CN111321471B - Low-weight monocrystalline silicon texturing additive and application thereof - Google Patents
Low-weight monocrystalline silicon texturing additive and application thereof Download PDFInfo
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- CN111321471B CN111321471B CN201910229648.9A CN201910229648A CN111321471B CN 111321471 B CN111321471 B CN 111321471B CN 201910229648 A CN201910229648 A CN 201910229648A CN 111321471 B CN111321471 B CN 111321471B
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Abstract
The invention relates to the field of monocrystalline silicon surface treatment, in particular to a low-weight monocrystalline silicon texturing additive and application thereof. The monocrystalline silicon texturing additive comprises the following components in percentage by weight: 0.01-1% of polysaccharide sulfonate, 0.1-3% of defoaming dispersant, 0.01-1% of corrosion inhibitor, 0.05-0.5% of water-soluble polymer protective agent, 0.05-2% of alkali and the balance of water. And mixing and compounding the texturing additive and an alkali solution to obtain the low-weight-reduction texturing corrosive liquid. The invention overcomes the defects of low production capacity, great reduction of texturing silicon wafers, high alkali consumption, short service life and the like in the prior art, and has the advantages of reducing the reflectivity of the silicon wafers, effectively improving the battery efficiency, shortening the texturing time and improving the single-groove capacity; meanwhile, the method is suitable for surface texturing of large-size and flaky silicon wafers, and has positive effects of reducing the consumption of alkali, prolonging the service life of a single groove and the like.
Description
Technical Field
The invention relates to the field of monocrystalline silicon surface treatment, in particular to a low-weight monocrystalline silicon texturing additive and application thereof.
Background
In the manufacturing process of the solar cell, in order to improve the absorption of sunlight and reduce the reflectivity of the surface of the silicon wafer, a pyramid structure needs to be manufactured on the surface of the silicon wafer, so that the sunlight is reflected and refracted on the surface of the silicon wafer for multiple times, and the solar cell with higher efficiency is finally obtained.
The efficiency of single crystal cell is increasing more and more, and in order to pursue lower cell manufacturing cost and higher module wattage output, the flaking of silicon wafer and large-size silicon wafer will become the current development direction. However, the flaking and large-size silicon wafers cause more serious fragmentation problems, and the existing diamond wire cutting technology causes serious silicon wafer wire marks, few damaged layers and difficult texturing.
The conventional wet-process texturing of the monocrystalline silicon wafer generally adopts sodium hydroxide or potassium hydroxide as a corrosive agent, and an alcohol-free texturing additive is added for texturing. The disadvantages are that: the texturing process generally has the problems of great silicon wafer weight reduction, long texturing time, non-uniform texturing of diamond wire cut silicon wafers, short service life of products and the like.
For example, an additive with the authorization publication number of CN102877135B for the alkaline environment-friendly alcohol-free texturing solution for monocrystalline silicon comprises the following components: 0.05-1% of protein, 0.01-1% of detergent, 0.001-0.003% of one or the combination of vitamin, donkey-hide gelatin and tea polyphenol and the balance of water. Compared with the additive which is not added, the additive and the use method can reduce the texturing temperature, do not use isopropanol, shorten the texturing time and obviously improve the texturing effect. However, the method still has many defects, such as long texturing time which needs to reach 700-1500 s, so that the texturing capacity is low, and the weight of a silicon slice in the texturing process is reduced to 0.4-0.6g, so that the weight reduction in the texturing process is excessive, and the alkali consumption is relatively high due to excessive weight reduction, and the service life of the texturing solution is short.
Disclosure of Invention
The invention provides a low-weight monocrystalline silicon texturing additive which has the advantages of reducing silicon wafer reflectivity, improving battery efficiency, shortening texturing time, reducing alkali consumption, prolonging service life of a single groove and the like, and application thereof, aiming at overcoming the defects of low production capacity, great reduction in texturing silicon wafers, high alkali consumption, short service life and the like in the prior art.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a low-weight-loss monocrystalline silicon texturing additive comprises the following components in percentage by weight: 0.01-1% of polysaccharide sulfonate, 0.1-3% of defoaming dispersant, 0.01-1% of corrosion inhibitor, 0.05-0.5% of water-soluble polymer protective agent, 0.05-2% of alkali and the balance of water.
The polysaccharide sulfonate in the monocrystalline silicon texturing additive can effectively play roles in texturing optimization and dispersion, provides texturing centers, and effectively disperses alkali on the surface of a silicon wafer, so that a small pyramid structure with high density and good uniformity is obtained. Meanwhile, in order to ensure that all components are dispersed more uniformly and help to remove hydrogen generated in the wool making process, the defoaming dispersant is added to help to perform the functions of defoaming assistance and dispersion assistance. In the existing texturing solution, effective alkali such as sodium hydroxide or potassium hydroxide does not usually have the protection of a corrosion inhibitor when reacting with a silicon wafer, so that the silicon wafer is seriously corroded in the using process, the problems of large weight loss of the silicon wafer and short service life of the texturing solution are caused.
