silver with small particle size and relatively uniform dispersion; the stabilizer can control the reaction process, reduce the surface activity of silver ions, control the nanometer order of magnitude of the generated silver particles, and the adipic acid and the sodium dodecyl sulfate have synergistic effect, so that a nano silver solution with small particle size and uniform dispersion can be obtained when the adipic acid and the sodium dodecyl sulfate are mixed for use.
Preferably, in the S2, the concentration of the solution A is 0.1-5 mol/L; the molar ratio of the reducing agent in the solution B to the silver nitrate in the solution A is (0.1-5) to 1; the mass ratio of the nano silver solution in the solution B to the silver nitrate in the solution A is (0.001-1): 1; the mass ratio of the dispersing agent in the solution C to the silver nitrate in the solution A is (0.001-1): 1.
Further preferably, in the S2, the concentration of the solution A is 0.5-3 mol/L; the molar ratio of the reducing agent in the solution B to the silver nitrate in the solution A is (0.2-2) to 1; the mass ratio of the nano silver solution in the solution B to the silver nitrate in the solution A is (0.005-0.5) to 1; the mass ratio of the dispersing agent in the solution C to the silver nitrate in the solution A is (0.005-0.5): 1.
By adopting the technical scheme, the molar ratio of the reducing agent to the silver nitrate is optimized, and the rate of chemical reaction is further controlled, so that the granularity, the morphology and the dispersion condition of the obtained silver powder are controlled, and the yield of the silver powder is controlled; when the amount of the dispersing agent is too large, the purity of the prepared silver powder is greatly reduced, and therefore, the obtained silver powder has good dispersibility and high purity by controlling the mass ratio of the dispersing agent to the silver nitrate.
Preferably, in S2, the reducing agent is one or more of glucose, ascorbic acid, triethanolamine, hydrazine hydrate, and formaldehyde, and is further preferably ascorbic acid; the acid solution is one or more of concentrated sulfuric acid, concentrated nitric acid, oxalic acid, formic acid and acetic acid, and is preferably concentrated nitric acid; the dispersing agent is one or more of polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, gelatin, arabic gum and Tween, and the polyvinylpyrrolidone is further preferred.
By adopting the technical scheme, the ascorbic acid as a reducing agent has a five-membered ring structure, so that on one hand, silver ions attack oxygen atoms in the ascorbic acid to generate an oxidation-reduction reaction; on the other hand, hydroxyl of the enol structure of the ascorbic acid can also be ionized to generate hydrogen ions, the hydrogen ions react with silver ions, finally, the ascorbic acid is oxidized into dehydroascorbic acid, and the silver ions are reduced into simple substance silver. After silver ions and ascorbic acid are contacted and react, the reduced silver is adsorbed around the dehydroascorbic acid, so that the agglomeration of silver particles can be reduced to a certain extent, and the silver powder has a dispersing effect, so that the prepared silver powder has a good dispersing effect by selecting the ascorbic acid as a reducing agent and has not only reducing property but also a good dispersing effect.
The dispersing agent selects the polyvinylpyrrolidone, and after the silver crystal nucleus is formed, polyvinylpyrrolidone molecules form a coating film on the crystal nucleus, and the good steric hindrance between the coating films prevents the silver crystal nucleus from contacting with each other, so that the silver crystal nucleus is prevented from colliding with each other and being adhered.
Preferably, in the S2, the temperature of the solution A, the solution B and the solution C is controlled to be 10-50 ℃.
By adopting the technical scheme, the reaction temperature is an important influence factor of chemical reaction, crystal nucleus formation and crystal growth. The reaction temperature not only determines the reaction rate, but also plays an important role in the formation and growth of the generated crystal nucleus, the reaction temperature is increased in a proper range, the reaction rate is accelerated, and the granularity of the prepared silver powder tends to be reduced, so that the subsequent reaction is favorably carried out, and the reaction rate and the effect of the prepared silver powder are accelerated by controlling the reaction temperature and controlling the solution A, the solution B and the solution C at the same temperature.
Preferably, in the step S3, under the condition of stirring, the solution A is rapidly added into the solution B for 1 to 20 seconds, after the addition is finished, the interval is 1 to 15 seconds, and then the solution C is added to obtain a reaction solution.
