CN116564579A - HJT low-temperature conductive silver paste containing silver nano short rods and preparation method thereof - Google Patents

HJT low-temperature conductive silver paste containing silver nano short rods and preparation method thereof Download PDF

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CN116564579A
CN116564579A CN202310750262.9A CN202310750262A CN116564579A CN 116564579 A CN116564579 A CN 116564579A CN 202310750262 A CN202310750262 A CN 202310750262A CN 116564579 A CN116564579 A CN 116564579A
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silver
solution
agent
hjt
paste containing
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闫仁泉
杨华荣
王翔
蔡幸然
刘韩
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Hunan Silver New Materials Co ltd
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Hunan Silver New Materials Co ltd
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract

The invention discloses HJT low-temperature conductive silver paste containing silver nano-rods and a preparation method thereof, comprising a silver nano-rod suitable for HJT low-temperature conductive silver paste, a preparation method thereof and a use method of the silver nano-rod in HJT silver paste, wherein when the silver nano-rod is applied to HJT low-temperature conductive silver paste, excellent ohmic contact performance can be generated, and the silver nano-rod can obviously reduce the resistance of a silver grid line (namely, the electric power of the silver grid line is less than or equal to 4 multiplied by 10) under the condition of the same silver content when the silver nano-rod is added into HJT low-temperature cured conductive silver paste ‑6 Omega cm), does not affect printing performance and welding tension, shows high conductivity and excellent photoelectric conversion efficiency, and has wide application prospect.

Description

HJT low-temperature conductive silver paste containing silver nano short rods and preparation method thereof
Technical Field
The invention belongs to the technical field of solar cell electronic paste, and particularly relates to HJT low-temperature conductive silver paste containing silver nano short rods and a preparation method thereof.
Background
Along with the iteration of the photovoltaic cell technology, the HJT (Heterojunction Technology) high-efficiency heterojunction cell has the advantages of high photoelectric conversion efficiency, high double-sided rate, simplified equipment process flow, low light attenuation of products, strong stability, large cost reduction and synergy space and the like, and has wide prospect, thus becoming the development direction of a new generation of cell technology.
The substrate of the HJT cell is N-type monocrystalline silicon, the monocrystalline silicon layers on two sides are hydrogenated amorphous silicon layers (a-Si: H N-layer), and the monocrystalline silicon and the amorphous silicon form heterojunction (N-N and p-N); meanwhile, in order to obtain a better passivation effect, an intrinsic hydrogenated amorphous silicon layer (a-Si: H i-layer) is added between the crystalline silicon and the amorphous silicon to form a passivation layer, so that surface recombination of the crystalline silicon is greatly reduced, but the conductivity of the amorphous silicon is relatively poor, therefore, transparent oxide conductive films (TCO) are deposited on two sides of the battery to collect current, and finally, screen printing technology is adopted on the conductive films to form double-sided electrodes.
There have been related studies, such as a HJT battery of chinese patent application No. CN202111399527.2 and a method for preparing the same, including: compared with the traditional HJT battery, the HJT battery provided by the invention has the advantages that the silver nanowire layer is added between the TCO conductive layer and the gate electrode, the conductivity of the TCO conductive layer can be greatly improved by arranging the silver nanowire layer on the TCO conductive layer, the electron collection rate is further improved, and the conductivity of the whole path is greatly improved by further low-temperature welding of the silver nanowire layer and the TCO conductive layer and the low-temperature welding of the silver nanowire layer and the gate electrode; meanwhile, the addition of the silver nanowire layer can reduce the sheet resistance of the TCO conductive layer to 30ohm, and the light is not affected (TT is more than 98%), namely the generation efficiency of photo-generated electrons is hardly affected.
Currently, HJT batteries mainly use low-temperature (200-250 ℃) cured conductive silver paste, and unlike the high-temperature (700-800 ℃) conductive silver paste used in traditional batteries, the low-temperature cured silver paste mostly uses micron-sized flake silver powder, micron-sized spherical silver powder, submicron-sized spherical silver powder and dendritic silver powder, wherein the low-temperature silver paste used for a main grid needs to have good conductivity and excellent tensile force, and the low-temperature silver paste used for a fine grid also needs to have good conductivity and good printing performance.
However, the prior art has some defects and shortcomings:
1. the conventional silver powder has no low melting point effect at 200-250 ℃, can not form good lap joint in the grid line, can not form a good conductive path, and causes higher grid line body resistivity;
2. the adopted flake silver powder has large size span, large particles in the flake silver powder are difficult to pass through a screen during screen printing, and the conditions of broken grid lines, virtual printing, low aspect ratio and the like are easily caused, so that the photoelectric conversion efficiency is reduced;
3. the spherical silver powder is adopted, and meanwhile, lower resistivity is achieved, so that the silver content of the silver paste is high (95%), and the cost of the silver paste is high.
Disclosure of Invention
To solve the technical defects, the invention provides HJT low-temperature conductive silver paste containing silver nano-rods and a preparation method thereof, and the silver nano-rods comprise silver nano-rods suitable for HJT low-temperature conductive silver paste, a preparation method thereof and a use method of the silver nano-rods in HJT silver paste, wherein when the silver nano-rods are applied to HJT low-temperature conductive silver paste, excellent ohmic contact performance can be generated, and the silver nano-rods can be added into HJT low-temperature cured conductive silver paste to remarkably reduce the resistance of silver grid lines under the condition of the same silver content (namely, the electric power of the silver grid lines is less than or equal to 4 multiplied by 10) -6 Omega cm), does not affect printing performance and welding tension, shows high conductivity and excellent photoelectric conversion efficiency, and has wide application prospect.
