WO2019085576A1 - 用于制备太阳能电池电极的多元纳米材料、包括其的糊剂组合物及太阳能电池电极和电池 - Google Patents

用于制备太阳能电池电极的多元纳米材料、包括其的糊剂组合物及太阳能电池电极和电池 Download PDF

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WO2019085576A1
WO2019085576A1 PCT/CN2018/099589 CN2018099589W WO2019085576A1 WO 2019085576 A1 WO2019085576 A1 WO 2019085576A1 CN 2018099589 W CN2018099589 W CN 2018099589W WO 2019085576 A1 WO2019085576 A1 WO 2019085576A1
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nano
oxide
component
mol
nanomaterial
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PCT/CN2018/099589
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French (fr)
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张洪旺
史卫利
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无锡帝科电子材料股份有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to the field of solar cell manufacturing technology, and in particular to a multi-component nano material for preparing a solar cell electrode, a paste composition including the same, and a solar cell electrode and a battery.
  • the manufacturing method of the front electrode of the crystalline silicon solar cell in the industry is to print the front electrode with the conductive silver paste on the crystalline silicon cell by screen printing technology, and then form a close contact with the n-type silicon through the process of rapid high-temperature sintering.
  • Front conductive electrode grid line is one of the main research directions in the industry.
  • the glass powder in the silver paste has a corrosive component, such as Pb, which gradually melts and reacts with the anti-reflection layer of silicon nitride, thereby corroding the anti-reflection layer and simultaneously dissolving a part of the slurry.
  • a corrosive component such as Pb
  • Silver powder During the subsequent cooling process, the silver melted in the glass gradually becomes supersaturated and precipitates, and island-shaped silver particles are formed on the surface of the n-type silicon.
  • the glass is also deposited on the surface of the n-type crystalline silicon as the temperature is lowered to form a glass layer having a thickness of about several tens of nanometers.
  • the inverted pyramid type silver island particles pass through the tunneling effect, and the photogenerated current generated by the n-type crystalline silicon is transmitted to the front silver electrode through the glass layer.
  • the number and volume of silver islands have a great influence on the series resistance of the entire cell. Reducing the series resistance requires a large number of silver islands, and the volume cannot be too large.
  • the current silver paste preparation sintering process generally requires increasing the sintering temperature or increasing the residence time in the high temperature region to increase the number of silver islands, but at the same time, the volume of the silver island is too large, which tends to cause the electrode to burn through.
  • a conductive silver paste that needs to be sintered into an electrode can etch away the antireflection layer at a relatively low sintering temperature, and the formed electrode is formed. It has good ohmic contact with the underlying n-type crystalline silicon.
  • the silver paste commonly used in the industry is a product of foreign companies such as DuPont of the United States, Heraeus of Germany, and Samsung of South Korea.
  • the products of domestic silver paste company are not perfect enough.
  • the main problems are as follows: the conversion efficiency of crystalline silicon battery is not high enough, the volume resistance of conductive silver paste is large, the bonding strength of silver layer and silicon is general, and the sintering temperature range of silver paste is narrow. Can only be applied to higher sintering temperatures.
  • the composition, content, particle size and softening temperature of the glass powder used in the positive silver paste directly affect the contact resistance, the ability to penetrate the anti-reflection layer, the conductivity of the electrode, and the adhesion between the electrode and the substrate. Thereby affecting the photoelectric conversion efficiency and service life of the solar cell.
  • the morphology and particle size of the glass frit also have an important influence on the sintering of the slurry.
  • the preparation of the glass frit is generally carried out by a physical pulverization method of high-temperature melting-low temperature water quenching-milling as described in the patent US8889980.
  • This top-down process has poor control over the morphology and particle size of the glass frit, and the particle size distribution is relatively broad, typically in the broad range of 1-10 microns. This will affect the uniformity of sintering, so that the distribution of series resistance across the battery is uneven and the resistance is high, thereby affecting the photoelectric conversion efficiency of the battery.
  • the use of a micron-sized powder is equivalent to the melting point of the bulk thereof, and the sintering temperature of the slurry prepared therefrom cannot be effectively reduced.
  • the present invention aims to provide a multi-component nano material for preparing a solar cell electrode, a paste composition comprising the same, and a solar cell electrode and a battery to solve the prior art paste composition due to the glass powder morphology contained therein
  • the uneven distribution of the series resistance of the battery and the high resistance caused by the unevenness of the particle size, and the use of the micron-sized powder, the sintering temperature is high, thereby affecting the technical problem of the photoelectric conversion efficiency of the battery.
  • a multi-component nanomaterial for preparing a solar cell electrode comprises 1.0 mol% to 60.0 mol% of nano lead oxide PbO, and 1.0 mol% to 65.0 mol% of nano cerium oxide TeO 2 .
  • the multi-component nano material further contains 0.1 mol% to 50 mol% of lithium oxide Li 2 O.
  • the multi-component nano material further comprises other nano materials, and the other nano materials are selected from the group consisting of nano sodium oxide Na 2 O, nano potassium oxide K 2 O, nano magnesium oxide MgO, nano calcium oxide CaO, nano cerium oxide SrO, nano cerium oxide BaO , nano bismuth oxide Bi 2 O 3 , nano phosphorus oxide P 2 O 5 , nano silicon oxide SiO 2 , nano boron oxide B 2 O 3 , nano zinc oxide ZnO, nano nickel oxide NiO, nano copper oxide CuO, nano tungsten oxide WO 3.
  • the multi-component nano material comprises 1.0 mol% to 50.0 mol% of nano lead oxide PbO, 1.0 mol% to 55.0 mol% of nano cerium oxide TeO 2 and 0.1 mol% to 45 mol% of nano Li 2 O.
  • the molar ratio of Pb to Te in the multi-component nanomaterial is 0.05 to 20:1, preferably 0.1 to 10:1.
  • the content of other nano materials accounts for 1 to 25 mol% of the multi-component nano material.
  • the particle diameter of the multi-component nano material includes one or more of three particle diameter ranges of 1 to 100 nm, 1 to 60 nm, and 5 to 50 nm.
  • a paste composition for preparing a solar cell electrode comprises 60 to 95% by weight of conductive powder, 1.0 to 20% by weight of an organic vehicle, 0.1 to 5% by weight of any of the above-mentioned multi-component nanomaterials, and the balance of additives.
  • the additive is one or more selected from the group consisting of a dispersant, a thixotropic agent, a plasticizer, a viscosity stabilizer, an antifoaming agent, a pigment, a UV stabilizer, an antioxidant, and a coupling agent.
  • the conductive powder is silver powder.
  • a solar cell electrode is provided.
  • the solar cell is prepared from the paste composition of any of the above.
  • a solar cell including an electrode is provided.
  • the electrode is the above-described solar cell electrode prepared from the paste composition of the present invention.
  • the particle size of the nanoparticles prepared by the method of the present invention can be reduced to less than one percent of the glass powder prepared by a conventional top-down process, and the particle size distribution is uniform. Since the particle size of the multi-component nano material particles is small, it can be more uniformly dispersed in the electron silver paste, and in particular, the melting point of the nanoparticles is significantly lower than that of the bulk and the micron material.
  • the optimum sintering temperature of the conductive silver paste using the nanoparticles can be significantly lower than the sintering temperature of the positive silver paste using the conventional glass powder, thereby forming a more uniform silver-silicon between the lower temperature sintering processes.
  • a thinner oxide layer results in a better ohmic contact, which reduces series resistance and makes it more uniform.
  • the paste composition of the invention can reduce the optimum sintering temperature while reducing the contact resistance, adapt to a more advanced battery process, can reduce the adverse effect of high surface resistance on the pn junction, thereby improving the efficiency of the solar cell, and Improve the academic performance of the electrodes made from it.
  • a front side conductive silver paste for a crystalline silicon solar cell is prepared by providing a glass powder widely used in the current silver paste by using a multi-component nano material.