By adopting the technical scheme, the reducing agent is added by adopting a rapid addition method, and is fully mixed with the silver nitrate solution under full stirring, so that the reaction can be uniformly carried out in the whole system. In the initial stage of the reaction, the concentration of the reactant is high, a large amount of silver atoms are generated instantly, and a large supersaturation degree is formed, so that after explosive nucleation occurs, the concentration of the reactant is reduced, and each process of the precipitation reaction can be synchronously and uniformly carried out at each part of the whole system. Therefore, the reaction rate is slowed down, the solute concentration is reduced, and the process of nucleation and growth is carried out, so that 'explosive nucleation and slow growth' are realized, then the dispersing agent is added after the reaction, the silver powder is prevented from agglomerating, the nucleation process and the growth process are separated, and the high sintering active silver powder with uniform particle size and good dispersibility is obtained.
Preferably, in S3, the alkali solution is one or more of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate, and more preferably ammonia water; the modifier is one or more of oleic acid, oleamide and stearic acid.
By adopting the technical scheme, the pH value of the reaction system is adjusted, so that the prepared silver powder has high dispersibility. When the pH value of the reaction solution is lower, H in the system + More, be unfavorable for the reaction to go on to the reduction direction, reduced the supersaturation and the nucleation rate of silver in the solution, under lower supersaturation, silver crystal nucleus in case form, the silver that the reaction obtained just grows on original crystal nucleus, is favorable to the crystal nucleus to grow up, and the silver powder that obtains is just thick and the reunion is serious. When the pH value is higher, OH in the system - The method is more, which is not beneficial to the reaction going towards the oxidation direction, the nucleation rate is accelerated, a large number of generated small crystal nuclei are seriously agglomerated due to instability, and the dispersibility is poor. Because the ammonia water is weak in the alkalinity,when the pH is adjusted, the pH is not easy to change greatly, so that the pH of the solution can be controlled in a desired range and is easy to control.
The modifier is used for carrying out surface treatment on the prepared silver powder, and the silver powder subjected to surface treatment can increase the wettability and affinity of the silver powder and a carrier, increase the leveling property of slurry and improve the printing performance, so that the surface modification of the silver powder is very important for obtaining the solar cell front silver paste with excellent performance.
Oleic acid is an unsaturated fatty acid containing an unsaturated double bond and a carboxyl group in the main chain, has an HLB value of less than 4, and is a water-insoluble surfactant. The unsaturated double bonds of the oleic acid can participate in the polymerization of the matrix, and have lipophilic property, and the carboxyl has hydrophilic property; the oleic acid also has the advantages of no toxicity, environmental protection, low price and easy obtainment, and the oleic acid is used for carrying out surface modification on the silver powder, thereby enhancing the stability of the silver particles and reducing the agglomeration among the silver particles; the oleamide can form a coating layer on the surface of the silver powder, so that the surface energy of the silver powder is reduced, the agglomeration of particles is prevented, the dispersion of the silver powder in a matrix is promoted, the mutual melting property is improved, and the bonding strength between the silver powder and the matrix is enhanced; the stearic acid coats the surface of the silver powder, so that the agglomeration effect among silver particles can be improved, and the dispersibility of silver ions is improved.
In a second aspect, the present application provides an application of a silver powder with high sintering activity, which adopts the following technical scheme:
the crystalline silicon solar cell front silver paste is prepared from the high-sintering activity silver powder.
By adopting the technical scheme, the high-sintering active silver powder has the advantages of small average particle size, small crystal grain size, high activity, high open circuit voltage after sintering of the prepared front silver paste, high photoelectric conversion efficiency and better application prospect in the field of front silver paste of the crystalline silicon solar cell.
In summary, the present application includes at least one of the following beneficial technical effects:
1. according to the preparation method of the high-sintering silver powder, no dispersing agent is added in the reaction process, the charging time is short, the reaction speed is high, a large number of fine crystal grains are generated instantly and cannot grow up under the interference of the dispersing agent, the fine crystal grains are directly combined into silver powder particles, the reaction process is delayed under the acidic condition, and the stability of the fine crystal grain combination process is ensured; meanwhile, by a method of adding the dispersing agent after the reaction, the adding time is controlled, the agglomeration of the combined silver powder particles is avoided, and the integral dispersibility of the prepared silver powder is improved;
2. the preparation method of the nano silver solution is simple and feasible, a dispersing agent is not introduced, and the average particle size of the prepared silver powder can be effectively controlled by using the self-made nano silver solution;
3. the preparation method is simple, easy to operate, capable of being implemented at normal temperature, free of complex subsequent treatment, beneficial to continuous stable production and high in practicability;
4. the silver powder with high sintering activity prepared by the application has the advantages of average particle size of 1.4-2 mu m, small average particle size, good dispersibility, crystal grain size of 55-112nm, small crystal grains, high activity, high open-circuit voltage after sintering and high photoelectric conversion efficiency when being used for preparing front silver paste, and has wide application prospect in the field of front silver paste of crystalline silicon solar cells.