The aim of the invention is achieved by the following technical scheme:
HJT low-temperature conductive silver paste containing silver nano-rods is prepared from the following components in percentage by mass:
85% -93% of silver powder, 2% -5% of resin, 3% -8% of organic solvent, 0.3% -0.5% of curing agent, 0.3% -0.5% of dispersing agent, 0.3% -0.5% of thixotropic agent and 1% -2% of coupling agent;
the silver powder is mixed powder of flaky silver powder, spherical silver powder and silver nano short rods, and the mass ratio of the flaky silver powder to the spherical silver powder to the silver nano short rods is 1:3:2; wherein the median particle diameter of the flake silver powder is 2-5 mu m, and the median particle diameter of the spherical silver powder is 0.2-1.0 mu m; the length of the silver nanometer short bar wire is 3-5 mu m, and the wire diameter is 200-500nm; the tap density of the spherical silver powder is 5.5-7.0g/cm 3 ；
The resin is selected from one of bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, carboxyl end-capped polyester resin, carboxyl acrylic resin, alicyclic epoxy resin, organosilicon modified epoxy resin, phenoxy resin, thermosetting acrylic resin and polyester resin;
the organic solvent is one or more selected from DBE, ethylene glycol tertiary butyl ether, diethylene glycol butyl ether acetate, terpineol, dihydro terpineol, alcohol ester twelve, tributyl citrate, diethylene glycol diethyl ether acetate, ethyl acetate, butyl acetate, acetonide glycerol, N-methyl pyrrolidone and propylene glycol butyl ether, and the mixture is in any proportion;
the curing agent is selected from one of dicyandiamide curing agent, imidazole curing agent, modified amine curing agent and anhydride curing agent;
the dispersing agent is one of BYK110, BYK111, tego 685, BYK 168, BYK102, BYK 3651, BYK4512, BYK ES80, liquid paraffin oil 300#, ED600JD, ANTI-TERRA-204, ED420 and ED 120;
the thixotropic agent is one selected from polyurea BYK410, castor oil THIXCIN R, hydrogenated castor oil ST-2, stearyl isocyanate BYKANOL-N and polyamide wax THIXATROL PLUS;
the coupling agent is selected from one of gamma-glycidoxypropyl trimethoxysilane (KH 560), gamma-methacryloxypropyl trimethoxysilane (KH-570), gamma-mercaptopropyl trimethoxysilane (KH 590), gamma-aminopropyl triethoxysilane (KH 550), neoalkoxy tri (dioctyl pyrophosphoric acid acyloxy) titanate, isopropyl trioleate acyloxy titanate and tetraisopropyl di (dioctyl phosphite) titanate (46B);
the preparation method of the silver nano short rod comprises the following steps:
s1-1: dissolving silver nitrate in polyalcohol to form solution A, wherein the molar concentration of the silver nitrate in the solution A is 0.1-3.0mol/L; the polyalcohol solvent is one of ethylene glycol, propylene glycol, butanediol, pentanediol and hexanediol;
s1-2: dissolving a nucleating agent in a polyol to form a solution B, wherein the concentration of the nucleating agent in the solution B is 0.001-0.008mol/L; the nucleating agent is salt, and is selected from one of sodium bromide, potassium iodide, ferric chloride, cupric chloride, manganese chloride, sodium chloride, nickel chloride, cobalt chloride, sodium carbonate, sodium hydroxide and sodium sulfate;
s1-3: dissolving a dispersing agent in polyalcohol to form a solution C, wherein the dosage of the dispersing agent is 0.5-2.0 times of the mass of the silver nitrate; the dispersing agent is one of polyethylene glycol, polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral and polyvinylpyrrolidone;
s1-4: adding a part of solution A and a part of solution B into solution C, mixing, wherein the silver nitrate consumption is 1% -5% of the solution A, the nucleating agent consumption is 0.1% -1.0% of the silver nitrate consumption, uniformly mixing, then transferring into an oil bath pool, heating to 100-150 ℃, reacting for 2-3h, and cooling to obtain silver nano short bar mother liquor D;
s1-5: dispersing the solution D into deionized water, wherein the dosage of the deionized water is 0.5-5 times of that of the solution D, adding a dispersing agent, wherein the dosage of the dispersing agent is 0.1-1.0 time of that of the silver nitrate, dissolving a reducing agent in the deionized water, wherein the dosage of the deionized water is 0.5-5 times of that of the solution D, and the weight of the reducing agent is 0.5-1.0 time of that of the silver nitrate to form a solution E, then simultaneously adding the solution E and the rest solution A into the solution D at a constant speed, and controlling the reaction temperature to be 20-30 ℃ and the charging time to be 0-5min; the dispersing agent is one of polyethylene glycol, polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral and polyvinylpyrrolidone; the reducing agent is selected from one of ascorbic acid, glucose, triethanolamine, formaldehyde, citric acid, hydrazine hydrate and sodium borohydride;
s1-6: after the reaction is finished, washing with water, washing with ethanol, centrifugally separating, and drying at 65 ℃ to obtain the silver nanometer short rod with the wire length of 3-5 mu m and the wire diameter of 200-500nm;
the preparation method of the HJT low-temperature conductive silver paste containing the silver nano-rods comprises the following steps of:
s1: mixing resin, an organic solvent, a dispersing agent, a thixotropic agent and a coupling agent according to the formula proportion, and dispersing for 2min at 800-1000rpm in a centrifugal dispersing machine to uniformly disperse the mixture;
s2: mixing the mixed organic matter and the curing agent at a low speed of 300-500rpm, and controlling the temperature at 20+/-5 ℃ to obtain an organic carrier;
s3: slowly adding silver powder into the organic carrier obtained in the step S2 in batches, and mixing for 2min at the rotating speed of 500-1000rpm to uniformly disperse the silver powder into the organic carrier to obtain coarse slurry;
s4: grinding the crude slurry through a three-roller mill:
first roller gap 90um and second roller gap 60um, mix 1 pass;
the first roller gap 60um and the second roller gap 30um, mixing 1 pass;
the first roller gap 30um and the second roller gap 20um are mixed for 1 time;
the first roller gap 20um and the second roller gap 10um are mixed for 3 times;
the first roller gap 15um and the second roller gap 6um are mixed for 3 times;
and after the silver paste is uniformly dispersed and the paste fineness is below 8 mu m, filtering to obtain HJT low-temperature conductive silver paste containing silver nano short rods.