Preferably, the preparation method of the polysaccharide sulfonate comprises the following steps:
(1) enzymolysis: crushing polysaccharide compound, adding the crushed polysaccharide compound into solution containing polysaccharide hydrolase, hydrolyzing at constant temperature for a certain time, raising the temperature of the system to the denaturation of the polysaccharide hydrolase, standing, cooling to room temperature, performing centrifugal separation, taking supernatant, and freeze-drying to obtain polysaccharide zymolyte with a certain polymerization degree;
(2) sulfonation: mixing the obtained polysaccharide zymolyte with an organic solvent, placing the mixture into a three-neck flask, slowly dropwise adding a sulfonation reagent while stirring, continuously reacting for a certain time after dropwise adding is finished to obtain a reaction solution, and adding a sodium hydroxide aqueous solution into the reaction solution for neutralization to neutrality;
(3) and (3) purification: and pouring the neutralized reaction solution into absolute ethyl alcohol, stirring and filtering, washing filter residues for a plurality of times by using the absolute ethyl alcohol, and drying to obtain the polysaccharide sulfonate.
The water solubility of polysaccharide compounds such as cellulose, starch, fructan and the like is poor, if the polysaccharide compounds are hydrolyzed to a certain degree, the molecular weight of the polysaccharide compounds is reduced, and the water solubility of the polysaccharide compounds can be improved to a certain degree. And the water solubility of the hydrolyzed polysaccharide zymolyte can be greatly improved after sulfonation. Meanwhile, the molecular surface of the degraded polysaccharide compound has more hydroxyl groups, and the hydroxyl groups can react with a sulfonation reagent, so that sulfonated groups are grafted on the molecules. After the sulfonated polysaccharide zymolyte is neutralized to be neutral by sodium hydroxide, sulfonic acid groups are converted into sulfonate, and the polysaccharide sulfonate can be effectively extracted and purified by the characteristic of poor solubility in absolute ethyl alcohol, so that the reaction is simple. Therefore, the method has the technical progress of high reaction efficiency, no pollution and mild conditions.
Preferably, the polysaccharide compound is cellulose, starch, glucan, fructan, galactan, mannan, araban, xylan, glycogen, chitosan, and the corresponding polysaccharide sulfonate is one or more of cellulose sodium sulfonate, starch sodium sulfonate, glucan sodium sulfonate, fructan sodium sulfonate, galactan sodium sulfonate, mannan sodium sulfonate, araban sodium sulfonate, xylan sodium sulfonate, glycogen sodium sulfonate, and chitosan sodium sulfonate.
Preferably, in the step (1), the hydrolysis temperature is 30-55 ℃, the hydrolysis time is 2-5 hours, and the concentration of the polysaccharide hydrolase is 10-25 u/g.
The traditional method using acid and alkali as hydrolytic agents needs to be carried out under the reflux condition, but the reaction can be carried out only under the condition of being close to room temperature, so that the reaction efficiency is greatly improved, and the reaction difficulty is greatly reduced.
Preferably, the mass ratio of the polysaccharide zymolyte to the sulfonating reagent in the step (2) is 1: 2.6-4.2, wherein the sulfonation reaction time is 1-3 h, the sulfonation reagent is one of chlorosulfonic acid, sulfonyl chloride or methylsulfonyl chloride, and the organic solvent is one of dichloromethane, ethyl acetate, n-hexane, tetrahydrofuran or toluene.
Preferably, the volume of the absolute ethyl alcohol in the step (3) is 5 to 15 times of the volume of the neutralized reaction solution.
Preferably, the defoaming dispersant is one of sodium carboxymethyl cellulose, sodium carboxymethyl starch, carboxymethyl chitosan and sodium alginate.
Preferably, the corrosion inhibitor is one or two of tannin, baicalein, puerarin, liquiritigenin, hesperetin, daidzein, catechin, cacao shell pigment, delphinidin, etc.