Drawings
FIG. 1 is an SEM image of a highly sintered active silver powder prepared in example 1 of the present application.
FIG. 2 is an SEM image of a high sintering activity silver powder prepared in example 8 of the present application.
FIG. 3 is an SEM photograph of a highly sintered active silver powder prepared in example 9 of the present application.
FIG. 4 is an SEM image of a silver powder prepared in comparative example 1 of the present application.
Fig. 5 is an SEM image of silver powder prepared in comparative example 2 of the present application.
FIG. 6 is an SEM image of a silver powder prepared in comparative example 3 of the present application.
Detailed Description
The present application will be described in further detail below with reference to examples and the accompanying drawings.
All the starting materials in the examples are commercially available.
Example 1
The embodiment discloses a preparation method of silver powder with high sintering activity, which comprises the following steps:
s1, adding 0.1g of adipic acid and 0.4g of sodium dodecyl sulfate into 1L of 0.05mmol/L formaldehyde solution at 25 ℃, uniformly stirring, then adding 1L of 0.1mmol/L silver nitrate solution, stirring for reaction, standing and curing for 25min to obtain a nano-silver solution;
s2, weighing 1020g of silver nitrate and 12L of deionized water, and stirring until the silver nitrate and the deionized water are completely dissolved to obtain a solution A with the concentration of 0.5 mol/L; weighing 816g of ascorbic acid and 12L of deionized water, stirring until the ascorbic acid and the deionized water are completely dissolved, adding concentrated nitric acid, adjusting the pH value to 1.5, then adding 51g of the nano-silver solution, and stirring uniformly to obtain a solution B; weighing 204g of polyvinylpyrrolidone K30 and 4L of deionized water, and stirring until the polyvinylpyrrolidone K30 and the deionized water are completely dissolved to obtain a solution C; controlling the solution A, the solution B and the solution C at 40 ℃;
s3, under the stirring condition, quickly adding the solution A into the solution B within 15S, and adding the solution C into the solution B at an interval of 15S after the solution A is added to obtain a reaction solution; adding ammonia water into the reaction liquid, adjusting the pH value to 7, adding 3g of oleamide and 2g of stearic acid, performing surface treatment, and curing for 25min to obtain a product; and washing the product with deionized water, separating and drying to obtain the silver powder with high sintering activity.
The embodiment also discloses a crystalline silicon solar cell front silver paste prepared by adopting the prepared high sintering activity silver powder.
Example 2
This example is substantially the same as example 1 except that 0.001g of adipic acid and 0.004g of sodium dodecyl sulfate were added to 1L of 0.001mmol/L formaldehyde solution at 5 ℃ in S1, followed by stirring to homogeneity, then 1L of 0.01mmol/L silver nitrate solution was added, followed by stirring reaction, standing and aging for 5min to obtain a nano-silver solution.
Example 3
This example is substantially the same as example 1 except that 0.01g of adipic acid and 0.04g of sodium lauryl sulfate were added to 1L of 5mmol/L formaldehyde solution at 50 ℃ in S1, followed by stirring to homogeneity, then 1L of 1mmol/L of silver nitrate solution was added, followed by stirring reaction and aging for 30min by standing to obtain a nano-silver solution.
Example 4
The embodiment is basically the same as the embodiment 1, except that in S2, 204g of silver nitrate and 12L of deionized water are weighed and stirred until the silver nitrate and the deionized water are completely dissolved, so as to obtain a solution A with the concentration of 0.1 mol/L; weighing 10.56g of ascorbic acid and 12L of deionized water, stirring until the ascorbic acid and the deionized water are completely dissolved, adding concentrated nitric acid, adjusting the pH value to be 1, then adding 204g of the nano-silver solution, and stirring uniformly to obtain a solution B; weighing 204g of polyvinylpyrrolidone K30 and 4L of deionized water, and stirring until the polyvinylpyrrolidone K30 and the deionized water are completely dissolved to obtain a solution C; the solution A, solution B and solution C were controlled at 10 ℃.