In the invention, the following components are added:
the median tap density of the flake silver powder is 4.5-5.5g/cm 3 Silver nano short bar tap density 1.2-2.0g/cm 3 。
The resin is selected from bisphenol A epoxy resin NPL-128P.
The organic solvent is selected from diethylene glycol butyl ether, diethylene glycol diethyl ether acetate and DBE according to the mass ratio of 1:2:1.
The curing agent is selected from imidazole curing agent PN23.
The dispersing agent is selected from 300# and BYK4512.
The thixotropic agent is selected from BYK410.
The coupling agent is selected from gamma-glycidyl ether oxypropyl trimethoxysilane (KH 560).
The molar concentration of the silver nitrate in the solution A in the step S1-1 is 0.3-1.5mol/L; the method comprises the steps of dissolving silver nitrate in polyol to form a solution A, wherein a solvent is polyol, and firstly, the polyol is partially decomposed to generate aldehyde groups under the condition of heating (120-180 ℃), and the generated aldehyde groups reduce silver ions into silver simple substances; secondly, the process of generating aldehyde groups by the decomposition of the polyalcohol is slower, so that the whole reduction reaction is milder, and the reduced silver simple substance is arranged and aggregated into silver nanowires under the coating of the nucleating agent and the dispersing agent; thirdly, the polyol and water can be mixed and dissolved in any proportion, so that the next reaction is facilitated.
The concentration of the nucleating agent in the solution B in the step S1-2 is 0.003-0.008mol/L; the nucleating agent is selected from one of manganese chloride, copper chloride and ferric chloride; the nucleating agent is preferably halogen ions, firstly, the chlorine ions can be combined with silver ions to form crystal nuclei, and the silver ions are slowly released in the reaction process, so that the reaction process is more gentle; second, the addition of chloride ions can promote the formation of decahedral twinning nuclei (MTP), only MTP can be grown finally into silver nanowires; thirdly, the addition of the metal cations can remove oxygen dissolved in the reaction system, eliminate the corrosion of the oxygen to the silver nanowires and promote the growth of the silver nanowires; fourth, the addition amount of the halogen ions is very small, so that the halogen ions are easy to remove in the subsequent reaction process, and the final product is not adversely affected.
The dosage of the dispersing agent in the step S1-3 is 1.0-1.5 times of the mass of the silver nitrate; the dispersing agent is selected from polyvinylpyrrolidone K60; the dispersing agent is preferably polyvinylpyrrolidone (K60), a strong polar group (such as carbonyl) contained in PVP can form a coordination compound with silver ions to promote the conversion of silver ions into silver simple substances, the interaction between PVP and {100} interface crystal faces of MTP is stronger than the interaction between PVP and {111} crystal faces, and in the MTP growth process, PVP is used as a structure guiding agent and also used as a coating agent to prevent silver nanowires from gathering so as to prevent MTP from growing along the radial direction and guide MTP to grow along the axial direction; in the initial reaction process, PVP and silver nitrate have a mass ratio which is too small to be effectively coated, so that silver nanowires cannot be obtained, too much coating is caused, and silver crystal nuclei only can be obtained through isotropic growth; PVP K60 molecular weight is higher than K30, the solution viscosity of the polyalcohol is higher, and the higher solution viscosity can reduce the diffusion of substances in the later stage of the initial reaction, thereby preventing the self-assembly lengthening of the silver nanowire, and finally obtaining the silver nano short rod with the wire length of 3-5 mu m and the wire diameter of 200-500 nm.
In the step S1-4, the silver nitrate accounts for 2% -4% of the solution A, and the nucleating agent accounts for 0.1% -0.5% of the silver nitrate; the reaction temperature is 115-135 ℃.
In the step S1-5, the dosage of the deionized water is 2-4 times of that of the solution D; the dosage of the dispersing agent is 0.4 to 0.6 times of the mass of the silver nitrate; the dispersing agent is selected from polyvinylpyrrolidone K60; the reducing agent is selected from ascorbic acid; the weight of the reducing agent is 0.50-0.65 times of that of the silver nitrate; the reaction temperature is controlled at 23-27 ℃, and the feeding time is 1-3min; the reducing agent is preferably ascorbic acid, the reducing capability of the ascorbic acid is moderate, the reaction can be completed at normal temperature, and the reaction process is mild and easy to control; the amount of the reducing agent influences the reaction speed, too much reducing agent is used for violently generating a large amount of silver particle byproducts, too little reducing agent is used for realizing slow reaction speed, low efficiency, incomplete reaction and low yield.
In the steps S1-1 to S1-6, the reaction process is divided into two stages, S1-1 to S1-4 are primary reactions, and a one-pot method is adopted to react in a polyalcohol solvent to generate silver nanowire crystal nuclei; s1-5 to S1-6 are final reactions, silver nanowire crystal nuclei generated by S1-1 to S1-4 are dispersed into water in a solution state, after a dispersing agent and a reducing agent are added, the rest silver nitrate solution is added into a reaction solution for continuous reactions, so that reduced silver simple substances grow on the silver nanowire crystal nuclei, and after the reaction is finished, the silver nanowire crystal nuclei are washed by water, washed by alcohol and dried at 65 ℃, and finally the silver nanowire short bars are obtained.
