WO2013032092A1 - Pâte métallique destinée à la formation d'une électrode de cellule solaire - Google Patents

Pâte métallique destinée à la formation d'une électrode de cellule solaire Download PDF

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Publication number
WO2013032092A1
WO2013032092A1 PCT/KR2012/002410 KR2012002410W WO2013032092A1 WO 2013032092 A1 WO2013032092 A1 WO 2013032092A1 KR 2012002410 W KR2012002410 W KR 2012002410W WO 2013032092 A1 WO2013032092 A1 WO 2013032092A1
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WO
WIPO (PCT)
Prior art keywords
metal paste
electrode
viscosity
paste
solar cell
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PCT/KR2012/002410
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English (en)
Korean (ko)
Inventor
공병선
김대진
조후
홍준의
김상호
Original Assignee
공주대학교 산학협력단
주식회사 케이씨씨
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Application filed by 공주대학교 산학협력단, 주식회사 케이씨씨 filed Critical 공주대학교 산학협력단
Publication of WO2013032092A1 publication Critical patent/WO2013032092A1/fr

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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
    • 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
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • 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
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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 a metal paste for forming an electrode of a solar cell. More particularly, the present invention relates to a metal paste in which an electrode having excellent electrical conductivity while minimizing shading loss by the electrode is minimized. .
  • the solar cell refers to a battery that generates current-voltage using a photovoltaic effect of absorbing light energy from sunlight and generating electrons and holes.
  • np diode-type silicon (Si) single crystal-based solar cells capable of producing photovoltaic energy conversion efficiency of more than 20% are used for photovoltaic power generation, and compound semiconductors such as gallium arsenide (GaAs), which are more efficient than this, are used.
  • GaAs gallium arsenide
  • the light absorption loss covers the incident light because the front electrode is printed on the surface of the solar cell, and thus, electrons and holes are not generated at the bottom of the electrode (the electrode is printed), thereby reducing the efficiency of the solar cell.
  • the front electrode formed on the light receiving surface of the solar cell includes a bus bar electrode extending in a band shape in one direction and a finger electrode connected to the bus bar electrode and extending in a direction orthogonal to the extending direction of the bus bar electrode. do. Furthermore, in general, the bus bar electrode occupies a 20 times larger area than the finger electrode, and serves as a large cause of efficiency reduction along with the finger electrode.
  • the electrode In order to reduce the loss of the light receiving area by the electrode, the electrode must be thinned to reduce the area occupied by the electrode. However, making the electrode thinner also lowers the conductivity of the electrode, which causes another efficiency reduction.
  • the electrode must be made thin while maintaining the constant cross-sectional area of the electrode, which increases the aspect ratio of the electrode. Therefore, in order to increase the efficiency of solar cells by reducing light absorption loss, development of front silver electrode material technology capable of realizing a high aspect ratio is urgently needed.
  • Korean Patent Laid-Open Publication No. 2011-0023776 provides a conductive composition comprising a conductive metal powder, a non-aqueous solvent, and a polymer coating enhancer, but Korean Patent Laid-Open Publication No. 2011-0023776 describes two or more non-aqueous materials having different volatile properties.
  • Korean Patent Laid-Open Publication No. 2010-0127619 discloses a metal paste composition for forming an electrode further comprising a glass-based powder, silver powder, and a carbon-based material powder with an organic binder
  • the Republic of Korea Patent Publication No. 2010-0127619 provides a composition that minimizes the consumption of expensive silver and does not substantially reduce the electrical properties of the electrode.
  • the present invention provides a metal paste for forming a solar cell electrode that minimizes the light loss (shadowing loss), and in particular, the rheological properties are controlled to provide a metal paste in which a high aspect ratio electrode is formed using a printing process will be.
  • the metal paste according to the present invention is characterized in that it is a paste for forming a solar cell electrode, and more particularly, is a paste for forming a solar cell electrode by printing, and more particularly screen printing.
  • the metal paste according to the present invention is characterized by containing conductive metal particles, glass frits, binders, thixotropy-imparting agents, and organic solvents, and is a metal paste that satisfies Equations 1 and 2 below. There is this.
  • TI 10 is the viscosity at shear rate 1s- 1 divided by the viscosity at shear rate 10s- 1
  • TI 100 is viscosity at shear rate 1s- 1 divided by shear rate 100s It is the value divided by the viscosity at -1 .
  • the metal paste satisfies Equation 1 and Equation 2, it is possible to manufacture an electrode having a high aspect ratio by a printing method, thereby having excellent electrical conductivity and minimizing the reduction of the light receiving area by the electrode, thereby providing a solar cell. It is characterized by increasing the efficiency of.
  • the electrode is formed with excellent precision without printing the line width of the designed electrode pattern by printing, more specifically screen printing, and when printing through the screen mesh It is possible to prevent clogging of dots after printing, to print a large area at high speed, and to prevent breakage of a printing pattern including a pinhole.
  • the thixotropic agent is a material that controls the rheological properties of the metal paste, and is a material that forms a hydrogen bonding network.
  • Paste according to the present invention is characterized by containing ethyl cellulose (ethyl cellulose) as a binder, it is characterized by containing hydroxypropyl cellulose (hydroxypropyl cellulose) as a thixotropic imparting agent.
  • the paste according to the present invention satisfies relations 1 and 2 above and contains hydroxypropyl cellulose as a thixotropic agent, thereby preventing clogging of dots, high-speed large-area printing, and breaking of print patterns.
  • the rate of change of the viscosity of the paste due to the change of the shear force is very fast, so that the spreading of the paste is prevented, and the electrode can be manufactured in which the aspect ratio (electrode height / electrode line width) of the electrode is 0.3 or more, more specifically 0.35 or more. At this time, the aspect ratio of the electrode is substantially 0.45 or less.
  • the conductive particles may be used as long as the conductive material is commonly used as an electrode material of an optical device including a solar cell.
  • the conductive material for example, silver, gold, platinum, copper, aluminum, nickel, iron, cobalt, palladium, tin, and alloys thereof One or two or more selected materials from the material.
  • the conductive particles When used as a front electrode of a solar cell, in view of low specific resistance, the conductive particles preferably contain silver. It is preferable that the average particle diameter of the said electroconductive particle is 0.1 micrometer-5 micrometers.
  • the glass frit may be used as long as it is a glass frit commonly used in manufacturing a solar cell front electrode, and includes a lead-containing or lead-free (lead-free) glass frit.
  • the glass frit include SiO 2 -PbO glass frit, SiO 2 -PbO-B 2 O 3 glass frit, Bi 2 O 3 -B 2 O 3 -SiO 2 glass frit, or a mixture thereof. have.
  • the glass frit has Li 2 O, Na 2 O, K 2 O, MgO, CaO, BaO, SrO, ZnO, Al 2 O 3 , TiO 2 , ZrO 2 , Ta 2 O 5 , Sb 2 O 5 , HfO 2 , In 2 O 3 , Ga 2 O 3 , Y 2 O 3 and Yb 2 O 3 It may contain one or more selected materials, the average particle diameter of the glass frit is preferably 0.5 ⁇ m to 3 ⁇ m. .
  • the organic solvent may be a hydrocarbon, an alcohol, an ether, an ester, a ketone, or a glycol solvent.
  • the organic solvent includes toluene, benzene, octanol, decanol, terpineol or carbitol.
  • the organic solvent is preferably carbitol.
  • the metal paste may contain 3 to 7 parts by weight of glass frit, 0.5 to 3 parts by weight of binder, 0.5 to 3 parts by weight of thixotropic agent and 10 to 20 parts by weight of an organic solvent based on 100 parts by weight of conductive metal particles. It is preferable to contain.
  • the content of the glass frit, the binder, the thixotropic agent and the organic solvent is that the front electrode formed by the printing of the metal paste has excellent interfacial bonding properties, and the rheological properties satisfying the above Equation 1 and Equation 2 are very 0.3 or more. It is a content in which a front electrode having a high aspect ratio and a very low resistivity and excellent interface bonding is produced.
  • the present invention includes a solar cell having the front electrode formed by printing the above-described metal paste, and preferably by screen printing.