Example 5
The embodiment is basically the same as the embodiment 1, except that 10200g of silver nitrate and 12L of deionized water are weighed in S2 and stirred until completely dissolved to obtain a solution A with the concentration of 5 mol/L; weighing 52800g of ascorbic acid and 12L of deionized water, stirring until the ascorbic acid and the deionized water are completely dissolved, adding concentrated nitric acid, adjusting the pH value to be 2, adding 10.2g of the nano silver solution, and stirring uniformly to obtain a solution B; weighing 10.2g of polyvinylpyrrolidone K30 and 4L of deionized water, and stirring until the polyvinylpyrrolidone K30 and the deionized water are completely dissolved to obtain a solution C; the solution A, solution B and solution C were controlled at 50 ℃.
Example 6
The embodiment is basically the same as the embodiment 1, except that 6120g of silver nitrate and 12L of deionized water are weighed in S2 and stirred until the silver nitrate and the deionized water are completely dissolved, so that a solution A with the concentration of 3mol/L is obtained; 1267.2g ascorbic acid and 12L deionized water are weighed, stirred to be completely dissolved, concentrated nitric acid is added, the pH value is adjusted to be 1.5, 30.6g of the nano silver solution is added, and the mixture is stirred uniformly to obtain a solution B; weighing 30.6g of polyvinylpyrrolidone K30 and 4L of deionized water, and stirring until the polyvinylpyrrolidone K30 and the deionized water are completely dissolved to obtain a solution C; the solution A, solution B and solution C were controlled at 40 ℃.
Example 7
The embodiment is basically the same as the embodiment 1, except that 6120g of silver nitrate and 12L of deionized water are weighed in S2 and stirred until the silver nitrate and the deionized water are completely dissolved, so that a solution A with the concentration of 3mol/L is obtained; weighing 12672g of ascorbic acid and 12L of deionized water, stirring until the ascorbic acid and the deionized water are completely dissolved, adding concentrated nitric acid, adjusting the pH value to 1.5, then adding 3060g of the nano-silver solution, and uniformly stirring to obtain a solution B; weighing 3060g of polyvinylpyrrolidone K30 and 4L of deionized water, and stirring until the polyvinylpyrrolidone K30 and the deionized water are completely dissolved to obtain a solution C; the solution A, solution B and solution C were controlled at 40 ℃.
Example 8
The embodiment is basically the same as the embodiment 1, except that in S2, 1020g of silver nitrate and 12L of deionized water are weighed and stirred until the silver nitrate and the deionized water are completely dissolved to obtain a solution A with the concentration of 0.5 mol/L; weighing 816g of ascorbic acid and 12L of deionized water, stirring until the ascorbic acid and the deionized water are completely dissolved, adding concentrated nitric acid, adjusting the pH value to 1.5, then adding 61.2g of the nano-silver solution, and stirring uniformly to obtain a solution B; weighing 204g of polyvinylpyrrolidone K30 and 4L of deionized water, and stirring until the polyvinylpyrrolidone K30 and the deionized water are completely dissolved to obtain a solution C; the solution A, solution B and solution C were controlled at 40 ℃.
Example 9
The embodiment is basically the same as the embodiment 1, except that in S2, 1020g of silver nitrate and 12L of deionized water are weighed and stirred until the silver nitrate and the deionized water are completely dissolved to obtain a solution A with the concentration of 0.5 mol/L; weighing 816g of ascorbic acid and 12L of deionized water, stirring until the ascorbic acid and the deionized water are completely dissolved, adding concentrated nitric acid, adjusting the pH value to 1.5, then adding 81.6g of the nano-silver solution, and stirring uniformly to obtain a solution B; weighing 204g of polyvinylpyrrolidone K30 and 4L of deionized water, and stirring until the polyvinylpyrrolidone K30 and the deionized water are completely dissolved to obtain a solution C; the solution A, solution B and solution C were controlled at 40 ℃.
Example 10
This example is substantially the same as example 1 except that, in S3, the solution A was rapidly added to the solution B within 1S with stirring, and the solution C was added thereto at an interval of 1S to obtain a reaction solution.
Example 11
This example is substantially the same as example 1 except that, in S3, the solution A was rapidly added to the solution B over 20 seconds with stirring, and the solution C was added thereto at an interval of 15 seconds after the addition to obtain a reaction solution.
Example 12
This example is substantially the same as example 1 except that, in S3, the solution A was rapidly added to the solution B over 60 seconds with stirring, and the solution C was added thereto at an interval of 30 seconds after the addition to obtain a reaction solution.
Comparative example
Comparative example 1
This comparative example is different from example 9 in that S1 is omitted and no nano silver solution is added to S2, and the remaining steps are the same as example 9.
Comparative example 2
The difference between the comparative example and example 9 is that in S2, solution C is directly added to solution B to form a mixed solution, and then solution a is added to the mixed solution to carry out a reaction, and the rest of the procedure is the same as that of example 9.