  • the technical scheme realized by the invention adopts a novel multi-component nano material, and the glass powder prepared by the traditional method can effectively lower the softening temperature, so that the nano powder can melt the silver powder particles at a relatively low sintering temperature, and can A large amount of silver nano-colloid particles are formed between the glass layer and the emitter, which reduces the series resistance of the battery and makes the resistance distribution more uniform.
  • the multi-component nanomaterial of the present invention has a softening temperature of less than 300 °C.
  • a multi-component nanomaterial for preparing a solar cell electrode comprises 1.0 mol% to 60.0 mol% of nano lead oxide PbO, and 1.0 mol% to 65.0 mol% of nano cerium oxide TeO 2 .
  • the particle size of the multi-component nanoparticles prepared by the invention can be reduced to less than one percent of the glass powder prepared by the conventional top-down process, and the particle size distribution is uniform, so that it can be more uniform. Dispersed in the electronic silver paste. Since the particle size of the multi-component nano material particles is small and the melting point is low, the sintering temperature can be lowered, thereby forming a more uniform and thinner oxide layer between the silver and silicon during the sintering process, thereby obtaining a better ohmic contact, thereby reducing the series connection. Resist and make it more evenly distributed.
  • the smaller particle size can also achieve the same volume filling in the case of a small amount (wt%), thereby increasing the silver content in the slurry and the conductivity after sintering of the slurry, and further reducing the series resistance, and finally improving the photoelectric conversion. effectiveness.
  • the solar cell electronic silver paste containing the multi-component nano material of the invention has simple production process, can adapt to lower sintering temperature, high conversion rate of crystalline silicon battery, low series resistance and good printability.
  • the paste composition containing the solar cell electronic silver paste of the invention can reduce the adverse resistance of the high surface resistance to the pn junction while reducing the contact resistance, thereby improving the efficiency of the solar cell and improving the performance of the electrode manufactured thereby. .
  • the multi-element nano material further contains 0.1 mol% to 50 mol% of nano Li 2 O. More preferably, the multi-component nanomaterial comprises 1.0 mol% to 50.0 mol% of nano lead oxide, 1.0 mol% to 55.0 mol% of nano cerium oxide, and 0.1 mol% to 45 mol% of nano Li 2 O. Further preferably, the multi-component nano material further comprises other nano materials, and the other nano materials are selected from the group consisting of nano sodium oxide Na 2 O, nano potassium oxide K 2 O, nano magnesium oxide MgO, nano calcium oxide CaO, nano cerium oxide SrO, nano cerium oxide.
  • the molar ratio of Pb to Te in the multi-component nanomaterial is 0.05-20:1.
  • the molar ratio of Pb to Te in the multi-component nanomaterial is from 0.1 to 10:1.
  • the multi-component nanomaterial can dissolve the silver at a lower temperature while still maintaining a good etching effect on the silicon substrate anti-reflection layer.
  • a thinner layer of oxide can be formed, reducing contact resistance and increasing conversion.
  • the other nanomaterials are present in an amount of from 1 to 25 mol% of the multi-element nanomaterial.
  • These multi-component nanomaterials can play different roles in this content, for example, nano-potassium oxide and nano-oxide nano-ring can play a role in reducing contact resistance.
  • Nano-ZnO helps to extend the vitrification range of multi-element nanomaterials.
  • Nano-cerium oxide helps to improve the durability of multi-component nanomaterials.
  • the alkaline oxide of the alkaline earth element helps to improve the reactivity of the multi-component nanomaterial with the anti-reflection layer.
  • a method for preparing a multi-element nanomaterial of the present invention is a bottom-up process comprising a chemistry performed at a certain temperature in an organic liquid phase. Synthesis is achieved by the following steps:
  • the second component nanoparticle then adding a second metal compound to the reaction solvent containing the first metal compound nanoparticle, the second metal compound reacts at a certain temperature, and is formed in a solvent
  • the nanoparticles of a certain compound of the first metal are seeds, and after a certain reaction time, nanoparticles of a certain compound of the second metal are grown beside the nanoparticles of the first metal compound;
  • reaction temperatures in steps a), b) and c) are 200 to 600 ° C, 200 to 500 ° C and 220 to 400 ° C, respectively.
  • the nanoparticles of the second metal compound in step b) are linked to the seed of the nanoparticles of the first metal compound by forming a chemical bond.
  • the metals in steps a), b) and c) include PbO, TeO 2 , Li 2 O, Na 2 O, K 2 O, MgO, CaO, SrO, BaO, Bi 2 O 3 , P 2 O 5 Two or more of the group consisting of SiO 2 , B 2 O 3 , ZnO, NiO, CuO, WO 3 , MoO 3 , CoO, RuO, and TiO 2 .
  • reaction time in steps a), b) and c) is 10 to 100 minutes, 15 to 80 minutes and 30 to 60 minutes, respectively;
  • the metal compound nanoparticles obtained by the reaction in steps a), b) and c) have particle diameters of 1 to 100 nm, 1 to 60 nm and 5 to 50 nm, respectively.
  • the cleaning solvent in the step e) is one or a mixture of two or more of water, acetone, methyl ethyl ketone, methyl ether, diethyl ether, methanol, ethanol, propanol and isopropanol.
  • a paste composition for preparing a solar cell electrode comprises 60 to 95% by weight of conductive powder, 1.0 to 20% by weight of an organic vehicle, 0.1 to 5% by weight of any of the above-mentioned multi-component nanomaterials, and the balance of additives.
  • the paste composition comprises 80 to 95% by weight of silver powder, 0.5 to 3% by weight of a multi-component nano material, 5 to 15% by weight of an organic vehicle, and 0.1 to 0.5% by weight of an additive.
  • the additive is one or more selected from the group consisting of a dispersant, a thixotropic agent, a plasticizer, a viscosity stabilizer, an antifoaming agent, a pigment, a UV stabilizer, an antioxidant, and a coupling agent.
  • the conductive powder is silver powder.
  • a solar cell electrode is provided.
  • the solar cell is prepared from the paste composition of any of the above.
  • a solar cell including an electrode is provided.
  • the electrode is the above-described solar cell electrode prepared from the paste composition of the present invention.
  • the solar cell electrode component comprises silver powder, a multi-component nanomaterial, and an organic vehicle.
  • the composition of the solar cell electrode of the present invention will be described in more detail.
  • a paste composition for preparing a solar cell electrode contains silver powder as a conductive powder.
  • the particle size of the silver powder can be on the order of nanometers or micrometers.
  • the silver powder may have a particle size of several tens to several hundreds of nanometers, or several to several tens of micrometers.
  • the silver powder may be a mixture of two or more silver powders having different particle sizes.
  • the silver powder may have a spherical shape, a flake or an amorphous shape.
  • the silver powder preferably has an average particle diameter (D50) of from about 0.1 ⁇ m to about 10 ⁇ m, more preferably an average particle diameter (D50) of from about 0.5 ⁇ m to about 5 ⁇ m.
  • the average particle diameter can be measured using an apparatus such as Mastersize 2000 (Malvern Co., Ltd.) after the conductive powder is ultrasonically dispersed in isopropyl alcohol (IPA) at 25 ° C for 3 minutes. Within this average particle size range, the composition can provide low contact resistance and low line resistance.
  • the silver powder may be present in an amount from about 60% to about 95% by weight, based on the total weight of the composition. Within this range, the conductive powder can prevent deterioration of conversion efficiency due to an increase in electrical resistance. More preferably, the electrically conductive powder is present in an amount of from about 80% by weight to about 95% by weight.
  • the present invention produces a multi-component nanomaterial containing lead oxide, cerium oxide and other oxides by employing a bottom-up process.
  • the particle size of such nanoparticles can be reduced to less than one percent of the glass powder prepared by a conventional top-down process, and the particle size distribution is uniform, enabling it to be more uniformly dispersed in the electrons.
  • the silver paste Since the particle size of the multi-component nano material particles is small, the melting point of the glass powder is significantly lower than that of the micron-sized glass powder.