  • the solar cell is characterized by having a high aspect ratio of the front electrode has a high electrical conductivity while minimizing the reduction in the light receiving area by the electrode, and has a high photoelectric efficiency.
  • the metal paste according to the present invention is capable of manufacturing a front electrode of a solar cell having a high aspect ratio by a printing method, so that the efficiency of the solar cell can be improved by minimizing the reduction of the light receiving area by the electrode while having excellent electrical conductivity. There is a characteristic to increase.
  • Example 1 illustrates the results of rheology measurement of the organic vehicle prepared in Example 1 of the present invention
  • Figure 2 shows the rheological measurement results of the organic vehicle prepared in Example 2 of the present invention
  • Figure 4 shows the rheological measurement results of the metal paste according to Example 1 of the present invention
  • Example 5 is a view illustrating a rheological measurement result of a metal paste according to Example 2 of the present invention.
  • Example 7 is a scanning electron microscope photograph of the electrode formed by screen printing a metal paste according to Example 1 of the present invention.
  • FIG. 8 is a scanning electron microscope photograph of the electrode formed by screen printing a metal paste according to Comparative Example 1.
  • FIG. 8 is a scanning electron microscope photograph of the electrode formed by screen printing a metal paste according to Comparative Example 1.
  • a metal paste was prepared in the same manner as in Example 1, except that 0.3 g of ethyl cellulose and 0.45 g of hydroxypropyl cellulose were dissolved in 6.75 g of carbitol to prepare an organic vehicle.
  • a metal paste was prepared in the same manner as in Example 1, except that 1.125 g of ethyl cellulose was dissolved in 6.375 g of carbitol to prepare an organic vehicle.
  • the rheological properties of the organic vehicles and metal pastes prepared in Examples 1, 2 and Comparative Example 1 were measured using a Physica MCR 301 rheometer from Anton Paar. Viscosity, thixotropy index (TI), loss modulus (G ”) and storage modulus (G ') were measured according to ASTM D4065, D4440, D5279, and shear rate with rheometer ) And the viscosity of the organic vehicle and paste prepared by changing 1 s ⁇ 1 , 10 s ⁇ 1 , and 100 s ⁇ 1 , respectively, and loss coefficients of the organic vehicles and pastes of Examples 1 to 2 and Comparative Example 1, respectively. (loss modulus) and storage modulus were measured before and after applying a shear rate of 1000 s -1 using a rheometer.
  • FIG. 1 shows the storage coefficient and the loss coefficient according to the viscosity according to the shear rate of the organic vehicle prepared in Example 1 and the time before and after applying the shear rate of 1000 s ⁇ 1
  • FIG. Viscosity according to the shear rate of the prepared organic vehicle and the storage coefficient and loss coefficient with time before and after applying the shear rate of 1000 s -1 is shown
  • Figure 3 is a shear rate of the organic vehicle prepared in Comparative Example 1
  • the storage coefficient and loss coefficient according to the viscosity and the time before and after applying the shear rate of 1000 s -1 are shown.
  • Figure 4 shows the storage coefficient and the loss coefficient according to the viscosity of the metal paste prepared in Example 1 according to the shear rate and the time before and after applying the shear rate of 1000 s -1
  • Figure 5 is in Example 2
  • Figure 6 is a shear rate of the metal paste prepared in Comparative Example 1
  • the storage coefficient ( ⁇ G ′) and loss coefficient ( ⁇ G ′′) according to the viscosity and the time before and after applying the shear rate of 1000 s ⁇ 1 are shown.
  • Table 1 summarizes the rheological properties measured in FIGS. 1 to 6.
  • T.I. thixotropic coefficient
  • FIG. 7 is a scanning electron microscope observing the electrode formed by screen printing the paste prepared in Example 1, the paste prepared in Comparative Example 1, as can be seen in Figures 7 to 8, according to the present invention
  • the electrode is manufactured by using a paste, an electrode having an aspect ratio of 0.35 or more is manufactured, whereas an electrode having an aspect ratio of 0.17 is prepared when an electrode is manufactured using the paste of Comparative Example 1.
  • the metal paste according to the present invention satisfy the relations 1 and 2, it can be seen that through the printing process to form a fine metal pattern with a narrow line width with high accuracy and high productivity Can be.

Abstract

La présente invention se rapporte à une pâte métallique destinée à la formation d'une électrode de cellule solaire. Plus particulièrement, la pâte métallique selon cette invention contient : des particules métalliques conductrices ; de la fritte de verre ; un liant ; un agent thixotropique ; et un solvant organique. Cette pâte est caractérisée en ce que TI10, qui est la valeur obtenue suite à la division de la viscosité à une vitesse de cisaillement de 1 s-1 par la viscosité à une vitesse de cisaillement de 10 s-1, s'inscrit dans une plage de 4 à 7, et en ce que TI100, qui est la valeur obtenue suite à la division de la viscosité à une vitesse de cisaillement de 1 s-1 par la viscosité à une vitesse de cisaillement de 100 s-1, s'inscrit dans une plage de 20 à 30.
PCT/KR2012/002410 2011-08-31 2012-03-30 Pâte métallique destinée à la formation d'une électrode de cellule solaire WO2013032092A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020110087817A KR101285551B1 (ko) 2011-08-31 2011-08-31 태양전지 전극 형성용 금속 페이스트
KR10-2011-0087817 2011-08-31

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016171359A1 (fr) * 2015-04-22 2016-10-27 삼성에스디아이 주식회사 Composition pour former une électrode de cellule solaire et électrode fabriquée avec cette dernière
WO2018084464A1 (fr) * 2016-11-01 2018-05-11 엘에스니꼬동제련 주식회사 Pâte conductrice pour électrode de cellule solaire, et cellule solaire fabriquée à l'aide de cette dernière
CN112525771A (zh) * 2020-11-30 2021-03-19 湖北亿纬动力有限公司 一种电池浆料储存性能评估方法

Families Citing this family (4)

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KR101882525B1 (ko) * 2013-04-11 2018-07-26 삼성에스디아이 주식회사 태양전지 전극 형성용 조성물 및 이로부터 제조된 전극
KR102269870B1 (ko) * 2015-04-22 2021-06-30 창저우 퓨전 뉴 머티리얼 씨오. 엘티디. 태양전지 전극 형성용 조성물 및 이로부터 제조된 전극
KR102040302B1 (ko) * 2017-08-24 2019-11-04 삼성에스디아이 주식회사 태양전지 전극 형성용 조성물 및 이로부터 제조된 전극
KR102340931B1 (ko) * 2019-12-31 2021-12-17 엘에스니꼬동제련 주식회사 도전성 페이스트의 인쇄 특성 향상을 위한 파라미터 및 이를 만족하는 도전성 페이스트

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WO2010024625A2 (fr) * 2008-08-29 2010-03-04 에스에스씨피 주식회사 Composition à base de pâte conductrice
KR100955496B1 (ko) * 2009-07-09 2010-04-30 주식회사 동진쎄미켐 태양전지 전극형성용 도전성 조성물

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KR20040083071A (ko) * 2001-12-27 2004-09-30 가부시키가이샤후지쿠라 도전성 조성물, 도전성 피막 및 도전성 피막의 형성 방법
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Publication number Priority date Publication date Assignee Title
WO2016171359A1 (fr) * 2015-04-22 2016-10-27 삼성에스디아이 주식회사 Composition pour former une électrode de cellule solaire et électrode fabriquée avec cette dernière
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WO2018084464A1 (fr) * 2016-11-01 2018-05-11 엘에스니꼬동제련 주식회사 Pâte conductrice pour électrode de cellule solaire, et cellule solaire fabriquée à l'aide de cette dernière
KR101930284B1 (ko) 2016-11-01 2018-12-19 엘에스니꼬동제련 주식회사 태양전지 전극용 도전성 페이스트 및 이를 사용하여 제조된 태양전지
CN110337727A (zh) * 2016-11-01 2019-10-15 LS-Nikko铜制炼株式会社 太阳能电池电极用导电性浆料以及使用上述浆料制造的太阳能电池
CN112525771A (zh) * 2020-11-30 2021-03-19 湖北亿纬动力有限公司 一种电池浆料储存性能评估方法
CN112525771B (zh) * 2020-11-30 2023-03-24 湖北亿纬动力有限公司 一种电池浆料储存性能评估方法

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