Comparative example 3
This comparative example is different from example 9 in that the above solution A was rapidly added to the above solution B in 15 seconds with stirring in S3, and the above solution C was added thereto at an interval of 45 seconds after the addition to obtain a reaction solution, and the rest of the procedure was the same as example 9.
Performance detection
1. Particle size detection
The silver powders in the examples and comparative examples were examined by a Malvern 2000 particle size Analyzer to measure the average particle size of the silver powders.
2. Grain size
The silver powders of the examples and comparative examples were examined by a Smart Lab X-ray diffractometer to measure the grain size of the silver powders.
TABLE 1 Table of data for testing the properties of examples 1 to 12 and comparative examples 1 to 3
Referring to table 1 and fig. 1-6, the silver powder with high sintering activity prepared in the examples of the present application has good dispersibility, small average particle size and small grain size as measured by JEOL JSM-7800 scanning electron microscopy in fig. 1-6, and by comparing examples 1-12 with comparative examples 1-3; the nano silver solution is not added in the preparation process of the comparative example 1, the average grain size of the silver powder cannot be effectively controlled, the nucleation growth process of the silver powder becomes disordered, the average grain size is large, and the grain size is large; comparative example 2 dispersant is added in the reaction process, thus hindering the combination process of crystal grains, causing the generation of coarse crystal grains and having large crystal grain size; comparative example 3 the interval time between the addition of the dispersant after the reaction was too long, resulting in agglomeration of a part of the silver powder particles, poor overall dispersibility, and large average particle size.
The silver powders prepared in the above examples 1, 8 and 9 and comparative examples 1 to 3 and the silver powder of 1.8 μm (available from shanghai science raman reagent limited) commercially available were used to prepare the front silver paste of the crystalline silicon solar cell, 92% by weight of the silver powder, 6% by weight of the organic vehicle and 2% by weight of the glass powder were uniformly mixed, ground by a three-roll mill to prepare the front silver paste of the 7 crystalline silicon solar cell, printed on the monocrystalline silicon cell by a screen printing process, subjected to a high-temperature short-time sintering process to prepare 7 samples of the crystalline silicon solar cell, and the open-circuit voltage and the photoelectric conversion efficiency of the 7 samples of the cell were tested and calculated by using a solar cell I-V test system, and the test results are shown in table 2.
TABLE 2 tables for testing the performance of the battery cells of examples 1, 8, 9, comparative examples 1 to 3 and commercially available silver powders
Referring to table 2, it can be seen that, through the test of the cell system, the open-circuit voltage and the photoelectric conversion efficiency of the front silver paste of the crystalline silicon solar cell prepared from the silver powder with high sintering activity in the embodiment of the present application are significantly higher than those of the front silver paste of the crystalline silicon solar cell prepared from the silver powder with comparative examples 1 to 3 and the commercially available silver powder with 1.8 μm, which indicates that the smaller the average particle size and the grain size of the silver powder is, the higher the activity is, the easier the sintering is to form a densified structure, so that the open-circuit voltage is high, and the photoelectric conversion efficiency is high; comparative examples 1 to 3 silver powders have large average particle size, large grain size, poor dispersibility, low activity, and low degree of sintering densification, so that the open circuit voltage is low and the photoelectric conversion efficiency is low.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Referring to Table 1 in conjunction with FIGS. 1 to 6, by comparing examples 1 to 12 with comparative examples 1 to 3, the silver powders having high sintering activity prepared in the examples of the present application are excellent in dispersibility, small in average particle diameter and small in crystal grain size; the nano silver solution is not added in the preparation process of the comparative example 1, the average grain size of the silver powder cannot be effectively controlled, the nucleation growth process of the silver powder becomes disordered, the average grain size is large, and the grain size is large; comparative example 2 dispersant is added in the reaction process, thus hindering the combination process of crystal grains, causing the generation of coarse crystal grains and having large crystal grain size; comparative example 3 the interval time between the addition of the dispersant after the reaction was too long, resulting in agglomeration of a part of the silver powder particles, poor overall dispersibility, and large average particle size.