  • the paste composition of the invention can be used to prepare the solar cell electrode at a lower sintering temperature, and can be in the silver-silicon phase during the sintering process. A more uniform and thinner oxide layer is formed between them, resulting in a better ohmic contact, which reduces the series resistance and makes the distribution more uniform.
  • the smaller particle size can achieve the same volume filling in the case of a small amount (wt%), thereby increasing the silver content in the slurry and the conductivity after sintering of the slurry, and further reducing the series resistance (Rs). Finally, the photoelectric conversion efficiency is improved.
  • the organic carrier imparts the appropriate viscosity and rheological properties required for the conductive paste printing process by mechanical mixing with the inorganic components in the solar cell electrodes.
  • the organic vehicle may be any typical organic vehicle used for the solar cell electrode composition, and may include a binder resin, a solvent, and the like.
  • the binder resin may be selected from an acrylate resin or a cellulose resin. Ethyl cellulose is usually used as the binder resin. Further, the binder resin may be selected from the group consisting of ethyl hydroxyethyl cellulose, nitrocellulose, a blend of ethyl cellulose and phenolic resin, alkyd resin, phenol, acrylate, xylene, polybutene, poly Ester, urea, melamine, vinyl acetate resin, wood rosin, polymethacrylate of alcohol, and the like.
  • the solvent may be selected, for example, from hexane, toluene, ethyl cellosolve, cyclohexanone, butyl cellosolve, butyl carbitol (diethylene glycol monobutyl ether), dibutyl carbitol (diethylene glycol) Butyl ether), butyl carbitol acetate (monobutyl ether acetate), propylene glycol monomethyl ether, hexanediol, terpineol, methyl ethyl ketone, benzyl alcohol, ⁇ -butyrolactone, Ethyl lactate and combinations thereof.
  • the organic vehicle may be present in an amount from about 1% to about 20% by weight, based on the total weight of the composition. Within this range, the organic vehicle can provide sufficient adhesive strength and excellent printability to the composition.
  • the composition may further include typical additives as needed to enhance flow properties, processability and stability.
  • the additive may include, but is not limited to, a dispersant, a thixotropic agent, a plasticizer, a viscosity stabilizer, an antifoaming agent, a pigment, a UV stabilizer, an antioxidant, a coupling agent and the like. These additives may be used singly or as a mixture thereof. These additives may be present in an amount from about 0.1% to about 3% by weight of the composition, although the amount may be varied as desired.
  • the preparation method of the multi-component nano material of the following examples includes the following steps:
  • the nano metal oxide obtained in the above process includes PbO, TeO 2 , Li 2 O, SiO 2 , Al 2 O 3 , ZnO, Bi 2 O 3 , B 2 O 3 , MgO, CaO, SrO, BaO, P 2 O. 5 , two or more of As 2 O 3 , Sb 2 O 3 , SeO 2 , MoO 3 , etc.; the nano metal oxides are connected by chemical bonds and the content of each component can be determined by the particle size Control, the larger the particle, the greater the weight, so the higher the content, the other metal oxide nanoparticles have a particle size of 1 to 100 nm.
  • the boiling point of the organic solvent is generally higher than 200 ° C, such as phenyl ether, octyl ether, 1-octadecene, oleylamine, oleic acid and the like.
  • a process for the preparation of a multi-component nanomaterial comprising an oxide of lead-tellurium-lithium.
  • This example provides a multi-element nanomaterial containing nano PbO, TeO 2 , and Li 2 O, which may be composed of a binary nano material containing PbO, TeO 2 or a ternary nano material.
  • the multi-component nanomaterial may also contain nano-oxide materials of other elements.
  • the preparation methods of several binary nano materials and ternary nano materials are listed below.
  • the preparation method of the PbO-Li 2 O and TeO 2 -Li 2 O binary nano material comprises the following steps, taking PbO-Li 2 O as an example: firstly adding lead tetraacetate and a surfactant to the phenol ether, and the temperature is raised to At 220 ° C, the lead acetate is decomposed to form PbO nanoparticles at 45 ° C; then lithium acetylacetonate is added to the organic solvent, lithium acetylacetonate decomposes at 260 ° C to form Li 2 O, and Li 2 O is seeded with PbO, in PbO
  • the nano-shells grow into a nanoshell of Li 2 O, ie, a crude product of the desired binary nanomaterial PbO-Li 2 O; then the crude material of the binary nanomaterial PbO-Li 2 O is rotated from the organic solvent by a rotary centrifuge.
  • the finally separated binary material PbO-Li 2 O is washed with alcohol and then dried into a powder to obtain a finished product of PbO-Li 2 O.
  • the TeO 2 -Li 2 O binary nanomaterial can be obtained in the same manner using ammonium hexabromophthalate.
  • the preparation method of the PbO-TeO 2 -SiO 2 ternary nano material comprises the following steps: firstly adding lead acetate and a surfactant in the diphenyl ether, and when the temperature is raised to 250 ° C, the lead acetate is decomposed to form PbO nanoparticles after being kept for 30 minutes.
  • the above-mentioned rice preparation method may also be carried out by using triethoxy(1-phenylvinyl)silane, 3-aminopropyltriethoxysilane, triethoxy-2-thiophenesilane or the like to prepare SiO 2 nanoparticles. PbO and SiO 2 are connected by a chemical bond.
  • the multi-component nanomaterial for preparing the solar cell conductive paste can be composed of a ternary or binary nano material prepared above, it can also be composed of various combinations.
  • the mol percentage of each component in each of the multi-component nanomaterials can be controlled by the particle size of the particles. The larger the particles, the larger the weight, so the higher the content. If the multi-component nanomaterial contains multiple, the final mol component can be determined by adjusting the amount of each multi-component nanomaterial.
  • Table 1 The percentages (mol%) of the different elements in the compounds of the multi-element nanomaterial are described in the following examples.
  • a method for preparing a conductive paste for a crystalline silicon solar cell of a multi-element nano material 3.
  • a solar cell conductive silver paste containing a multi-component nano material the composition and weight percentage of the silver paste being: 60 to 95 wt% of silver powder, 0.1 to 5 wt% of multi-component nano material, and 1 to 20 wt% of organic carrier And the balance of additives.
  • the composition and weight percentage of the silver paste are preferably: 80 to 95% of silver powder, 0.1 to 5% of a multi-component nanomaterial, 5 to 15% of an organic vehicle, and 0.1 to 3% of an additive.
  • the organic vehicle to be used may be one or more of an organic solvent, a thickener, a plasticizer, a surfactant, and a thixotropic agent.
  • the present invention uses a solar cell electronic silver paste prepared by using a multi-component nano material.
  • the composition and weight percentage of the silver paste are: 88% silver powder, 1.5% multi-component nano material, 10% organic system and 0.5. % of additives.
  • the multi-nanomaterial particles have a particle size of less than 100 nm and are uniformly distributed, and contain nano-lead oxide-nano-cerium oxide and other nano materials.
  • ethyl cellulose as an organic binder was sufficiently dissolved in 9.0 wt% of butyl carbitol at 60 ° C, 88 wt% of spherical silver powder having an average particle diameter of 1.5 ⁇ m, 1.5 wt%
  • the multi-component nanomaterial as described in Table 1 and 0.5 wt% of the thixotropic agent ThixatrolST were added to the binder solution, and then mixed and ground in a three-roll mill, thereby preparing a solar cell electrode composition.
  • the electrode composition prepared as above was deposited by screen printing on a front surface of a single crystal silicon wafer in a predetermined pattern, followed by drying in an infrared drying oven. Then, the composition for preparing the back aluminum electrode was printed on the back surface of the wafer and dried in the same manner.
  • the cell sheets processed by the above steps were fired in a belt firing furnace at 800-950 ° C for 40 seconds.
  • the solar energy efficiency tester PSS10, BERGER
  • the solar energy efficiency tester was used to measure the conversion efficiency (%) of the battery, the series resistance Rs (m ⁇ ), the open circuit voltage (Voc), and the like. Then, the electrode of the battery is welded to the ribbon with a solder using a soldering iron at 300 ° C to 400 ° C.