Preferably, the water-soluble polymer protective agent is hyperbranched polyacrylamide with high hydrophilicity, and the preparation method is as follows:
(a) surface activation of titanium dioxide particles: placing the nano titanium dioxide powder and water in a hydrothermal reaction kettle according to the water-solid ratio of 15-30: 1, adding 0.001-0.05% of acetic acid, and carrying out hydrothermal reaction at 120-150 ℃ for 8-12 h to obtain surface-activated titanium dioxide particles;
(b) surface modification: uniformly dispersing 10 parts of surface-activated titanium dioxide particles in 50 parts of dichloromethane at 0 ℃, then dropwise adding a solution of 10-15 parts of methacryloyl chloride dissolved in 50 parts of dichloromethane, completing dropwise adding within 30min, continuing to react for 2-5 h, then adding a sodium hydroxide aqueous solution to neutralize to neutrality, filtering, washing filter residues with deionized water for three times, and drying to obtain surface-modified titanium dioxide particles;
(c) graft polymerization: sequentially adding the surface modified titanium dioxide particles, acrylamide, water and ammonium persulfate into a reaction kettle according to the weight ratio of 5:20:100:0.5, stirring and reacting for 1-5 h at 80-95 ℃, and performing reduced pressure dehydration to obtain the high-hydrophilicity hyperbranched polyacrylamide.
The water-soluble polymer protective agent is of a hyperbranched structure, the core of the water-soluble polymer protective agent is nano titanium dioxide, and the nano titanium dioxide is firstly activated under the hydrothermal condition, so that the purposes of: (1) although the nano titanium dioxide is in a nano size, the nano titanium dioxide still generates an agglomeration phenomenon, and the agglomerated nano titanium dioxide can be effectively separated under a hydrothermal environment to obtain titanium dioxide particles with smaller sizes. (2) Although the surface of the common nano titanium dioxide has certain hydroxyl groups, the number of the hydroxyl groups is small, and more hydroxyl groups can be grafted on the surface of the titanium dioxide particles through a hydrothermal reaction, so that modified connection points can be provided for surface modification in the step (b). And then the modified titanium dioxide particles react with methacryloyl chloride to ensure that the surfaces of the titanium dioxide particles are grafted with methacrylic groups, so that the modified titanium dioxide particles can be effectively copolymerized with acrylamide to obtain a hyperbranched molecule taking nano titanium dioxide as a core and acrylamide as a side chain, and the hyperbranched molecule has extremely high water solubility so as to ensure the compatibility between the modified titanium dioxide particles and other components.
Preferably, the alkali is one of tetramethylammonium hydroxide, cesium hydroxide, sodium hydroxide or potassium hydroxide.
The application of the monocrystalline silicon texturing additive is characterized in that the texturing additive is mixed and compounded with an alkali solution to obtain a low-weight texturing corrosive liquid; the mass of the wool making additive accounts for 0.2-5wt% of the mass of the alkali solution, the concentration of the alkali solution is 0.2-5wt%, the wool making time of the wool making corrosive solution is 150-600s, and the wool making temperature is 75-90 ℃.
The texturing additive and the alkaline solution are mixed and compounded to obtain the low-weight-reduction texturing corrosive liquid, the texturing time is 150-600s, compared with the texturing liquid in the prior art, the texturing time is greatly shortened, the single-tank capacity is improved by more than one time, the texturing weight in the texturing process is greatly reduced, and the problem of fragment rate caused by flaking and large size is effectively solved. In addition, the alkali consumption in the wool making process can be effectively reduced, the initial alkali consumption is only 1.0% or less, the unit consumption of alkali is reduced, the cost is saved, the content of the generated sodium silicate or potassium silicate is reduced due to weight reduction, the longer batch life is obtained, the batch life can reach more than 200 batches, the liquid changing time is reduced, the yield is improved, and the production cost is also reduced.
Meanwhile, the monocrystalline silicon texturing additive disclosed by the invention can effectively reduce the reflectivity of the surface of a monocrystalline silicon piece, so that the efficiency of a battery piece can be greatly improved.
Therefore, the invention has the following beneficial effects:
(1) the texturing time is effectively shortened, and the single-groove capacity is improved;
(2) the density of the pyramid obtained by texturing is improved, the volume of the pyramid is reduced, the reflectivity of the surface of the monocrystalline silicon piece is reduced, and the efficiency of the cell piece is improved;
(3) the weight loss of the silicon wafer during texturing is reduced, the alkali consumption is reduced, and the service life of the texturing liquid is prolonged; reduce the fragmentation rate and is suitable for thin slices and large-size silicon wafers.
Drawings
FIG. 1 is an SEM image of a textured silicon wafer surface according to the present invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby.
Example 1
A low-weight-loss monocrystalline silicon texturing additive comprises the following components in percentage by weight: 0.01% of sodium cellulose sulfonate, 0.1% of sodium carboxymethylcellulose, 0.01% of tannic acid, 0.05% of water-soluble polymer protective agent, 1% of potassium hydroxide and the balance of water.