The silver powders prepared in the above examples 1, 8 and 9 and comparative examples 1 to 3 and the silver powder of 1.8 μm (available from shanghai science raman reagent limited) commercially available were used to prepare the front silver paste of the crystalline silicon solar cell, 92% by weight of the silver powder, 6% by weight of the organic vehicle and 2% by weight of the glass powder were uniformly mixed, ground by a three-roll mill to prepare the front silver paste of the 7 crystalline silicon solar cell, printed on the monocrystalline silicon cell by a screen printing process, subjected to a high-temperature short-time sintering process to prepare 7 samples of the crystalline silicon solar cell, and the open-circuit voltage and the photoelectric conversion efficiency of the 7 samples of the cell were tested and calculated by using a solar cell I-V test system, and the test results are shown in table 2.
TABLE 2 tables for testing the performance of the battery cells of examples 1, 8, 9, comparative examples 1 to 3 and commercially available silver powders
Referring to table 2, it can be seen that, through the test of the cell system, the open-circuit voltage and the photoelectric conversion efficiency of the front silver paste of the crystalline silicon solar cell prepared from the silver powder with high sintering activity in the embodiment of the present application are significantly higher than those of the front silver paste of the crystalline silicon solar cell prepared from the silver powder with comparative examples 1 to 3 and the silver powder with 1.8 μm commercially available, which indicates that the smaller the average particle size and the grain size of the silver powder is, the higher the activity is, the easier the silver powder is sintered to form a densified structure, so that the open-circuit voltage is high, and the photoelectric conversion efficiency is high; comparative examples 1 to 3 silver powders have large average particle size, large grain size, poor dispersibility, low activity, and low degree of sintering densification, so that the open circuit voltage is low and the photoelectric conversion efficiency is low.
The specific embodiments are only for explaining the present application and are not limiting to the present application, and those skilled in the art can make modifications to the embodiments without inventive contribution as required after reading the present specification, but all the embodiments are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A preparation method of silver powder with high sintering activity is characterized by comprising the following steps: the method comprises the following steps:
s1, nano silver solution: adding a stabilizer into the reducing agent solution, uniformly stirring, adding a silver nitrate solution, stirring for reaction, standing and curing to obtain a nano silver solution;
s2, preparing a reaction solution: weighing silver nitrate and deionized water, and stirring until the silver nitrate and the deionized water are completely dissolved to obtain a solution A; weighing a reducing agent and deionized water, stirring until the reducing agent and the deionized water are completely dissolved, adding an acid liquor to adjust the pH value to 1-2, adding the nano-silver solution, and stirring uniformly to obtain a solution B; weighing a dispersing agent and deionized water, and stirring until the dispersing agent and the deionized water are completely dissolved to obtain a solution C; controlling the solution A, the solution B and the solution C at the same temperature;
s3: high sinterability silver powder: under the condition of stirring, quickly adding the solution A into the solution B for 1-60s of feeding time, after the addition is finished, adding the solution C at an interval of 1-30s, and then adding the solution C to obtain a reaction solution; adding alkali liquor into the reaction solution, adjusting the pH to 5-8, adding a modifier, performing surface treatment and curing to obtain a product; and washing the product with deionized water, separating and drying to obtain the silver powder with high sintering activity.
2. The method for preparing a silver powder with high sintering activity according to claim 1, wherein: in the S1, the concentration of the silver nitrate solution is 0.01-1mmol/L; the mass ratio of the stabilizer to the silver nitrate is (0.5-50): 1.7; the molar ratio of the reducing agent to the silver nitrate is (0.1-5): 1; the curing time is 5-30min.
3. The method for preparing a silver powder with high sintering activity according to claim 1, wherein the method comprises the following steps: in the S1, the reducing agent is one or more of glucose, ascorbic acid, hydrazine hydrate, sodium borohydride, hydroxylamine and formaldehyde; the stabilizer is one or more of adipic acid, terephthalic acid, citric acid, malic acid, maleic acid, sodium citrate and sodium dodecyl sulfate.
4. The method for preparing a silver powder with high sintering activity according to claim 1, wherein: in the S2, the concentration of the solution A is 0.1-5 mol/L; the molar ratio of the reducing agent in the solution B to the silver nitrate in the solution A is (0.1-5) to 1; the mass ratio of the nano silver solution in the solution B to the silver nitrate in the solution A is (0.001-1) to 1; the mass ratio of the dispersing agent in the solution C to the silver nitrate in the solution A is (0.001-1): 1.
5. The method for preparing a silver powder with high sintering activity according to claim 4, wherein: in the S2, the concentration of the solution A is 0.5-3 mol/L; the molar ratio of the reducing agent in the solution B to the silver nitrate in the solution A is (0.2-2) to 1; the mass ratio of the nano silver solution in the solution B to the silver nitrate in the solution A is (0.005-0.5) to 1; the mass ratio of the dispersing agent in the solution C to the silver nitrate in the solution A is (0.005-0.5): 1.