  • the adhesive strength (N/mm) of the battery electrode and the ribbon was measured using a tensile tester at a peel angle of 180° and a tensile rate of 50 mm/min.
  • the measured series resistance, conversion efficiency and tensile test are shown in Table 2.
  • Examples 1 to 10 and Comparative Examples 1 to 3 were prepared using the composition of the multi-element nanomaterials as shown in Table 1, and the compositions for solar cell electrodes were prepared in the same manner, and physical properties were evaluated. It is to be noted that the examples and comparative examples in Table 2 are intended to highlight the features of one or more of the inventions, and are not intended to limit the scope of the invention, nor to illustrate that the comparative examples are outside the scope of the invention. Further, the inventive subject matter is not limited to the specific details described in the examples and the comparative examples.
  • the composition of the multi-component nano-material composition prepared in Examples 1-10 was used within the preferred range of the present invention as compared with Comparative Examples 1-3, and the solar cell electrodes fabricated therefrom were compared with respect to the solder.
  • the tape exhibits a relatively high bond strength as well as excellent series resistance (Rs).
  • Comparative Examples 1-3 show lower pull and higher series resistance and lower efficiency.
  • Comparative Examples 1 and 2 show that the multi-component nanomaterials have higher series resistance and lower battery conversion efficiency if they do not contain nano-PbO or do not contain nano-TeO 2 as compared with the embodiment of the present invention.
  • Comparative Example 3 shows that the molar ratio of Te/Pb of the multi-element nanomaterial is not in the preferred range, and the series resistance of the prepared solar electrode is higher than that of the embodiment of the present invention.
  • the examples show that the multi-component nanomaterial contains 1.0 to 60.0 mol% of nano lead oxide, 1.0 to 65.0 mol% of nano TeO 2 and 0.1 to 50 mol% of nano Li 2 O.
  • the glass powder composition is 1.0 to 50.0 mol% of the lead-containing nano-oxide
  • the nano-TeO 2 is 1.0 to 55.0 mol%
  • the nano-Li 2 O is 1.0 to 45.0 mol%
  • the molar ratio of TeO 2 and PbO is 0.05 to 20:1
  • the formed solar cell has better performance.
  • Comparative Examples 4 to 5 in Table 3 are glass powders prepared by a conventional method, the composition of which is the same as that of the multi-component nanomaterials 3 and 7 shown in Table 1, and the combination for solar cell electrodes is prepared in the same manner. And evaluate the physical properties to compare the advantages of multi-component nanomaterials in replacing glass powder in solar cell conductive silver paste.
  • the examples and the comparative examples in Table 3 are intended to highlight the features of one or more of the inventions, and are not intended to limit the scope of the invention, nor to illustrate that the comparative examples are outside the scope of the invention. Further, the inventive subject matter is not limited to the specific details described in the examples and the comparative examples.
  • Comparative Examples 4 and 5 show that the glass powder has the same composition as the multi-component nano material as compared with the embodiment of the present invention, and the prepared solar electrode has a relatively low tensile strength, a relatively high series resistance, and a low conversion efficiency.
  • Table 4 shows compositions for solar cell electrodes prepared using multi-component nanomaterials of different compositions and micro glass frits, and the efficiency comparison of solar cells made therefrom at different sintering peak temperatures was measured.
  • Comparative Examples 4 to 5 are micron-sized glass frits prepared by a conventional method, the compositions of which are shown in the table, and compositions for solar cell electrodes are prepared in the same manner as in the case of using multi-component nano-materials.
  • the compositional composition of the multi-component nanomaterial composition prepared in Examples 1-9 was used within the preferred range of the present invention as compared with Comparative Example 4-5, and the optimum sintering temperature of the solar cell electrode produced therefrom was remarkably low.
  • the invention examples show that the multi-component nano material replaces the glass powder, and the solar cells made of 1.0-60.0 mol% of nano lead oxide, 1.0-65.0 mol% of nano TeO 2 and 0.1-50 mol% of nano Li 2 O have higher solar cells. Physical properties and lower suitability for sintering temperatures. Further, the multi-component nano material replaces the glass powder, and the solar cell made of 1.0 to 50.0 mol% of nano lead oxide, 1.0 to 55.0 mol% of nano TeO 2 and 0.1 to 45 mol% of nano Li 2 O is more excellent. performance.
  • the particle diameter of the nanoparticles prepared by the method of the present invention can be reduced to one hundredth of the micron-sized glass powder prepared by the conventional top-down process.
  • the particle size distribution is uniform. Since the particle size of the multi-component nano material particles is small, it can be more uniformly dispersed in the electron silver paste, and in particular, the melting point of the nanoparticles is significantly lower than that of the bulk and the micron material.
  • the optimum sintering temperature of the conductive silver paste using the nanoparticles can be significantly lower than that of the conventional silver powder, so that a more uniform and more silver-silicon formation can be formed in the lower temperature sintering process.
  • a thin oxide layer results in a better ohmic contact, which reduces series resistance and makes it more uniform.
  • the paste composition of the invention can reduce the optimum sintering temperature while reducing the contact resistance, adapt to the advanced battery industry, can reduce the adverse effect of high surface resistance on the pn junction, thereby improving the efficiency of the solar cell, and Improve the academic performance of the electrodes made from it.

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Abstract

一种用于制备太阳能电池电极的多元纳米材料、包括其的糊剂组合物及太阳能电池电极和电池。其中，多元纳米材料包含1.0mol％～60.0mol％的铅氧化物PbO，1.0mol％～65.0mol％的碲氧化物TeO2。该多元纳米材料的粒径可以减小到用传统自上而下(top-down)的工艺制备的玻璃粉的百分之一以下，并且粒径分布均一。

Description

用于制备太阳能电池电极的多元纳米材料、包括其的糊剂组合物及太阳能电池电极和电池 技术领域
本发明涉及太阳能电池制造技术领域，具体而言，涉及一种用于制备太阳能电池电极的多元纳米材料、包括其的糊剂组合物及太阳能电池电极和电池。
背景技术
由于日益紧迫的能源危机、日趋严重的环境污染和温室效应等问题，发展可再生的绿色清洁能源成为世界各国的共识。在目前有所研究的各种可再生的绿色能源中，太阳能取之不尽用之不竭。阳光照射在地球上每分钟的能量相当于人类每年耗能的总合。并且太阳能没有污染，运用其的设备易于安装和维护，因此最具有大规模应用的前景。而大规模开发和利用光伏太阳能发电，提高电池的光电转换效率和降低其度电生产成本是其核心所在。
传统的太阳能电池有正电极、减反射层、n-型半导体(正面向光面)、P-型半导体、背电极组成等重要组成部分。其中正电极本身的电导率、电极和n-型硅的接触电阻、电极的高宽比对太阳能晶硅电池的光电转化效率有着重要的影响，是行业内的主要研究方向之一。目前，工业上晶硅太阳能电池正面电极的制作方法是通过丝网打印技术，将正面电极用导电银浆打印在晶硅电池片上，然后通过快速高温烧结的过程，形成与n型硅紧密接触的正面导电电极栅线。在烧结的过程中，银浆中玻璃粉具有腐蚀性的成分，例如Pb等，会逐渐熔融并和氮化硅的减反层发生反应，进而腐蚀掉减反层，同时溶解浆料中的一部分银粉。在随后的降温过程中，融解在玻璃中的银会逐渐变得过饱和而析出，而在n型硅表面形成岛状的银颗粒。玻璃也会随着温度的降低铺在n型晶硅的表面形成厚度约为几十纳米玻璃层。倒金字塔型的银岛颗粒通过隧道效应，将n型晶硅产生的光生电流透过玻璃层传导到正面银电极。其中，银岛的数量和体积对整个电池片的串联电阻的影响非常大。降低串联电阻要求银岛的数目多，且体积不能过大。但现在的银浆制备烧结过程，一般要求提高烧结的温度或者增加在高温区的停留时间来增加银岛的数目，但是同时也会造成银岛的体积过大，容易导致电极烧穿。为了提供一种廉价的太阳能电池的生产，并且具有较高的光电转化效率，需要烧结成电极的导电银浆可以在相对的较低的烧结温度下能够腐蚀掉防反射层，并且使形成的电极和下面的n型晶硅有很好的欧姆接触。
目前工业界普遍使用的银浆料为美国杜邦、德国贺利氏、韩国三星等国外公司的产品。国产银浆公司的产品还不够完善，主要存在以下问题：晶体硅电池转化效率不够高，导电银浆料的体积电阻较大，银层与硅结合强度一般，并且银浆烧结温度范围较窄，只能适用于较高的烧结温度。
目前正银浆料中采用的玻璃粉的成分、含量、粒径大小和软化温度会直接影响接触电阻， 穿透减反射层的能力、电极的导电性能和电极与基板之间的附着力等，从而影响太阳能电池的光电转化效率和使用寿命。玻璃粉的形貌和粒度对浆料的烧结也有重要影响，目前玻璃粉的制备通常采用如专利US8889980所述的一种高温熔融–低温水淬-碾磨的物理粉碎的方法。这种自上而下(top-down)的工艺对玻璃粉的形貌和粒度的控制不佳，颗粒大小的分布比较宽，一般在1-10微米的大范围内。这样会影响烧结的均一性，使电池各处串联电阻的分布不均且电阻较高，从而影响电池的光电转化效率。特别是采用微米级的粉体与其本体的熔点相当，不能有效降低由其制备的浆料的烧结温度。
发明内容
本发明旨在提供一种用于制备太阳能电池电极的多元纳米材料、包括其的糊剂组合物及太阳能电池电极和电池，以解决现有技术中糊剂组合物由于所含有的玻璃粉形貌和粒度不均一而导致的电池各处串联电阻的分布不均且电阻较高，采用微米级粉体带来的烧结温度较高从而影响电池的光电转化效率的技术问题。
为了实现上述目的，根据本发明的一个方面，提供了一种用于制备太阳能电池电极的多元纳米材料。该多元纳米材料包含1.0mol％～60.0mol％的纳米铅氧化物PbO，1.0mol％～65.0mol％的纳米碲氧化物TeO 2。
进一步地，多元纳米材料还包含0.1mol％～50mol％的纳米氧化锂Li 2O。
进一步地，多元纳米材料还包含其它纳米材料，其它纳米材料选自由纳米氧化钠Na 2O、纳米氧化钾K 2O、纳米氧化镁MgO、纳米氧化钙CaO、纳米氧化锶SrO、纳米氧化钡BaO、纳米氧化铋Bi 2O 3、纳米氧化磷P 2O 5、纳米氧化硅SiO 2、纳米氧化硼B 2O 3、纳米氧化锌ZnO、纳米氧化镍NiO、纳米氧化铜CuO、纳米氧化钨WO 3、纳米氧化钼MoO 3、纳米氧化钴CoO、纳米氧化钌RuO和纳米氧化钛TiO 2组成的组中的一种或多种。
进一步地，多元纳米材料包含1.0mol％～50.0mol％的纳米铅氧化物PbO，1.0mol％～55.0mol％的纳米碲氧化物TeO 2和0.1mol％～45mol％的纳米Li 2O。
进一步地，多元纳米材料中Pb与Te的mol比为0.05～20:1，优选为0.1～10:1。
进一步地，其它纳米材料的含量占多元纳米材料的1～25mol％。
进一步地，采用自下而上的工艺方法制备得到。
进一步地，多元纳米材料的粒径包括1～100纳米、1～60纳米和5～50纳米三种粒径范围中的一种或多种。
根据本发明的另一个方面，提供一种用于制备太阳能电池电极的糊剂组合物。该糊剂组合物包含60～95wt％的导电粉末、1.0～20wt％的有机载体、0.1～5wt％的上述任一种多元纳米材料，以及余量的添加剂。
进一步地，添加剂为选自由分散剂、触变剂、增塑剂、粘度稳定剂、消泡剂、颜料、UV稳定剂、抗氧化剂和偶联剂组成的组中的一种或多种。
进一步地，导电粉末为银粉。
根据本发明的再一个方面，提供一种太阳能电池电极。该太阳能电池由上述任一种的糊剂组合物制备而成。
根据本发明的又一方面，提供了一种太阳能电池，包括电极。该电极为上述由本发明的糊剂组合物制备而成的太阳能电池电极。
本发明方法制备的纳米粒子的粒径，可以减小到用传统自上而下(top-down)的工艺制备的玻璃粉的百分之一以下，并且粒径分布均一。由于多元纳米材料颗粒的粒径小，使其能够更均一的分散在电子银浆料中，特别是纳米粒子的熔点会显著低于其本体及微米材料。这样采用纳米粒子的导电银浆的最佳烧结温度可以显著低于采用传统玻璃粉的正银浆料的烧结温度，从而在较低温度的烧结过程中能够在银-硅之间形成更均一和更薄的氧化层，得到更优的欧姆接触，从而降低串联电阻并使其分布更均匀。本发明的糊剂组合物，其在降低接触电阻的同时，能够降低其最佳烧结温度，适应较先进的电池工艺，可以降低高表面电阻对p-n结的不利影响，从而提高太阳能电池效率，以及提高由其制造的电极的学性能。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。
为了解决目前银浆技术存在的不足，特别是针对现有银浆所采用的玻璃粉在自上而下(top-down)工艺制备存在的如前面(背景技术)所述的不可避免的问题，提供一种用多元纳米材料取代目前银浆所广泛使用的玻璃粉，来制备晶体硅太阳能电池用正面导电银浆。
本发明实现的工艺技术方案：采用一种新型的多元纳米材料，相对传统方法制备的玻璃粉，能够有效地降低软化温度，使纳米粉体能够在相对低的烧结温度下熔融银粉颗粒，可以在玻璃层和发射极之间形成大量的银纳米胶体粒子，降低电池串联电阻，并使电阻分布更加均一。本发明的多元纳米材料的软化温度为低于300℃。
根据本发明一种典型的实施方式，提供一种用于制备太阳能电池电极的多元纳米材料。该多元纳米材料包含1.0mol％～60.0mol％的纳米铅氧化物PbO，1.0mol％～65.0mol％的纳米碲氧化物TeO 2。
本发明制备的的多元纳米粒子的粒径可以减小到用传统自上而下(top-down)的工艺制备的玻璃粉的百分之一以下，并且粒径分布均一，使其能够更均一的分散在电子银浆料中。由于多元纳米材料颗粒的粒径小、熔点低，可以降低烧结温度，从而在烧结过程中能够在银-硅之间形成更均一和更薄的氧化层，得到更优的欧姆接触，从而降低串联电阻并使其分布更均 匀。更小的粒径还能在用量(wt％)小的情况下达到同样的体积填充，从而提高浆料中的银含量和浆料烧结后的导电性，并进一步降低串联电阻，最终提高光电转换效率。含有本发明的多元纳米材料的太阳能电池电子银浆料，生产工艺方法简单、可以适应较低的烧结温度、晶体硅电池转化率高、低串联电阻、打印性较好。本发明含太阳能电池电子银浆料的糊剂组合物，其在降低接触电阻的同时，能够降低高表面电阻对p-n结的不利影响，从而提高太阳能电池效率，以及提高由其制造的电极的性能。
为了改善多元纳米材料的性能，优选的，多元纳米材料还包含0.1mol％～50mol％的纳米Li 2O。更优选的，多元纳米材料包含1.0mol％～50.0mol％的纳米铅氧化物，1.0mol％～55.0mol％的纳米碲氧化物和0.1mol％～45mol％的纳米Li 2O。进一步优选的，多元纳米材料还包含其它纳米材料，其它纳米材料选自由纳米氧化钠Na 2O、纳米氧化钾K 2O、纳米氧化镁MgO、纳米氧化钙CaO、纳米氧化锶SrO、纳米氧化钡BaO、纳米氧化铋Bi 2O 3、纳米氧化磷P 2O 5、纳米氧化硅SiO 2、纳米氧化硼B 2O 3、纳米氧化锌ZnO、纳米氧化镍NiO、纳米氧化铜CuO、纳米氧化钨WO 3、纳米氧化钼MoO 3、纳米氧化钴CoO、纳米氧化钌RuO和纳米氧化钛TiO 2组成的组中的一种或多种。优选的，多元纳米材料中Pb与Te的mol比为0.05～20:1。优选的，多元纳米材料中Pb与Te的mol比为0.1～10:1。在此优选范围内，多元纳米材料既可以在较低的温度下将银溶解，同时还可以保持对硅基片减反层很好地刻蚀作用。在较低的烧结温度下，可以形成较薄的一层氧化物，降低接触电阻，提高转化率。
优选的，其它纳米材料的含量占多元纳米材料的1～25mol％。这些多元纳米材料在此含量内可以分别起到不同的作用，例如纳米氧化钾、纳米氧化纳可以起降低接触电阻的作用。纳米氧化锌有助于扩展多元纳米材料的玻璃化范围。纳米氧化铋有助于改善多元纳米材料的耐久性。碱土元素的纳米氧化物有助于改善多元纳米材料与减反层的反应性。
根据本发明一种典型的实施方式，本发明的多元纳米材料的制备方法是采用的自下而上(bottom-up)工艺方法，其包括一种在有机液相中，一定温度下进行的化学合成，是通过以下步骤实现的：
a)第一组分纳米颗粒的生长：在耐高温的有机溶剂中，加入第一种金属化合物和表面活性剂，待温度升至一定程度时，保温一定的时间，则第一种金属化合物分解，并通过反应形成第一种金属的某种化合物的纳米颗粒；
b)第二组分纳米颗粒的生长：接着将第二种金属化合物加入到含有第一种金属化合物纳米颗粒的反应溶剂中，第二种金属化合物在一定温度下发生反应，并且以溶剂中生成的第一种金属的某种化合物的纳米粒子为种子，经过一定的反应时间，在第一种金属化合物的纳米颗粒旁边生长成第二种金属的某种化合物的纳米颗粒；
c)其它多元组分纳米颗粒的生长：依次加入含有所需的其它种类的金属化合物，按照上面所述方法，经过一定的反应时间，直至形成所需的多元纳米材料；
d)反应制备多元纳米材料通过旋转离心机从有机溶剂中分离出来；
e)分离出来的多元纳米材料经过清洗剂清洗后烘干成粉末状即获得多元纳米材料成品。
优选的，步骤a)、b)和c)中的反应温度分别为200～600℃、200～500℃和220～400℃。
优选的，步骤b)中的第二种金属化合物的纳米颗粒之间通过形成化学键与第一种金属化合物的纳米颗粒的种子相连接。
优选的，步骤a)、b)和c)中的金属包括PbO、TeO 2、Li 2O、Na 2O、K 2O、MgO、CaO、SrO、BaO、Bi 2O 3、P 2O 5、SiO 2、B 2O 3、ZnO、NiO、CuO、WO 3、MoO 3、CoO、RuO和TiO 2组成的组中的两种或两种以上。
优选的，步骤a)、b)和c)中的反应时间分别为10～100分钟、15～80分钟和30～60分钟；
优选的，步骤a)、b)和c)中反应制得的金属化合物纳米颗粒粒径分别为1～100纳米、1～60纳米和5～50纳米。
优选的，步骤e)中的清洗溶剂为水、丙酮、丁酮、甲醚、乙醚、甲醇、乙醇、丙醇和异丙醇组成的组中的一种或两种或两种以上的混合溶剂。
根据本发明一种典型的实施方式，提供一种用于制备太阳能电池电极的糊剂组合物。该糊剂组合物包含60～95wt％的导电粉末、1.0～20wt％的有机载体、0.1～5wt％的上述任一种多元纳米材料，以及余量的添加剂。优选的，该糊剂组合物包含80～95wt％的银粉、0.5～3wt％的多元纳米材料、5～15wt％的有机载体和0.1～0.5wt％的添加剂。其中，添加剂为选自由分散剂、触变剂、增塑剂、粘度稳定剂、消泡剂、颜料、UV稳定剂、抗氧化剂和偶联剂组成的组中的一种或多种。优选的，导电粉末为银粉。
根据本发明的再一个方面，提供一种太阳能电池电极。该太阳能电池由上述任一种的糊剂组合物制备而成。
根据本发明的又一方面，提供了一种太阳能电池，包括电极。该电极为上述由本发明的糊剂组合物制备而成的太阳能电池电极。
根据本发明一种典型的实施方式，太阳能电池电极组分包括银粉、多元纳米材料和有机载体。现在，将更详细地描述本发明的太阳能电池电极的组成。
(A)银粉
根据本发明一种典型的实施方式，用于制备太阳能电池电极的糊剂组合物包含银粉作为导电粉末。银粉的粒度可以是纳米或微米级。例如，银粉可以具有几十至几百纳米，或几至几十微米的粒度。或者，银粉可以是具有不同粒径的两种或更多种银粉的混合物。
银粉可以具有球形、薄片或无定形形状。
银粉优选具有约0.1μm至约10μm的平均粒径(D50)，更优选约0.5μm至约5μm的平均粒径(D50)。平均粒径可以使用仪器，如Mastersize 2000(Malvern Co.，Ltd。)在将导 电粉末在25℃下通过超声波分散在异丙醇(IPA)中3分钟之后测量。在该平均粒径范围内，组合物可以提供低接触电阻和低线电阻。
基于组合物的总重量，银粉可以约60wt％至约95wt％的量存在。在该范围内，导电粉末可以防止由于电阻的增加而导致的转换效率的劣化。更佳情况下，导电粉末以约80wt％至约95wt％的量存在。
(B)基于纳米氧化铅和纳米氧化碲的多元纳米材料
本发明通过采用自下而上(bottom-up)工艺制备含有氧化铅、氧化碲和其它氧化物的多元纳米材料。这种纳米粒子的粒径可以减小至用传统自上而下(top-down)的工艺制备的玻璃粉的百分之一以下，并且粒径分布均一，使其能够更均一的分散在电子银浆料中。由于多元纳米材料颗粒的粒径小，相比微米级的玻璃粉体熔点会显著降低。本发明制备的多元纳米材料替代银浆料中的常规玻璃粉后，应用本发明的糊剂组合物可以在较低的烧结温度下制备太阳能电池电极，且在烧结过程中能够在银-硅之间形成更均一和更薄的氧化层，得到更优的欧姆接触，从而降低串联电阻并使其分布更均匀。同时更小的粒径还能在用量(wt％)小的情况下达到同样的体积填充，从而提高浆料中的银含量和浆料烧结后的导电性，并进一步降低串联电阻(Rs)，最终提高光电转换效率。
(C)有机载体
通过与太阳能电池电极中的无机组分的机械混合，有机载体赋予导电浆料打印过程所需的适当的粘度和流变特性。
有机载体可以是用于太阳能电池电极组合物的任何典型的有机载体，并且可以包括粘合剂树脂，溶剂等。
粘合剂树脂可以选自丙烯酸酯树脂或纤维素树脂。通常使用乙基纤维素作为粘合剂树脂。此外，粘合剂树脂可以选自乙基羟乙基纤维素、硝化纤维素、乙基纤维素和酚醛树脂的共混物、醇酸树脂、苯酚、丙烯酸酯、二甲苯、聚丁烯、聚酯、脲、三聚氰胺、乙酸乙烯酯树脂、木松香、醇的聚甲基丙烯酸酯等。
溶剂可以选自例如己烷、甲苯、乙基溶纤剂、环己酮、丁基溶纤剂、丁基卡必醇(二甘醇单丁基醚)、二丁基卡必醇(二甘醇二丁基醚)、丁基卡必醇乙酸酯(单丁醚乙酸酯)、丙二醇单甲醚、己二醇、萜品醇、甲基乙基酮、苄醇、γ-丁内酯、乳酸乙酯及其组合。
基于组合物的总重量，有机载体可以约1wt％至约20wt％的量存在。在该范围内，有机载体可以为组合物提供足够的粘合强度和优异的可印刷性。
(D)添加剂
根据需要，组合物可以进一步包括典型的添加剂，以增强流动性能，加工性能和稳定性。添加剂可以包括分散剂、触变剂、增塑剂、粘度稳定剂、消泡剂、颜料、UV稳定剂、抗氧化 剂、偶联剂等，但不限于此。这些添加剂可以单独使用或作为其混合物使用。这些添加剂可以以组合物中约0.1wt％至约3wt％的量存在，但该量可根据需要改变。
接下来，本发明将通过参考实施例更详细地描述。然而，应当注意，这些实施例的提供仅用于说明本发明，不应以任何方式解释为限制本发明。
为了清楚的目的，省略了本领域技术人员清楚的详细描述。
实施例及对比例
以下实施例的多元纳米材料的制备方法包括以下步骤：
a)在耐高温的有机溶剂中，加入第一种金属化合物和表面活性剂，待温度升至一定程度时，保温一定的时间，则第一种金属化合物分解，并通过反应形成第一种金属的某种化合物的纳米颗粒；b)接着将第二种金属化合物加入到含有第一种金属化合物纳米颗粒的反应溶剂中，第二种金属化合物在一定温度下发生反应，并且以溶剂中生成的第一种金属的某种化合物的纳米粒子为种子，经过一定的反应时间，在第一种金属化合物的纳米颗粒旁边生长成第二种金属的某种化合物的纳米颗粒；c)依次加入含有所需的其它种类的金属化合物，按照上面所述方法，经过一定的反应时间，直至形成所需的多元纳米材料；d)反应制备多元纳米材料通过旋转离心机从有机溶剂中分离出来；e)分离出来的多元纳米材料经过清洗剂清洗后烘干成粉末状即获得多元纳米材料成品。
上述过程中获得的纳米金属氧化物包括PbO、TeO 2、Li 2O、SiO 2、Al 2O 3、ZnO、Bi 2O 3、B 2O 3、MgO、CaO、SrO、BaO、P 2O 5、As 2O 3、Sb 2O 3、SeO 2、MoO 3等中的两种或两种以上；纳米金属氧化物之间通过化学键连接且各个组分的含量可以通过粒子粒径的大小来控制，颗粒越大，重量越大，所以含量越高，另外金属氧化物纳米颗粒粒径为1～100nm。在该制备方法中，有机溶剂的沸点一般高于200℃，例如苯基醚、辛基醚、1-十八烷烯、油胺、油酸等。
1.含有铅-碲-锂的氧化物的多元纳米材料的制备方法。
本实例提供一种含有纳米PbO、TeO 2、和Li 2O的多元纳米材料，可以由含PbO、TeO 2的二元纳米材料或三元纳米材料组成。
多元纳米材料还可以包含其它元素的纳米氧化物材料。下面列举几种二元纳米材料和三元纳米材料的制备方法。
PbO-Li 2O及TeO 2-Li 2O二元纳米材料的制备方法包括以下步骤，以PbO-Li 2O为例：首先在苯酚醚中，加入醋酸铅Leadtetraacetate和表面活性剂，待温度升至220℃时，保温45min则醋酸铅分解形成PbO的纳米颗粒；接着将乙酰丙酮锂加入到有机溶剂中，乙酰丙酮锂在260℃下分解形成Li 2O，且Li 2O以PbO为种子，在PbO的纳米颗粒周围生长成Li 2O的纳米壳，即形成所需的二元纳材料PbO-Li 2O的粗品；然后二元纳材料PbO-Li 2O的粗品通过旋转离心机从有机溶剂中分离出来；最终分离出来的二元纳材料PbO-Li 2O经过酒精清洗后烘干成粉末状即获得二元纳材料PbO-Li 2O成品。TeO 2-Li 2O二元纳米材料可以用同样的方法，使用 六溴碲酸铵制得。
PbO-TeO 2-SiO 2三元纳米材料的制备方法包括以下步骤：首先在二苯醚中，加入醋酸铅和表面活性剂，待温度升至250℃时，保温30min则醋酸铅分解形成PbO的纳米颗粒；接着将六溴碲酸铵加入到有机溶剂中，六溴碲酸铵在300℃下分解形成TeO 2，且TeO 2以PbO为种子，在PbO的纳米颗粒旁边生长成TeO 2纳米颗粒；接着将正硅酸加入到二苯醚中，正硅酸在200℃下分解形成SiO 2，且SiO 2以PbO-TeO 2为种子，即形成所需的三元纳材料PbO-TeO 2-SiO 2的粗品；然后三元纳材料PbO-TeO 2-SiO 2的粗品通过旋转离心机从有机溶剂中分离出来。最终分离出来的三元纳材料PbO-TeO 2-SiO 2经过酒精清洗后烘干成粉末状即获得三元纳材料PbO-TeO 2-SiO 2成品。
上述制备米方法中亦可采用三乙氧基(1-苯基乙烯基)硅烷、3-氨基丙基三乙氧基硅烷、三乙氧基-2-噻吩硅烷等来制备SiO 2纳米颗粒。PbO和SiO 2之间通过化学键连接。
由于制备太阳能电池导电浆料的多元纳米材料可以由以上制备的一种三元或二元纳米材料组成，也可以由多种组合而成。
2.含有铅-碲-锂-硅的氧化物的多元纳米材料的组分的确定。
每种多元纳米材料中的各个组分mol百分比可以通过粒子粒径的大小来控制，颗粒越大，重量越大，所以含量越高。如果多元纳米材料含有多种，最终mol组分可以通过调整每种多元纳米材料的量来确定。
表1：下面实例中描述的是多元纳米材料的化合物中，不同元素所占的mol百分比(mol％)。
表1：
Figure PCTCN2018099589-appb-000001
3.多元纳米材料的晶硅太阳能电池用导电浆料的制备方法。
一种含有多元纳米材料的太阳能电池导电银浆料，该银浆料的组成及重量百分含量为：60～95wt％的银粉、0.1～5wt％的多元纳米材料、1～20wt％的有机载体及余量的添加剂。为进一步的提升性能，银浆料的组成及重量百分含量优选为：80～95％的银粉、0.1～5％的多元纳米材料、5～15％的有机载体和0.1～3％的添加剂。采用的有机载体可为有机溶剂、增稠剂、增塑剂、表面活性剂和触变剂中的一种或一种以上。
进一步，本发明实例采用多元纳米材料制备的太阳能电池电子银浆料，该银浆料的组成及重量百分含量为：88％的银粉、1.5％的多元纳米材料、10％的有机体系和0.5％的添加剂。
根据表1所示的组成采用自下而上(bottom-up)工艺，制备的多元纳米材料。该多元纳米材料颗粒的粒径小于100nm，分布均一，含有纳米铅氧化物-纳米氧化碲和其它纳米材料。
将1.0wt％的作为有机粘合剂的乙基纤维素在60℃下充分溶解于9.0wt％的丁基卡必醇中，88wt％的平均粒径为1.5μm的球形银粉末，1.5wt％的如表一中所述多元纳米材料和0.5wt％的触变剂ThixatrolST加入到粘合剂溶液中，然后在三辊机中混合研磨，由此制备太阳能电池电极组合物。
将如上所制备的电极组合物通过丝网印刷，以预定图案沉积在单晶硅片的前表面上，随后在红外干燥炉中干燥。然后，将用于制备背铝电极的组合物印刷在晶片的背面上并以相同的方式干燥。将通过以上步骤处理的电池片在带式烧成炉中，于800-950℃之间烧成40秒。使用太阳能效率测试仪(PSS10，BERGER)来测量电池的转换效率(％)，串联电阻Rs(mΩ)，开路电压(Voc)等。然后，使用烙铁在300℃至400℃下用焊剂将电池的电极与焊带焊接。然后，电池电极与焊带的的粘合强度(N/mm)使用张力测试仪在180°的剥离角和50mm/min的拉伸速率下测量。测量的串联电阻、转换效率和拉力测试显示于表2中。
实施例1-10和对比例1-3
实施例1～10和对比例1～3采用如表1所示的多元纳米材料的组成，以相同的方式制备用于太阳能电池电极的组合物，并评价物理性能。需要表明的是表2中的实施例和对比例是为了突出一个或多个发明例的特点，而不是为限制本发明的范围，也不是说明对比例在本发明的范围之外。此外，发明主体并不局限于实施例和对比例中所描述的特定细节。
表2：
Figure PCTCN2018099589-appb-000002
Figure PCTCN2018099589-appb-000003
如表2所示，与对比例1-3相比，使用实施例1-10中制备的多元纳米材料组合物的成份组成在本发明优选的范围内，由其制造的太阳能电池电极相对于焊带显示出相当高的粘合强度以及优异的串联电阻(Rs)。对比例1-3显示较低的拉力和较高串联电阻及较低的效率。
对比例1和2表明，与本发明的实施例相比，多元纳米材料如果不含有纳米PbO或者不含有纳米TeO 2，所制备的太阳能电极的串联电阻较高，而电池转化效率相对较低。对比例3表明，多元纳米材料的Te/Pb的摩尔比不在优选范围内，与本发明的实施例相比，所制备的太阳能电极的串联电阻较高。类似地，实施例表明多元纳米材料含有1.0～60.0mol％的纳米铅氧化物，1.0～65.0mol％的纳米TeO 2和和0.1～50mol％的纳米Li 2O。更优选玻璃粉料组合物为含铅的纳米氧化物的1.0～50.0mol％，纳米TeO 2为1.0～55.0mol％，纳米Li 2O为1.0～45.0mol％，TeO 2和PbO的摩尔比为0.05～20:1，形成的太阳能电池具有更好的性能。
表3中的对比例4～5是用传统方法制备的玻璃粉，其组成采用如表1所示的多元纳米材料3和7相对应的组成，以相同的方式制备用于太阳能电池电极的组合物，并评价物理性能，来对比多元纳米材料取代玻璃粉在太阳能电池导电银浆的优势。需要表明的是表3中的实施例和对比例是为了突出一个或多个发明例的特点，而不是为限制本发明的范围，也不是说明对比例在本发明的范围之外。此外，发明主体并不局限于实施例和对比例中所描述的特定细节。
表3：
Figure PCTCN2018099589-appb-000004
对比例4、5表明，与本发明的实施例相比，玻璃粉料采用与多元纳米材料相同的组成，制备的太阳能电极的拉伸强度相对较低，串联电阻相对较高，转化效率低。
表4中显示采用不同组成的多元纳米材料和微米玻璃粉制备的用于太阳能电池电极的组合物，并测量由其制得的太阳能电池在不同烧结峰值温度下的效率对比。
表4：
Figure PCTCN2018099589-appb-000005
如表4所示，对比例4～5是用传统方法制备的微米级玻璃粉，其组成如表所示，并以与采用多元纳米材料相同的方式制备用于太阳能电池电极的组合物。与对比例4-5相比，使用实施例1-9中制备的多元纳米材料组合物的成份组成在本发明优选的范围内，由其制造的太阳能电池电极的最佳烧结温度明显较低。
发明实例表明，多元纳米材料替代玻璃粉，1.0～60.0mol％的纳米铅氧化物，1.0～65.0mol％的纳米TeO 2和和0.1～50mol％的纳米Li 2O制成的太阳能电池有更高的物理性能及较低的适合烧结温度。进一步的，多元纳米材料替代玻璃粉，1.0～50.0mol％的纳米铅氧化物，1.0～55.0mol％的纳米TeO 2和和0.1～45mol％的纳米Li 2O制成的太阳能电池有更加优异的性能。
从以上的实验结果中可以看出，通过本发明方法制备的纳米粒子的粒径，可以减小到用传统自上而下(top-down)的工艺制备的微米级玻璃粉的百分之一以下，并且粒径分布均一。由于多元纳米材料颗粒的粒径小，使其能够更均一的分散在电子银浆料中，特别是纳米粒子的熔点会显著低于其本体及微米材料。这样采用纳米粒子的导电银浆的最佳烧结温度可以明显低于采用传统玻璃粉的正银浆料烧结温度，从而在较低温度的烧结过程中能够在银-硅之间形成更均一和更薄的氧化层，得到更优的欧姆接触，从而降低串联电阻并使其分布更均匀。本发明的糊剂组合物，其在降低接触电阻的同时，能够降低其最佳烧结温度，适应较先进的电池工业，可以降低高表面电阻对p-n结的不利影响，从而提高太阳能电池效率，以及提高由其制造的电极的学性能。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员 来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (14)

  1. 一种用于制备太阳能电池电极的多元纳米材料，其特征在于，所述多元纳米材料包含1.0mol％～60.0mol％的纳米铅氧化物PbO，1.0mol％～65.0mol％的纳米碲氧化物TeO 2。
  2. 根据权利要求1所述的多元纳米材料，其特征在于，所述多元纳米材料还包含0.1mol％～50mol％的纳米氧化锂Li 2O。
  3. 根据权利要求1或2中所述的多元纳米材料，其特征在于，所述多元纳米材料还包含其它纳米材料，所述其它纳米材料选自由纳米氧化钠Na 2O、纳米氧化钾K 2O、纳米氧化镁MgO、纳米氧化钙CaO、纳米氧化锶SrO、纳米氧化钡BaO、纳米氧化铋Bi 2O 3、纳米氧化磷P 2O 5、纳米氧化硅SiO 2、纳米氧化硼B 2O 3、纳米氧化锌ZnO、纳米氧化镍NiO、纳米氧化铜CuO、纳米氧化钨WO 3、纳米氧化钼MoO 3、纳米氧化钴CoO、纳米氧化钌RuO和纳米氧化钛TiO 2组成的组中的一种或多种。
  4. 根据权利要求2所述的多元纳米材料，其特征在于，所述多元纳米材料包含1.0mol％～50.0mol％的纳米铅氧化物PbO，1.0mol％～55.0mol％的纳米碲氧化物TeO 2和0.1mol％～45mol％的纳米氧化锂Li 2O。
  5. 根据权利要求1或2或4中任一项所述的多元纳米材料，其特征在于，所述多元纳米材料中Pb与Te的mol比为0.05～20:1，优选为0.1～10:1。
  6. 根据权利要求3所述的多元纳米材料，其特征在于，所述多元纳米材料中Pb与Te的mol比为0.05～20:1，优选为0.1～10:1。
  7. 根据权利要求6所述的多元纳米材料，其特征在于，所述其它纳米材料的含量占所述多元纳米材料的1～25mol％。
  8. 根据权利要求1或2所述的多元纳米材料，其特征在于，采用自下而上bottom-up的工艺方法制备得到。
  9. 根据权利要求1或2所述的多元纳米材料，其特征在于，所述多元纳米材料的粒径包括1～100纳米、1～60纳米和5～50纳米三种粒径范围中的一种或多种。
  10. 一种用于制备太阳能电池电极的糊剂组合物，其特征在于，包含60～95wt％的导电粉末、1.0～20wt％的有机载体、0.1～5wt％的如权利要求1至9中任一项所述多元纳米材料，以及余量的添加剂。
  11. 根据权利要求10所述的糊剂组合物，其特征在于，所述添加剂为选自由分散剂、触变剂、增塑剂、粘度稳定剂、消泡剂、颜料、UV稳定剂、抗氧化剂和偶联剂组成的组中的一种或多种。
  12. 根据权利要求10所述的糊剂组合物，其特征在于，所述导电粉末为银粉。
  13. 一种太阳能电池电极，其特征在于，由权利要求10至12中任一项所述的糊剂组合物制备而成。
  14. 一种太阳能电池，包括电极，其特征在于，所述电极为如权利要求13所述的太阳能电池电极。
PCT/CN2018/099589 2017-10-30 2018-08-09 用于制备太阳能电池电极的多元纳米材料、包括其的糊剂组合物及太阳能电池电极和电池 WO2019085576A1 (zh)

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