And (3) filtering in the step S4, wherein the mesh number of the sieve is 500 meshes.
Compared with the prior art, the invention has the following advantages:
1. the invention discloses HJT low-temperature conductive silver paste containing silver nano short rods, which is found by the inventor in research that the silver nano short rods can be added into HJT low-temperature cured conductive silver paste to reduce the resistance of a silver grid line to (3.2-3.8) multiplied by 10 under the condition of the same silver content -6 Omega cm, and does not affect printing performance and soldering tension.
2. According to the HJT low-temperature conductive silver paste containing the silver nano-rods, the used silver nano-rods have the length of 3-5 mu m, the diameter of 200-500nm and the length of 3-5 mu m, and the silver nano-rods can form effective lap joints in the silver paste while meeting the printing performance of the silver paste, so that the resistance of the silver paste is reduced; the silver nano-rod with the diameter of 200-500nm has the effect of nano low melting point, can realize partial liquid phase sintering at low temperature, increases the contact area, forms a good conductive path, is beneficial to reducing the contact resistance, and meanwhile, when the silver nano-rod with the size is sintered, only partial micro-melting is realized, and the phenomenon that holes shrink severely like silver nano-particles are increased, so that the tensile force is reduced and the resistance is increased is avoided.
3. According to the HJT low-temperature conductive silver paste containing the silver nano-rods, the used silver nano-rods take high-purity silver nanowires as seed crystals, silver ions are reduced on the silver nanowires at a constant speed under the action of PVP, and the obtained product is almost free of silver nano-particles, high in purity, high in crystallinity and less in defect-free in the axial direction of the silver rods, so that the intrinsic resistivity of the silver nano-rods is extremely low.
4. The HJT low-temperature conductive silver paste containing the silver nano-rods has the advantages of mild reaction conditions, short reaction time and high efficiency. The silver powder yield is more than 99.5%, and the method is suitable for mass industrialized production.
Drawings
FIG. 1 is a scanning electron microscope (a: wire diameter; b: wire length) of a silver nano-rod prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope (a: wire diameter; b: wire length) of a silver nano-rod prepared in example 2 of the present invention;
FIG. 3 is a scanning electron microscope (a: wire diameter; b: wire length) of a silver nano-rod prepared in example 3 of the present invention;
FIG. 4 is a scanning electron microscope (a: wire diameter; b: wire length) of a silver nano-rod prepared in example 4 of the present invention;
FIG. 5 is a scanning electron micrograph (a: wire diameter; b: wire length) of a silver nano-rod prepared in comparative example 1 of the present invention;
FIG. 6 is a scanning electron micrograph (a: wire diameter; b: wire length) of a silver nano-rod prepared in comparative example 2 of the present invention;
FIG. 7 is a scanning electron micrograph (a: wire diameter; b: wire length) of a silver nano-rod prepared in comparative example 3 of the present invention;
fig. 8 is a schematic diagram of resistivity test printing of the low temperature cured conductive silver paste of the present invention HJT.
Detailed Description
The present invention is described in further detail by the following examples, which should not be construed as limiting the invention. Unless otherwise indicated, all starting materials and equipment used in the examples herein were purchased commercially, and all methods used in the examples, unless otherwise indicated, were conventional in the art.
Example 1:
HJT low-temperature conductive silver paste containing silver nano-rods is prepared from the following components in percentage by mass:
s1, 180g of silver nitrate is dissolved in 1L of propylene glycol to form a solution A, 28mL of the solution A1 is taken to form a solution A2, and the rest of the solution A2 is formed;
s2, 0.7520g of manganese chloride is dissolved in 1L of ethylene glycol, and 10mL of manganese chloride is taken to form a solution B;
s3 dissolving 6.3g PVP K60 in 462mL propylene glycol to form solution C
S4, adding the solution A1 and the solution B into the solution C, uniformly mixing, then moving to an oil bath pool, heating to 120 ℃, reacting for 2 hours, and cooling to obtain 500mL of silver nano short bar mother liquor D;
s5, dispersing 500mL of solution D into 1.5L of deionized water, dissolving 72g of PVP K60 completely, adding 900mL of deionized water into 99g of ascorbic acid to form solution E, adding the solution E and the solution A2 into the solution D at a constant speed by a peristaltic pump for 2min, and reacting at 23-27 ℃;
s6: after the reaction is finished, washing the silver nano short rod 1# by water until the electric conductivity is below 10 mu S/cm, washing the silver nano short rod by ethanol, centrifugally separating and drying the silver nano short rod at 65 ℃;
the silver nano short rod 1# obtained through the process is prepared into HJT conductive silver paste 1# according to the following formula and preparation method:
submicron spherical silver powder (D50:0.2-0.5 μm), 60g of spherical silver powder (D50:1.0-1.5 μm), 30g of silver nano-rod (1#);
bisphenol A epoxy resin NPL-128P 3g, solvent diethylene glycol butyl ether 1.25g, diethylene glycol diethyl ether acetate 2.5g and DBE 1.25g;
curing agent PN 23.3 g, dispersant 300#0.6g,BYK4512 0.2g, thixotropic agent BYK4100.3g and coupling agent KH560 0.6g;
s1: mixing resin, an organic solvent, a dispersing agent, a thixotropic agent and a coupling agent according to the formula proportion, and dispersing for 2min at 900rpm in a centrifugal dispersing machine to uniformly disperse the mixture;
s2: uniformly mixing the mixed organic matter and the curing agent at a low speed, and controlling the temperature to be 20+/-5 ℃ to obtain an organic carrier;
s3: slowly adding silver powder into the organic carrier obtained in the step S2 in batches, and mixing for 2min at the rotating speed of 600rpm to uniformly disperse the silver powder into the organic carrier to obtain coarse slurry;
s4: grinding the crude slurry through a three-roller mill:
first roller gap 90um and second roller gap 60um, mix 1 pass;
the first roller gap 60um and the second roller gap 30um, mixing 1 pass;
the first roller gap 30um and the second roller gap 20um are mixed for 1 time;
the first roller gap 20um and the second roller gap 10um are mixed for 3 times;
the first roller gap 15um and the second roller gap 6um are mixed for 3 times;
the silver paste is uniformly dispersed, the fineness of the paste is below 8 mu m, and the silver paste is filtered by a 500-mesh screen to obtain silver paste No. 1.