6. The method for preparing a silver powder with high sintering activity according to claim 1, wherein: in the S2, the reducing agent is one or more of glucose, ascorbic acid, triethanolamine, hydrazine hydrate and formaldehyde; the acid solution is one or more of concentrated sulfuric acid, concentrated nitric acid, oxalic acid, formic acid and acetic acid; the dispersant is one or more of polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, gelatin, acacia and tween.
7. The method for preparing a silver powder with high sintering activity according to claim 5, wherein: in the S2, the temperature of the solution A, the solution B and the solution C is controlled to be 10-50 ℃.
8. The method for preparing a silver powder with high sintering activity according to claim 1, wherein: and in the S3, under the stirring condition, quickly adding the solution A into the solution B for 1-20S of feeding time, and adding the solution C to obtain a reaction solution at an interval of 1-15S after the solution A is added.
9. The method for preparing a silver powder with high sintering activity according to claim 1, wherein: in the S3, the alkali liquor is one or more of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate and sodium bicarbonate; the modifier is one or more of oleic acid, oleamide and aliphatic carboxylic acid.
10. The crystalline silicon solar cell front silver paste is prepared by adopting the silver powder with high sintering activity in any one of claims 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310043190.4A CN115780824B (en) | 2023-01-29 | 2023-01-29 | Preparation method and application of silver powder with high sintering activity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310043190.4A CN115780824B (en) | 2023-01-29 | 2023-01-29 | Preparation method and application of silver powder with high sintering activity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115780824A true CN115780824A (en) | 2023-03-14 |
| CN115780824B CN115780824B (en) | 2023-05-30 |
Family
ID=85429039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310043190.4A Active CN115780824B (en) | 2023-01-29 | 2023-01-29 | Preparation method and application of silver powder with high sintering activity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115780824B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116984621A (en) * | 2023-08-15 | 2023-11-03 | 深圳市哈深智材科技有限公司 | Silver powder preparation method with adjustable sintering activity |
| CN116984622A (en) * | 2023-09-26 | 2023-11-03 | 东方电气集团科学技术研究院有限公司 | Preparation method of nano seed crystal for inducing growth of crystallization type micron-sized silver powder |
| CN117086323A (en) * | 2023-08-08 | 2023-11-21 | 湖北银科新材料股份有限公司 | Method for regulating and controlling crystallite size of silver powder |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1088206A (en) * | 1996-09-12 | 1998-04-07 | Dowa Mining Co Ltd | Silver powder and manufacture of silver powder |
| CN1651169A (en) * | 2004-02-03 | 2005-08-10 | 同和矿业株式会社 | Silver powder and method for producing same |
| WO2017043837A1 (en) * | 2015-09-10 | 2017-03-16 | 엘에스니꼬동제련 주식회사 | Method for preparing silver powder using silver grains |
| CN109079152A (en) * | 2018-07-18 | 2018-12-25 | 湖州贝斯特包装科技有限公司 | A kind of solar battery silver powder preparation method |
| CN110102777A (en) * | 2019-06-04 | 2019-08-09 | 刘焕明 | A kind of preparation method of the highly crystalline silver powder of induced growth |
| CN110434355A (en) * | 2019-09-24 | 2019-11-12 | 广东先导稀材股份有限公司 | A kind of preparation method of high-tap density high dispersiveness spherical silver powder |
| CN113275586A (en) * | 2021-05-31 | 2021-08-20 | 广东省江门市质量计量监督检测所 | Method for preparing nano silver with different particle sizes by using surfactant |
| CN114273666A (en) * | 2021-12-24 | 2022-04-05 | 浙江光达电子科技有限公司 | Silver powder for solar cell silver paste and preparation method thereof |
| CN115055690A (en) * | 2022-06-01 | 2022-09-16 | 山东建邦胶体材料有限公司 | Full-spherical polycrystalline silver powder with directionally-aggregated crystal grains and preparation method thereof |
-
2023
- 2023-01-29 CN CN202310043190.4A patent/CN115780824B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1088206A (en) * | 1996-09-12 | 1998-04-07 | Dowa Mining Co Ltd | Silver powder and manufacture of silver powder |
| CN1651169A (en) * | 2004-02-03 | 2005-08-10 | 同和矿业株式会社 | Silver powder and method for producing same |
| WO2017043837A1 (en) * | 2015-09-10 | 2017-03-16 | 엘에스니꼬동제련 주식회사 | Method for preparing silver powder using silver grains |