Wherein: the preparation method of the sodium cellulose sulfonate comprises the following steps:
(1) enzymolysis: crushing cellulose, adding the crushed cellulose into a solution containing polysaccharide hydrolase with the concentration of 10u/g, hydrolyzing for 2 hours at 30 ℃, raising the temperature of the system to modify the polysaccharide hydrolase, standing, cooling to room temperature, then carrying out centrifugal separation, taking supernatant, and freeze-drying to obtain a cellulose hydrolysate with a certain polymerization degree;
(2) sulfonation: mixing the obtained cellulase hydrolysate with dichloromethane according to the mass ratio of 1:5, placing the mixture into a three-neck flask, slowly dropwise adding chlorosulfonic acid with the mass 2.6 times that of the cellulase hydrolysate while stirring, continuously reacting for 1h after dropwise adding is finished to obtain a reaction solution, and adding a sodium hydroxide aqueous solution into the reaction solution to neutralize the reaction solution to neutrality;
(3) and (3) purification: and pouring the neutralized reaction solution into absolute ethyl alcohol with the volume 5 times that of the neutralized reaction solution, stirring and filtering, washing filter residues for 3 times by using the absolute ethyl alcohol, and drying to obtain the sodium cellulose sulfonate.
The water-soluble polymer protective agent is hyperbranched polyacrylamide with high hydrophilicity, and the preparation method is as follows:
(a) surface activation of titanium dioxide particles: placing the nano titanium dioxide powder and water in a hydrothermal reaction kettle according to the water-solid ratio of 15:1, then adding 0.001% acetic acid, and carrying out hydrothermal reaction at 120 ℃ for 12h to obtain surface-activated titanium dioxide particles;
(b) surface modification: uniformly dispersing 10 parts of surface-activated titanium dioxide particles in 50 parts of dichloromethane at 0 ℃, then dropwise adding a solution of 10 parts of methacryloyl chloride dissolved in 50 parts of dichloromethane, continuing to react for 2 hours within 30min, then adding a sodium hydroxide aqueous solution to neutralize to neutrality, filtering, washing filter residues for three times by deionized water, and drying to obtain surface-modified titanium dioxide particles;
(c) graft polymerization: sequentially adding the surface modified titanium dioxide particles, acrylamide, water and ammonium persulfate into a reaction kettle according to the weight ratio of 5:20:100:0.5, stirring and reacting for 1h at 80 ℃, and performing reduced pressure dehydration to obtain the high-hydrophilicity hyperbranched polyacrylamide.
Example 2
A low-weight-loss monocrystalline silicon texturing additive comprises the following components in percentage by weight: 1% of sodium starch sulfonate, 3% of sodium carboxymethyl starch, 1% of baicalein, 0.5% of water-soluble polymer protective agent, 2% of sodium hydroxide and the balance of water.
Wherein: the preparation method of the sodium starch sulfonate comprises the following steps:
(1) enzymolysis: crushing starch, adding the crushed starch into a solution containing polysaccharide hydrolase with the concentration of 25u/g, hydrolyzing for 5 hours at 55 ℃, raising the temperature of the system to modify the polysaccharide hydrolase at most, standing, cooling to room temperature, then carrying out centrifugal separation, taking supernatant, and freeze-drying to obtain a starch zymolyte with a certain degree of polymerization;
(2) sulfonation: mixing the obtained starch zymolyte and ethyl acetate according to the mass ratio of 1:10, putting the mixture into a three-neck flask, slowly dropwise adding sulfonyl chloride with the mass of 4.2 times that of the starch zymolyte while stirring, continuously reacting for 3 hours after dropwise adding is finished to obtain reaction liquid, and adding a sodium hydroxide aqueous solution into the reaction liquid to neutralize the reaction liquid to be neutral;
(3) and (3) purification: pouring the neutralized reaction solution into absolute ethyl alcohol with the volume 15 times that of the neutralized reaction solution, stirring and filtering, washing filter residues for 3 times by using the absolute ethyl alcohol, and drying to obtain sodium starch sulfonate.
The water-soluble polymer protective agent is hyperbranched polyacrylamide with high hydrophilicity, and the preparation method is as follows:
(a) surface activation of titanium dioxide particles: placing the nano titanium dioxide powder and water in a hydrothermal reaction kettle according to the water-solid ratio of 30:1, then adding 0.05% acetic acid, and carrying out hydrothermal reaction for 8 hours at 150 ℃ to obtain surface-activated titanium dioxide particles;
(b) surface modification: uniformly dispersing 10 parts of surface-activated titanium dioxide particles in 50 parts of dichloromethane at 0 ℃, then dropwise adding a solution of 15 parts of methacryloyl chloride dissolved in 50 parts of dichloromethane, continuing to react for 5 hours within 30min, then adding a sodium hydroxide aqueous solution to neutralize to neutrality, filtering, washing filter residues for three times by deionized water, and drying to obtain surface-modified titanium dioxide particles;
(c) graft polymerization: sequentially adding the surface modified titanium dioxide particles, acrylamide, water and ammonium persulfate into a reaction kettle according to the weight ratio of 5:20:100:0.5, stirring and reacting for 5 hours at 95 ℃, and performing reduced pressure dehydration to obtain the high-hydrophilicity hyperbranched polyacrylamide.
Example 3
A low-weight-loss monocrystalline silicon texturing additive comprises the following components in percentage by weight: 0.5% of fructan sodium sulfonate, 2% of carboxymethyl chitosan or sodium alginate, 0.5% of liquiritigenin, 0.25% of water-soluble polymer protective agent, 0.15% of cesium hydroxide and the balance of water.
Wherein: the preparation method of the levan sodium sulfonate comprises the following steps:
(1) enzymolysis: crushing levan, adding the crushed levan into solution containing polysaccharide hydrolase with the concentration of 20u/g, hydrolyzing for 3 hours at 50 ℃, raising the temperature of the system to the denaturation of the polysaccharide hydrolase, standing, cooling to room temperature, then carrying out centrifugal separation, taking supernatant, and freeze-drying to obtain a levan zymolyte with a certain polymerization degree;
(2) sulfonation: mixing the obtained levan zymolyte and normal hexane according to the mass ratio of 1:8, putting the mixture into a three-neck flask, slowly dropwise adding methylsulfonyl chloride with the mass being 3 times that of the levan zymolyte into the mixture while stirring, continuously reacting for 2 hours after dropwise adding is finished to obtain reaction liquid, and adding a sodium hydroxide aqueous solution into the reaction liquid to neutralize the reaction liquid to be neutral;
(3) and (3) purification: pouring the neutralized reaction solution into absolute ethyl alcohol with the volume of 12 times, stirring and filtering, washing filter residues with absolute ethyl alcohol for 3 times, and drying to obtain the levan sodium sulfonate.
The water-soluble polymer protective agent is hyperbranched polyacrylamide with high hydrophilicity, and the preparation method is as follows:
(a) surface activation of titanium dioxide particles: placing the nano titanium dioxide powder and water in a hydrothermal reaction kettle according to the water-solid ratio of 25:1, then adding 0.015% of acetic acid, and carrying out hydrothermal reaction for 10 hours at 135 ℃ to obtain surface-activated titanium dioxide particles;
(b) surface modification: uniformly dispersing 10 parts of surface-activated titanium dioxide particles in 50 parts of dichloromethane at 0 ℃, then dropwise adding a solution of 12 parts of methacryloyl chloride dissolved in 50 parts of dichloromethane, continuing to react for 3 hours within 30min, then adding an aqueous solution of sodium hydroxide to neutralize to neutrality, filtering, washing filter residues for three times by deionized water, and drying to obtain surface-modified titanium dioxide particles;
(c) graft polymerization: sequentially adding the surface modified titanium dioxide particles, acrylamide, water and ammonium persulfate into a reaction kettle according to the weight ratio of 5:20:100:0.5, stirring at 90 ℃ for reaction for 3 hours, and performing reduced pressure dehydration to obtain the high-hydrophilicity hyperbranched polyacrylamide.
Example 4
A low-weight-loss monocrystalline silicon texturing additive comprises the following components in percentage by weight: 0.6% of xylan sodium sulfonate, 2% of sodium alginate, 0.8% of a 1:1 mixture of tannic acid and delphinium, 0.45% of a water-soluble polymer protective agent, 1.5% of potassium hydroxide and the balance of water.
Wherein: the preparation method of the sodium xylan sulfonate comprises the following steps:
(1) enzymolysis: crushing xylan, adding the crushed xylan into a solution containing polysaccharide hydrolase with the concentration of 18u/g, hydrolyzing for 3 hours at 50 ℃, raising the temperature of the system until the xylan hydrolase is denatured, standing, cooling to room temperature, performing centrifugal separation, and freeze-drying supernatant to obtain xylan zymolyte with a certain polymerization degree;
(2) sulfonation: mixing the obtained xylan zymolyte and tetrahydrofuran toluene according to the mass ratio of 1:8, placing the mixture into a three-neck flask, slowly dropwise adding chlorosulfonic acid with the mass being 4 times that of the xylan zymolyte while stirring, continuously reacting for 2.5 hours after dropwise adding is finished to obtain reaction liquid, and adding a sodium hydroxide aqueous solution into the reaction liquid to neutralize the reaction liquid to be neutral;
(3) and (3) purification: pouring the neutralized reaction solution into absolute ethyl alcohol with the volume of 12 times, stirring and filtering, washing filter residues for 3 times by using the absolute ethyl alcohol, and drying to obtain the sodium xylan sulfonate.
The water-soluble polymer protective agent is hyperbranched polyacrylamide with high hydrophilicity, and the preparation method is as follows:
(a) surface activation of titanium dioxide particles: placing the nano titanium dioxide powder and water in a hydrothermal reaction kettle according to the water-solid ratio of 25:1, then adding 0.085% acetic acid, and carrying out hydrothermal reaction at 145 ℃ for 10h to obtain surface-activated titanium dioxide particles;
(b) surface modification: uniformly dispersing 10 parts of surface-activated titanium dioxide particles in 50 parts of dichloromethane at 0 ℃, then dropwise adding a solution of 12 parts of methacryloyl chloride dissolved in 50 parts of dichloromethane, continuing to react for 4 hours within 30min, then adding an aqueous solution of sodium hydroxide to neutralize to neutrality, filtering, washing filter residues for three times by deionized water, and drying to obtain surface-modified titanium dioxide particles;
(c) graft polymerization: sequentially adding the surface modified titanium dioxide particles, acrylamide, water and ammonium persulfate into a reaction kettle according to the weight ratio of 5:20:100:0.5, stirring and reacting for 2.5h at 90 ℃, and performing reduced pressure water removal to obtain the high-hydrophilicity hyperbranched polyacrylamide.
Example 5
A low-weight-loss monocrystalline silicon texturing additive comprises the following components in percentage by weight: 0.85% of chitosan sodium sulfonate, 1.8% of sodium carboxymethylcellulose, 0.85% of cocoa shell pigment, 0.35% of water-soluble high-molecular protective agent, 1% of tetramethyl ammonium hydroxide and the balance of water.
Wherein: the preparation method of the sodium chitosan sulfonate comprises the following steps:
(1) enzymolysis: crushing chitosan, adding the crushed chitosan into a solution containing polysaccharide hydrolase with the concentration of 12u/g, hydrolyzing for 3 hours at 50 ℃, raising the temperature of the system until the chitosan hydrolase is denatured, standing, cooling to room temperature, then performing centrifugal separation, and taking supernatant to perform freeze drying to obtain chitosan zymolyte with a certain polymerization degree;
(2) sulfonation: mixing the obtained chitosan zymolyte and dichloromethane according to the mass ratio of 1:6, putting the mixture into a three-neck flask, slowly dropwise adding chlorosulfonic acid with the mass 3 times that of the chitosan zymolyte while stirring, continuously reacting for 1.5h after dropwise adding is finished to obtain reaction liquid, and adding a sodium hydroxide aqueous solution into the reaction liquid for neutralization to neutrality;
(3) and (3) purification: pouring the neutralized reaction solution into absolute ethyl alcohol with the volume 15 times that of the neutralized reaction solution, stirring and filtering, washing filter residues for 3 times by using the absolute ethyl alcohol, and drying to obtain the sodium chitosan sulfonate.
The water-soluble polymer protective agent is hyperbranched polyacrylamide with high hydrophilicity, and the preparation method is as follows:
(a) surface activation of titanium dioxide particles: placing the nano titanium dioxide powder and water in a hydrothermal reaction kettle according to the water-solid ratio of 20:1, then adding 0.025% acetic acid, and carrying out hydrothermal reaction for 8h at 140 ℃ to obtain surface-activated titanium dioxide particles;
(b) surface modification: uniformly dispersing 10 parts of surface-activated titanium dioxide particles in 50 parts of dichloromethane at 0 ℃, then dropwise adding a solution of 12 parts of methacryloyl chloride dissolved in 50 parts of dichloromethane, continuing to react for 2 hours within 30min, then adding an aqueous solution of sodium hydroxide to neutralize to neutrality, filtering, washing filter residues for three times by deionized water, and drying to obtain surface-modified titanium dioxide particles;
(c) graft polymerization: sequentially adding the surface modified titanium dioxide particles, acrylamide, water and ammonium persulfate into a reaction kettle according to the weight ratio of 5:20:100:0.5, stirring and reacting for 4 hours at 95 ℃, and performing reduced pressure dehydration to obtain the high-hydrophilicity hyperbranched polyacrylamide.
Example 6
The application of the monocrystalline silicon texturing additive is characterized in that the texturing additive and an alkaline solution are mixed and compounded to obtain the low-weight-loss texturing corrosive liquid, wherein the mass of the texturing additive accounts for 0.2 wt% of the mass of the alkaline solution, and the concentration of the alkaline solution is 5 wt%.
Example 7
The application of the monocrystalline silicon texturing additive is characterized in that the texturing additive and an alkaline solution are mixed and compounded to obtain the low-weight-loss texturing corrosive liquid, wherein the mass of the texturing additive accounts for 5wt% of that of the alkaline solution, and the concentration of the alkaline solution is 0.2 wt%.
Example 8
The application of the monocrystalline silicon texturing additive is characterized in that the texturing additive and an alkaline solution are mixed and compounded to obtain the low-weight-loss texturing corrosive liquid, the mass of the texturing additive accounts for 3.5 wt% of the mass of the alkaline solution, and the concentration of the alkaline solution is 1 wt%.
Example 9
The application of the monocrystalline silicon texturing additive is characterized in that the texturing additive and an alkaline solution are mixed and compounded to obtain the low-weight-loss texturing corrosive liquid, wherein the mass of the texturing additive accounts for 1.6 wt% of the mass of the alkaline solution, and the concentration of the alkaline solution is 2 wt%.
Example 10
The application of the monocrystalline silicon texturing additive is characterized in that the texturing additive and an alkaline solution are mixed and compounded to obtain a low-weight-loss texturing corrosive solution, wherein the mass of the texturing additive accounts for 4 wt% of that of the alkaline solution, and the concentration of the alkaline solution is 2 wt%.
FIG. 1 is an SEM image of the surface of a silicon wafer treated with a texturing etching solution according to example 7 of the present invention, in which small pyramids obtained on the surface have a higher density, a smaller volume and a uniform thickness, and thus the optical properties thereof are more excellent
The results of comparative tests of examples 6 to 10 with a commercially available etching solution for texturing are shown in the following table:
comparative table of performance of inventive example and comparative example
As can be seen from the data in the table, the texturing time of the texturing corrosive liquid obtained by the method is effectively reduced on the premise that the texturing temperature is closer to that of a commercial comparative example, and the texturing weight is greatly reduced. Reduce the problem of chip rate caused by flaking and large size. The silicon wafer surface reflectivity range after texturing by the texturing corrosive liquid is 10.0-11.0%, and the silicon wafer surface reflectivity range after texturing in the commercial comparative example is 11.0-12.0%, so that the silicon wafer surface reflectivity after texturing can be effectively reduced by using the method, and the efficiency of the battery piece can be further improved. In addition, the alkali consumption in the wool making process can be effectively reduced, the initial alkali consumption is only 1.0% or less, the unit consumption of alkali is reduced, the cost is saved, the content of the generated sodium silicate or potassium silicate is reduced due to weight reduction, the longer batch life is obtained, the batch life can reach more than 200 batches, the liquid changing time is reduced, the yield is improved, and the production cost is also reduced.
Claims (9)
1. The monocrystalline silicon texturing additive with low weight loss is characterized by comprising the following components in percentage by weight: 0.01-1% of polysaccharide sulfonate, 0.1-3% of defoaming dispersant, 0.01-1% of corrosion inhibitor, 0.05-0.5% of hyperbranched polyacrylamide with high hydrophilicity, 0.05-2% of alkali and the balance of water;
the preparation method of the polysaccharide sulfonate comprises the following steps:
(1) enzymolysis: crushing polysaccharide compound, adding the crushed polysaccharide compound into solution containing polysaccharide hydrolase, hydrolyzing at constant temperature for a certain time, raising the temperature of the system to the denaturation of the polysaccharide hydrolase, standing, cooling to room temperature, performing centrifugal separation, taking supernatant, and freeze-drying to obtain polysaccharide zymolyte with a certain polymerization degree;
(2) sulfonation: mixing the obtained polysaccharide zymolyte with an organic solvent, placing the mixture into a three-neck flask, slowly dropwise adding a sulfonation reagent while stirring, continuously reacting for a certain time after dropwise adding is finished to obtain a reaction solution, and adding a sodium hydroxide aqueous solution into the reaction solution for neutralization to neutrality;
(3) and (3) purification: and pouring the neutralized reaction solution into absolute ethyl alcohol, stirring and filtering, washing filter residues for a plurality of times by using the absolute ethyl alcohol, and drying to obtain the polysaccharide sulfonate.
2. The additive for texturing monocrystalline silicon with low weight loss as claimed in claim 1, wherein the hydrolysis temperature in step (1) is 30-55 ℃, the hydrolysis time is 2-5 h, and the concentration of polysaccharide hydrolase is 10-25 u/g.
3. The additive for texturing monocrystalline silicon with low weight loss as claimed in claim 1, wherein the mass ratio of the polysaccharide zymolyte to the sulfonating agent in step (2) is 1: 2.6-4.2, wherein the sulfonation reaction time is 1-3 h, the sulfonation reagent is one of chlorosulfonic acid, sulfonyl chloride or methylsulfonyl chloride, and the organic solvent is one of dichloromethane, ethyl acetate, n-hexane, tetrahydrofuran or toluene.
4. The additive for texturing monocrystalline silicon with low weight loss as claimed in claim 1, wherein the volume of the absolute ethyl alcohol in the step (3) is 5-15 times of the neutralized reaction solution.
5. A low weight loss, single crystal silicon texturing additive as claimed in claim 1 wherein the polysaccharide compound is cellulose, starch, dextran, fructan, galactan, mannan, arabinoan, xylan, glycogen, chitosan and the corresponding polysaccharide sulfonate is one or more of sodium cellulose sulfonate, sodium starch sulfonate, sodium dextran sulfonate, sodium fructan sulfonate, sodium galactan sulfonate, sodium mannan sulfonate, sodium arabinoan sulfonate, sodium xylan sulfonate, sodium glycogen sulfonate, sodium chitosan sulfonate.
6. The additive for texturing monocrystalline silicon with low weight loss as claimed in claim 1, wherein the defoaming dispersant is one of sodium carboxymethyl cellulose, sodium carboxymethyl starch, carboxymethyl chitosan or sodium alginate.
7. The additive as claimed in claim 1, wherein the corrosion inhibitor is one or two of tannin, baicalein, puerarin, liquiritigenin, hesperetin, daidzein, catechin, cocoa shell pigment, and delphinidin.
8. The additive for texturing monocrystalline silicon with low weight loss according to claim 1, wherein the hyperbranched polyacrylamide with high hydrophilicity is prepared by the following steps:
(a) surface activation of titanium dioxide particles: placing the nano titanium dioxide powder and water in a hydrothermal reaction kettle according to the water-solid ratio of 15-30: 1, adding 0.001-0.05% of acetic acid, and carrying out hydrothermal reaction at 120-150 ℃ for 8-12 h to obtain surface-activated titanium dioxide particles;
(b) surface modification: uniformly dispersing 10 parts of surface-activated titanium dioxide particles in 50 parts of dichloromethane at 0 ℃, then dropwise adding a solution of 10-15 parts of methacryloyl chloride dissolved in 50 parts of dichloromethane, completing dropwise adding within 30min, continuing to react for 2-5 h, then adding a sodium hydroxide aqueous solution to neutralize to neutrality, filtering, washing filter residues with deionized water for three times, and drying to obtain surface-modified titanium dioxide particles;
(c) graft polymerization: sequentially adding the surface modified titanium dioxide particles, acrylamide, water and ammonium persulfate into a reaction kettle according to the weight ratio of 5:20:100:0.5, stirring and reacting for 1-5 h at 80-95 ℃, and performing reduced pressure dehydration to obtain the high-hydrophilicity hyperbranched polyacrylamide.
9. The application of the additive for texturing monocrystalline silicon according to any one of claims 1 to 8, characterized in that the additive for texturing is mixed with an alkaline solution to obtain a low-weight-reduction texturing corrosive solution, the mass of the additive for texturing accounts for 0.2-5wt% of the mass of the alkaline solution, the concentration of the alkaline solution is 0.2-5wt%, the texturing time of the etching corrosive solution for texturing is 150-600s, and the texturing temperature is 75-90 ℃.
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| CN112144122A (en) * | 2020-10-21 | 2020-12-29 | 常州时创能源股份有限公司 | Texturing additive and texturing liquid suitable for large-size monocrystalline silicon wafers and application |
| CN112466995A (en) * | 2020-11-23 | 2021-03-09 | 宁波尤利卡太阳能股份有限公司 | Monocrystalline texturing method of PERC battery |
| CN112813502B (en) * | 2020-12-30 | 2022-05-20 | 常州高特新材料股份有限公司 | Monocrystalline silicon etching texturing additive and application thereof |
| CN113817472B (en) * | 2021-11-23 | 2022-02-11 | 绍兴拓邦电子科技有限公司 | Texturing process of solar cell silicon wafer |
| CN114318550A (en) * | 2021-12-15 | 2022-04-12 | 嘉兴市小辰光伏科技有限公司 | Additive for secondary texturing of monocrystalline silicon and texturing process thereof |
| CN114481332A (en) * | 2022-01-27 | 2022-05-13 | 江苏捷捷半导体新材料有限公司 | Low-weight-loss monocrystalline silicon piece texturing additive, preparation method and application thereof |
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