Example 2:
HJT low-temperature conductive silver paste containing silver nano-rods is prepared from the following components in percentage by mass:
s1, 180g of silver nitrate is dissolved in 1L of glycol to form a solution A, and 28mL of silver nitrate is taken to form a solution A 1 Remaining to form solution A 2 ；
S2, 0.7520g of manganese chloride is dissolved in 1L of ethylene glycol, and 10mL of manganese chloride is taken to form a solution B;
s3, 6.3g PVP K60 is dissolved in 462mL glycol to form a solution C;
s4 solution A 1 Adding the solution B and the solution C into the solution C, uniformly mixing, then transferring to an oil bath pool, heating to 120 ℃, reacting for 2 hours, and cooling to obtain 500mL of silver nano short bar mother solution D;
s5, dispersing 500mL of solution D into 1.5L of deionized water, dissolving 72g of PVP K60 completely, adding 900mL of deionized water into 99g of ascorbic acid to form solution E, adding the solution E and the solution A2 into the solution D at a constant speed by a peristaltic pump for 2min, and reacting at 23-27 ℃;
s6: after the reaction is finished, washing the silver nano short rod 2# by water until the electric conductivity is below 10 mu S/cm, washing the silver nano short rod by ethanol, centrifugally separating and drying the silver nano short rod 2# at 65 ℃;
the silver nano short rod No. 2 obtained through the process is prepared into HJT conductive silver paste No. 2 according to the following formula and preparation method:
submicron spherical silver powder (D50:0.2-0.5 μm), 60g of spherical silver powder (D50:1.0-1.5 μm), 30g of silver nanometer short rod (2#);
bisphenol A epoxy resin NPL-128P 3g, solvent diethylene glycol butyl ether 1.25g, diethylene glycol diethyl ether acetate 2.5g and DBE 1.25g;
curing agent PN 23.3 g, dispersant 300#0.6g,BYK4512 0.2g, thixotropic agent BYK4100.3g and coupling agent KH560 0.6g;
s1: mixing resin, an organic solvent, a dispersing agent, a thixotropic agent and a coupling agent according to the formula proportion, and dispersing for 2min at 900rpm in a centrifugal dispersing machine to uniformly disperse the mixture;
s2: uniformly mixing the mixed organic matter and the curing agent at a low speed, and controlling the temperature to be 20+/-5 ℃ to obtain an organic carrier;
s3: slowly adding silver powder into the organic carrier obtained in the step S2 in batches, and mixing for 2min at the rotating speed of 600rpm to uniformly disperse the silver powder into the organic carrier to obtain coarse slurry;
s4: grinding the crude slurry through a three-roller mill:
first roller gap 90um and second roller gap 60um, mix 1 pass;
the first roller gap 60um and the second roller gap 30um, mixing 1 pass;
the first roller gap 30um and the second roller gap 20um are mixed for 1 time;
the first roller gap 20um and the second roller gap 10um are mixed for 3 times;
the first roller gap 15um and the second roller gap 6um are mixed for 3 times;
the silver paste is uniformly dispersed, the fineness of the paste is below 8 mu m, and the silver paste is filtered by a 500-mesh screen to obtain silver paste No. 2.
Example 3:
HJT low-temperature conductive silver paste containing silver nano-rods is prepared from the following components in percentage by mass:
s1, 180g of silver nitrate is dissolved in 1L of glycol to form a solution A, 28mL of the solution A1 is taken to form a solution A2, and the rest of the solution A2 is formed;
s2, 0.7167g of copper chloride is dissolved in 1L of propylene glycol, and 10mL of copper chloride is taken to form a solution B;
s3, 6.3g PVP K60 is dissolved in 462mL glycol to form a solution C;
s4, adding the solution A1 and the solution B into the solution C, uniformly mixing, then moving to an oil bath pool, heating to 120 ℃, reacting for 2 hours, and cooling to obtain 500mL of silver nano short bar mother liquor D;
s5, dispersing 500mL of solution D into 1.5L of deionized water, dissolving 72g of PVP K60 completely, adding 900mL of deionized water into 99g of ascorbic acid to form solution E, adding the solution E and the solution A2 into the solution D at a constant speed by a peristaltic pump for 2min, and reacting at 23-27 ℃;
s6: after the reaction is finished, washing the silver nanometer short rod 3# by water until the electric conductivity is below 10 mu S/cm, washing the silver nanometer short rod by ethanol, centrifugally separating, and drying at 65 ℃;
the silver nano short rod 3# obtained through the process is prepared into HJT conductive silver paste 3# according to the following formula and preparation method:
15g of submicron spherical silver powder (D50:0.2-0.5 mu m), 60g of spherical silver powder (D50:1.0-1.5 mu m) and 30g of silver nanometer short rod (3#);
bisphenol A epoxy resin NPL-128P 3g, solvent diethylene glycol butyl ether 1.25g, diethylene glycol diethyl ether acetate 2.5g and DBE 1.25g;
curing agent PN 23.3 g, dispersant 300#0.6g,BYK4512 0.2g, thixotropic agent BYK4100.3g and coupling agent KH560 0.6g;
s1: mixing resin, an organic solvent, a dispersing agent, a thixotropic agent and a coupling agent according to the formula proportion, and dispersing for 2min at 900rpm in a centrifugal dispersing machine to uniformly disperse the mixture;
s2: uniformly mixing the mixed organic matter and the curing agent at a low speed, and controlling the temperature to be 20+/-5 ℃ to obtain an organic carrier;
s3: slowly adding silver powder into the organic carrier obtained in the step S2 in batches, and mixing for 2min at the rotating speed of 600rpm to uniformly disperse the silver powder into the organic carrier to obtain coarse slurry;
s4: grinding the crude slurry through a three-roller mill:
first roller gap 90um and second roller gap 60um, mix 1 pass;
the first roller gap 60um and the second roller gap 30um, mixing 1 pass;
the first roller gap 30um and the second roller gap 20um are mixed for 1 time;
the first roller gap 20um and the second roller gap 10um are mixed for 3 times;
the first roller gap 15um and the second roller gap 6um are mixed for 3 times;
the silver paste is uniformly dispersed, the fineness of the paste is below 8 mu m, and the silver paste is filtered by a 500-mesh screen to obtain silver paste No. 3.
Example 4:
HJT low-temperature conductive silver paste containing silver nano-rods is prepared from the following components in percentage by mass:
s1, 180g of silver nitrate is dissolved in 1L of glycol to form a solution A, 28mL of the solution A1 is taken to form a solution A2, and the rest of the solution A2 is formed;
s2, 0.4866g of ferric chloride is dissolved in 1L of ethylene glycol, and 10mL of the solution is taken to form a solution B;
s3, 6.3g PVP K60 is dissolved in 462mL glycol to form a solution C;
s4, adding the solution A1 and the solution B into the solution C, uniformly mixing, then moving to an oil bath pool, heating to 120 ℃, reacting for 2 hours, and cooling to obtain 500mL of silver nano short bar mother liquor D;
s5, dispersing 500mL of solution D into 1.5L of deionized water, dissolving 72g of PVP K60 completely, adding 900mL of deionized water into 99g of ascorbic acid to form solution E, adding the solution E and the solution A2 into the solution D at a constant speed by a peristaltic pump for 2min, and reacting at 23-27 ℃;
s6: after the reaction is finished, washing the silver nanometer short rod 4# by water until the electric conductivity is below 10 mu S/cm, washing the silver nanometer short rod by ethanol, centrifugally separating, and drying at 65 ℃;
the silver nano short rod 4# obtained through the process is prepared into HJT conductive silver paste 4# according to the following formula and preparation method:
submicron spherical silver powder (D50:0.2-0.5 μm), 60g of spherical silver powder (D50:1.0-1.5 μm), 30g of silver nanometer short rod (4#);
bisphenol A epoxy resin NPL-128P 3g, solvent diethylene glycol butyl ether 1.25g, diethylene glycol diethyl ether acetate 2.5g and DBE 1.25g;
0.3g of curing agent PN23, 300#0.6g,BYK4512 0.2g g of dispersing agent BYK410, 0.3g of thixotropic agent KH560, and 0.6g of coupling agent;
s1: mixing resin, an organic solvent, a dispersing agent, a thixotropic agent and a coupling agent according to the formula proportion, and dispersing for 2min at 900rpm in a centrifugal dispersing machine to uniformly disperse the mixture;
s2: uniformly mixing the mixed organic matter and the curing agent at a low speed, and controlling the temperature to be 20+/-5 ℃ to obtain an organic carrier;
s3: slowly adding silver powder into the organic carrier obtained in the step S2 in batches, and mixing for 2min at the rotating speed of 600rpm to uniformly disperse the silver powder into the organic carrier to obtain coarse slurry;
s4: grinding the crude slurry through a three-roller mill:
first roller gap 90um and second roller gap 60um, mix 1 pass;
the first roller gap 60um and the second roller gap 30um, mixing 1 pass;
the first roller gap 30um and the second roller gap 20um are mixed for 1 time;
the first roller gap 20um and the second roller gap 10um are mixed for 3 times;
the first roller gap 15um and the second roller gap 6um are mixed for 3 times;
the silver paste is uniformly dispersed, the fineness of the paste is below 8 mu m, and the silver paste is filtered by a 500-mesh screen to obtain silver paste No. 4.
Comparative example 1
The initial reaction temperature was increased to 140℃as compared with example 1, except that example 1 was conducted.
Comparative example 2
The initial reaction time was prolonged to 4 hours as compared with example 1, except that example 1 was followed.
Comparative example 3
The final reaction feed time was reduced to 3s compared to example 1, except that example 1 was followed.
Comparative example 4
Compared with example 1, the silver nano-rods were replaced with plate-like silver powder (D50: 2-5 μm) at the stage of paste preparation, and the same as in example 1 was followed.
The performance test method comprises the following steps:
1. the morphology analysis and the diameter and length measurement were carried out on each example and comparative example using a field emission scanning electron microscope MIRA4 LMH eds: ultim Max 40. The NOVA 4200e type specific surface area tester is used for testing the specific surface area, the JZ-7 type powder tap density tester is used for testing the tap density, and the viscosity tester is used for testing the viscosity at the temperature of 10rpm and 25 ℃ and Brookf i led HB SC-14. The test results are shown in table 1;
2. resistivity tests were performed on each of the examples and comparative examples, and the resistivity was calculated according to the formula ρ=rs/L; wherein ρ is resistivity, L is the length of the material, S is the cross-sectional area of the material, and R is the resistance value; printing the silver paste prepared in each embodiment into lines shown in fig. 8 by a screen printing mode, curing for 30min at 200 ℃, wherein the width of the lines is 1mm and the length of the lines is 100mm, and then performing omnibearing scanning test on the lines by using a super-depth-of-field 3D microscope to obtain average film thickness data; and finally, multiplying the average film thickness data by the line width (1 mm) to obtain the sectional area of the line, wherein the line length is a fixed value (100 mm), and the R data is measured by a universal meter. The resistivity of the printed lines can be obtained through calculation and unit conversion, and the average resistivity of the sample can be obtained through the average of a plurality of lines; the test results are shown in table 1;
3. screen printing is adopted for each example and comparative example, grid lines are printed on the surface of an ITO silicon wafer, the condition of the grid lines is observed under a 3D microscope, and the test results are shown in Table 1;
table 1 main performance indexes of the silver nanorods and silver paste obtained in examples and comparative examples:
analysis of results:
1. the silver nano short rod used by the HJT conductive silver paste is obtained by adopting a one-pot method and a step method, the silver nano short rod has moderate length (3-5 mu m) and moderate diameter (200-500 nm), the silver rod has few defects, high crystallinity and small specific surface, the bridge effect can be achieved by adding the silver paste, the lap joint between silver powder is easy to realize, the resistance of the silver paste can be obviously reduced, and the silver paste has good dispersibility (examples 1-3).
2. Example 1 illustrates in comparison with comparative examples 1-2: increasing the reaction temperature or prolonging the reaction time in the initial reaction stage can lead to thickening and lengthening of the initial reaction product, further lead to the final reaction product exceeding a reasonable line length and line diameter range, lead to subsequent incapability of pulping and printing.
3. Example 1 illustrates in comparison with comparative example 3: shortening the charging time in the final reaction stage can lead to uneven size distribution of the product, increased content of the particle powder, increased specific surface area, poor dispersibility of silver powder, increased resistivity after paste preparation and poor printing performance.
4. Examples 1-3 illustrate in comparison with comparative example 4: under the same silver content and the same preparation process of the formula, the resistivity of the HJT conductive silver paste added with the silver nano-shorting bar is obviously reduced, and the printing performance is basically kept unchanged.
The formulation and silver powder preparation process of the examples are obviously superior to those of the comparative examples by comparing the basic performances of the examples and the comparative examples.
The above examples of the present invention are only examples for clearly illustrating the present invention, and are not limiting of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.

Claims (10)

1. HJT low-temperature conductive silver paste containing silver nano-rods is characterized in that: the composition is prepared from the following components in percentage by mass:
85% -93% of silver powder, 2% -5% of resin, 3% -8% of organic solvent, 0.3% -0.5% of curing agent, 0.3% -0.5% of dispersing agent, 0.3% -0.5% of thixotropic agent and 1% -2% of coupling agent;
the silver powder is mixed powder of flaky silver powder, spherical silver powder and silver nano short rods, and the mass ratio of the flaky silver powder to the spherical silver powder to the silver nano short rods is 1:3:2; wherein the median particle diameter of the flake silver powder is 2-5 mu m, and the median particle diameter of the spherical silver powder is 0.2-1.0 mu m; the length of the silver nanometer short bar wire is 3-5 mu m, and the wire diameter is 200-500nm; the tap density of the spherical silver powder is 5.5-7.0g/cm 3 ；
The resin is selected from one of bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, carboxyl end-capped polyester resin, carboxyl acrylic resin, alicyclic epoxy resin, organosilicon modified epoxy resin, phenoxy resin, thermosetting acrylic resin and polyester resin;
the organic solvent is one or more selected from DBE, ethylene glycol tertiary butyl ether, diethylene glycol butyl ether acetate, terpineol, dihydro terpineol, alcohol ester twelve, tributyl citrate, diethylene glycol diethyl ether acetate, ethyl acetate, butyl acetate, acetonide glycerol, N-methyl pyrrolidone and propylene glycol butyl ether, and the mixture is in any proportion;
the curing agent is selected from one of dicyandiamide curing agent, imidazole curing agent, modified amine curing agent and anhydride curing agent;
the dispersing agent is one of BYK110, BYK111, tego 685, BYK 168, BYK102, BYK 3651, BYK4512, BYK ES80, liquid paraffin oil 300#, ED600JD, ANTI-TERRA-204, ED420 and ED 120;
the thixotropic agent is one selected from polyurea BYK410, castor oil THIXCIN R, hydrogenated castor oil ST-2, stearyl isocyanate BYKANOL-N and polyamide wax THIXATROL PLUS;
the coupling agent is selected from one of gamma-glycidol ether oxypropyl trimethoxy silane, gamma-methacryloxypropyl trimethoxy silane, gamma-mercaptopropyl trimethoxy silane, gamma-aminopropyl triethoxy silane, neoalkoxy tri (dioctyl pyrophosphoryl) titanate, isopropyl trioleate acyloxy titanate and tetraisopropyl di (dioctyl phosphite) titanate;
the preparation method of the silver nano short rod comprises the following steps:
s1-1: dissolving silver nitrate in polyalcohol to form solution A, wherein the molar concentration of the silver nitrate in the solution A is 0.1-3.0mol/L; the polyalcohol solvent is one of ethylene glycol, propylene glycol, butanediol, pentanediol and hexanediol;
s1-2: dissolving a nucleating agent in a polyol to form a solution B, wherein the concentration of the nucleating agent in the solution B is 0.001-0.008mol/L; the nucleating agent is salt, and is selected from one of sodium bromide, potassium iodide, ferric chloride, cupric chloride, manganese chloride, sodium chloride, nickel chloride, cobalt chloride, sodium carbonate, sodium hydroxide and sodium sulfate;
s1-3: dissolving a dispersing agent in polyalcohol to form a solution C, wherein the dosage of the dispersing agent is 0.5-2.0 times of the mass of the silver nitrate; the dispersing agent is one of polyethylene glycol, polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral and polyvinylpyrrolidone;
s1-4: adding a part of solution A and a part of solution B into solution C, mixing, wherein the silver nitrate consumption is 1% -5% of the solution A, the nucleating agent consumption is 0.1% -1.0% of the silver nitrate consumption, uniformly mixing, then transferring into an oil bath pool, heating to 100-150 ℃, reacting for 2-3h, and cooling to obtain silver nano short bar mother liquor D;
s1-5: dispersing the solution D into deionized water, wherein the dosage of the deionized water is 0.5-5 times of that of the solution D, adding a dispersing agent, wherein the dosage of the dispersing agent is 0.1-1.0 time of that of silver nitrate, dissolving a reducing agent into a certain amount of deionized water, wherein the dosage of the deionized water is 0.5-5 times of that of the solution D, and the weight of the reducing agent is 0.5-1.0 time of that of the silver nitrate to form a solution E, then simultaneously adding the solution E and the rest solution A into the solution D at a constant speed, and controlling the reaction temperature to be 20-30 ℃ and the charging time to be 0-5min; the dispersing agent is one of polyethylene glycol, polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral and polyvinylpyrrolidone; the reducing agent is selected from one of ascorbic acid, glucose, triethanolamine, formaldehyde, citric acid, hydrazine hydrate and sodium borohydride;
s1-6: after the reaction is finished, washing with water, washing with ethanol, centrifugally separating, and drying at 65 ℃ to obtain the silver nanometer short rod with the wire length of 3-5 mu m and the wire diameter of 200-500nm;
the preparation method of the HJT low-temperature conductive silver paste containing the silver nano-rods comprises the following steps of:
s1: mixing resin, an organic solvent, a dispersing agent, a thixotropic agent and a coupling agent according to the formula proportion, and dispersing for 2min at 800-1000rpm in a centrifugal dispersing machine to uniformly disperse the mixture;
s2: mixing the mixed organic matter and the curing agent at a low speed of 300-500rpm, and controlling the temperature at 20+/-5 ℃ to obtain an organic carrier;
s3: slowly adding silver powder into the organic carrier obtained in the step S2 in batches, and mixing for 2min at the rotating speed of 500-1000rpm to uniformly disperse the silver powder into the organic carrier to obtain coarse slurry;
s4: grinding the crude slurry through a three-roller mill:
first roller gap 90um and second roller gap 60um, mix 1 pass;
the first roller gap 60um and the second roller gap 30um, mixing 1 pass;
the first roller gap 30um and the second roller gap 20um are mixed for 1 time;
the first roller gap 20um and the second roller gap 10um are mixed for 3 times;
the first roller gap 15um and the second roller gap 6um are mixed for 3 times;
and after the silver paste is uniformly dispersed and the paste fineness is below 8 mu m, filtering to obtain HJT low-temperature conductive silver paste containing silver nano short rods.
2. A HJT low temperature conductive silver paste containing silver nanorods according to claim 1, wherein: the median tap density of the flake silver powder is 4.5-5.5g/cm 3 Silver nano short bar tap density 1.2-2.0g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The resin is selected from bisphenol A epoxy resin NPL-128P.
3. A HJT low temperature conductive silver paste containing silver nanorods according to claim 1, wherein: the organic solvent is selected from diethylene glycol butyl ether, diethylene glycol diethyl ether acetate and DBE according to the mass ratio of 1:2:1.
4. A HJT low temperature conductive silver paste containing silver nanorods according to claim 1, wherein: the curing agent is selected from imidazole curing agent PN23; the dispersing agent is selected from 300# and BYK4512; the thixotropic agent is selected from BYK410; the coupling agent is selected from gamma-glycidyl ether oxypropyl trimethoxy silane.
5. A HJT low temperature conductive silver paste containing silver nanorods according to claim 1, wherein: the molar concentration of the silver nitrate in the solution A in the step S1-1 is 0.3-1.5mol/L; the silver nitrate is dissolved in the polyol to form a solution A, and the solvent is the polyol.
6. A HJT low temperature conductive silver paste containing silver nanorods according to claim 1, wherein: the concentration of the nucleating agent in the solution B in the step S1-2 is 0.003-0.008mol/L; the nucleating agent is selected from one of manganese chloride, copper chloride and ferric chloride.
7. A HJT low temperature conductive silver paste containing silver nanorods according to claim 1, wherein: the dosage of the dispersing agent in the step S1-3 is 1.0-1.5 times of the mass of the silver nitrate; the dispersing agent is selected from polyvinylpyrrolidone K60.
8. A HJT low temperature conductive silver paste containing silver nanorods according to claim 1, wherein: in the step S1-4, the silver nitrate accounts for 2% -4% of the solution A, and the nucleating agent accounts for 0.1% -0.5% of the silver nitrate; the reaction temperature is 115-135 ℃.
9. A HJT low temperature conductive silver paste containing silver nanorods according to claim 1, wherein: in the step S1-5, the dosage of the deionized water is 2-4 times of that of the solution D; the dosage of the dispersing agent is 0.4 to 0.6 times of the mass of the silver nitrate; the dispersing agent is selected from polyvinylpyrrolidone K60; the reducing agent is selected from ascorbic acid; the weight of the reducing agent is 0.50-0.65 times of that of the silver nitrate; the reaction temperature is controlled at 23-27 ℃, and the feeding time is 1-3min.
10. A HJT low temperature conductive silver paste containing silver nanorods according to claim 1, wherein: and (3) filtering in the step S4, wherein the mesh number of the sieve is 500 meshes.
CN202310750262.9A 2023-06-25 2023-06-25 HJT low-temperature conductive silver paste containing silver nano short rods and preparation method thereof Pending CN116564579A (en)

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