| CN109079152A (en) * | 2018-07-18 | 2018-12-25 | 湖州贝斯特包装科技有限公司 | A kind of solar battery silver powder preparation method |
| CN110102777A (en) * | 2019-06-04 | 2019-08-09 | 刘焕明 | A kind of preparation method of the highly crystalline silver powder of induced growth |
| CN110434355A (en) * | 2019-09-24 | 2019-11-12 | 广东先导稀材股份有限公司 | A kind of preparation method of high-tap density high dispersiveness spherical silver powder |
| CN113275586A (en) * | 2021-05-31 | 2021-08-20 | 广东省江门市质量计量监督检测所 | Method for preparing nano silver with different particle sizes by using surfactant |
| CN114273666A (en) * | 2021-12-24 | 2022-04-05 | 浙江光达电子科技有限公司 | Silver powder for solar cell silver paste and preparation method thereof |
| CN115055690A (en) * | 2022-06-01 | 2022-09-16 | 山东建邦胶体材料有限公司 | Full-spherical polycrystalline silver powder with directionally-aggregated crystal grains and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117086323A (en) * | 2023-08-08 | 2023-11-21 | 湖北银科新材料股份有限公司 | Method for regulating and controlling crystallite size of silver powder |
| CN116984621A (en) * | 2023-08-15 | 2023-11-03 | 深圳市哈深智材科技有限公司 | Silver powder preparation method with adjustable sintering activity |
| CN116984621B (en) * | 2023-08-15 | 2024-02-13 | 深圳市哈深智材科技有限公司 | Silver powder preparation method with adjustable sintering activity |
| CN116984622A (en) * | 2023-09-26 | 2023-11-03 | 东方电气集团科学技术研究院有限公司 | Preparation method of nano seed crystal for inducing growth of crystallization type micron-sized silver powder |
| CN116984622B (en) * | 2023-09-26 | 2024-02-09 | 东方电气集团科学技术研究院有限公司 | Preparation method of nano seed crystal for inducing growth of crystallization type micron-sized silver powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115780824B (en) | 2023-05-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115780824A (en) | Preparation method and application of silver powder with high sintering activity | |
| CN110434355B (en) | Preparation method of high-tap-density and high-dispersibility spherical silver powder | |
| CN111922356B (en) | Microcrystalline silver powder with nano-silver surface structure and preparation method thereof | |
| CN113658739B (en) | Spherical-like silver powder with controllable particle size distribution and preparation method and application thereof | |
| CN115055690B (en) | Full-spherical polycrystalline silver powder with directionally-aggregated crystal grains and preparation method thereof | |
| JP5827341B2 (en) | Reactor for silver powder production and continuous production method | |
| CN111804905B (en) | Micron-sized spherical hollow gold powder and preparation method thereof | |
| CN113649557B (en) | Large-particle silver powder and preparation method and application thereof | |
| CN112296351B (en) | Preparation method of high-tap-density ultrafine silver powder | |
| CN112536445A (en) | Micro-nano dendritic silver powder and preparation method and application thereof | |
| CN115055673B (en) | Full-spherical polycrystalline silver powder and preparation method thereof | |
| JP2002180110A (en) | Method for manufacturing metallic colloidal solution | |
| CN116251961A (en) | Method for preparing silver powder with assistance of ultrasonic waves, silver powder prepared by method and application of silver powder | |
| CN111590086A (en) | Ultrathin flake silver powder with smooth surface and preparation method thereof | |
| CN112264629A (en) | Preparation method and application of low-cost high-dispersion silver powder | |
| CN111659901A (en) | Preparation method of submicron silver powder | |
| CN116329567A (en) | Method for preparing high-dispersion microcrystalline silver powder by two-step method and microchannel reaction equipment | |
| CN114192769B (en) | Silver powder with flower-like structure and preparation method thereof | |
| CN115055691B (en) | Cluster-shaped silver powder with large particle size and preparation method thereof | |
| CN117862497A (en) | Silver powder surface nanocrystallization preparation method | |
| CN111599507A (en) | Conductive silver paste based on smooth ultrathin flake silver powder and preparation method thereof | |
| CN111014717A (en) | Silver powder for low-temperature curing conductive silver paste and preparation method thereof | |
| CN117862488A (en) | Silver powder with surface modified by silver carboxylate and preparation method thereof | |
| CN115846648B (en) | High-activity spherical silver powder with cracking-shaped rough surface structure and preparation method thereof | |
| CN116984621B (en) | Silver powder preparation method with adjustable sintering activity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |