CN103177791B - A method of preparing the conductive paste and solar cell aluminum - Google Patents

A method of preparing the conductive paste and solar cell aluminum Download PDF

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CN103177791B
CN103177791B CN 201110437783 CN201110437783A CN103177791B CN 103177791 B CN103177791 B CN 103177791B CN 201110437783 CN201110437783 CN 201110437783 CN 201110437783 A CN201110437783 A CN 201110437783A CN 103177791 B CN103177791 B CN 103177791B
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solar cell
aluminum
powder
conductive paste
glass frit
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CN 201110437783
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CN103177791A (en )
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谭伟华
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比亚迪股份有限公司
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Abstract

本发明提供了一种太阳能电池用铝导电浆料及其制备方法,所述太阳能电池用铝导电浆料的组分包括铝粉、玻璃粉、有机载体和无机添加剂粉体;所述无机添加剂粉体的中粒径D50为0.1-5.0μm,且选自β-锂霞石、钨酸锆或钒酸锆的一种或多种。 The present invention provides a conductive paste for a solar cell and its preparation method of aluminum, an aluminum component of the solar cell conductive paste comprises aluminum powder, glass frit, an organic vehicle and an inorganic additive powders; powders of the inorganic additive particle size D50 body is 0.1-5.0 m, and is selected from β- eucryptite, one or more zirconium tungstate or vanadate zirconium. 采用本发明提供的太阳能电池用铝导电浆料丝网印刷到晶体硅太阳电池上并烧结成膜后,金属膜对硅基体附着牢固,表面光滑致密,无铝珠、铝疱,光电转换效率高,电池片翘曲度小,156×156型多晶硅太阳电池片的平均翘曲度小于0.50mm。 Aluminum solar cell using the conductive paste of the present invention provides a screen printing onto the crystalline silicon solar cell deposition and sintering, a metal film of the silicon substrate attached to a solid, smooth and compact surface, no aluminum beads, aluminum blisters, high photoelectric conversion efficiency , small cell sheet warping, the average degree of warpage 156 × 156-type polycrystalline silicon solar cell sheet is less than 0.50mm.

Description

-种太阳能电池用错导电浆料及其制备方法 - the wrong kind of the conductive paste for a solar cell and its preparation method

技术领域 FIELD

[0001] 本发明属于太阳能电池技术领域,具体设及一种太阳能电池用侣导电浆料及其制备方法。 [0001] The present invention belongs to the technical field of solar cell, and a solar cell using the conductive paste and preparation method companion specifically provided.

背景技术 Background technique

[0002] 太阳能电池是一种取之不竭的绿色环保可再生能源,当前国际研究非常活跃。 [0002] The solar cell is an inexhaustible green renewable energy, the current international research is very active. 侣导电浆料属于电子信息材料之一,同时也是制作太阳能电池的主要辅助材料。 Lu conductive paste is one of electronic information materials, but also the auxiliary production of primary material for solar cells. 目前的晶娃太阳能电池制作工艺中,侣导电浆料几乎印刷在电池的整个背光面上,由于金属侣(膨胀系数为232X10 ,20-300°C)与娃(膨胀系数为26X10V°C,20-300°C)的热膨胀系数的差异,导致侣导电浆料在烧结时,在娃片内产生应力,造成娃片弯曲。 Baby present crystalline solar cell fabrication process, Lu conductive paste printed on the almost entire back surface of the battery, since the companion metal (expansion coefficient 232X10, 20-300 ° C) and Wa (expansion coefficient 26X10V ° C, 20 difference -300 ° C) coefficient of thermal expansion, resulting in companion conductive paste during sintering stress is generated in the sheet baby, baby sheet causing bending.

[0003] 为了进一步降低晶体娃太阳电池的制造成本,增强其与传统能源发电的竞争力, 娃片的厚度从W前的210ym逐渐降低到目前的180ym,并仍下降的趋势。 [0003] In order to further reduce the manufacturing cost of crystalline solar cells baby, which enhance the competitiveness of conventional power generation, the thickness of the sheet is gradually decreased from the baby before 210ym W to the current 180ym, and still decline. 随着娃片厚度的不断减薄,传统的侣浆烧结后,电池片更容易翅曲,直接影响太阳能电池的成品率及后续的组件工艺。 With the thin sheet Wa thickness, the companion pulp after conventional sintering, cell warpage easier, directly affects the yield of the solar cell and the subsequent assembly process. 现有技术中,减少娃片翅曲有许多方法,例如可减少侣浆印刷时的转移量、降低烧结溫度或通过特殊冷却技术使基体产生塑性变形等。 In the prior art, reducing the sheet warpage baby There are many ways, for example, reduce the amount of companion slurry transfer printing, or by lowering the sintering temperature of the base body of special cooling techniques to produce plastic deformation.

[0004] CN101728439A公开了一种娃太阳电池背场侣导电浆料的组成和制备方法,该方法中通过添加0. 5-6.Owt%的2-6ym的金属或非金属粉末添加剂(棚、娃、锋、錬、锡中的一种或几种)来改善所制得的侣浆烧结后形成的电池的弯曲度及电性能。 [0004] CN101728439A discloses a composition and method for producing a solar cell back surface field companion baby conductive paste, the method by adding 0. 5-6.Owt% of metal or non-metallic powder additives 2-6ym (shed, baby, front, and chain, one or more of tin) to improve the electrical performance of the battery and the curvature of the companion slurry formed after firing was prepared. 但该类添加剂中,非金属粉末棚和娃的烙点很高,远超过侣的烙点,其与侣仅通过简单机械混合,因此在目前通用的晶体娃电池的烧结工艺下并不能与主体金属侣形成均匀的合金,因此不能改善电池片的弯曲度,甚至可能因引入杂质而降低电池的光电转换效率。 However, such additives, baked high point and a non-metallic powder shed baby, far more than the companion branded point, with companion simply by mechanical mixing, and therefore the current in the sintering process common crystal cell and not with the doll body Lu metal alloy to form a uniform, and therefore can not improve the degree of curvature of the cell sheets may even be reduced due to the introduction of impurities in the photoelectric conversion efficiency of the cell. 而该类添加剂中的金属粉末锋、 錬、锡,即使烧结后与侣粉形成合金,但其形成的合金的膨胀系数与电池片娃基体的膨胀系数相差较大,因此添加金属粉对改善电池片的弯曲度也无益。 And the metal powder in front of such additives, and chain, tin, even after sintering powders alloyed with companion, but the expansion coefficient of the expansion coefficient of an alloy formed with the battery plate substrate baby quite different, so metal powder added to improve the battery bending the sheet is also good. 因此,采用目前现有技术中公开的侣导电浆料仍然难W满足电池片的低翅曲度要求。 Thus, using the prior art disclosed in the conductive paste is still difficult companion W satisfy the requirements of low battery plate fin curvature.

发明内容阳〇化]本发明解决了现有技术中存在的太阳能电池侣导电浆料烧结后造成娃片弯曲、光电转换效率不能满足电池进一步发展的问题。 Summary of the male square] The present invention solves the sintering conductive paste companion solar cell in the prior art sheet bending causes baby, the photoelectric conversion efficiency can not meet the further development of the battery.

[0006] 本发明提供了一种太阳能电池用侣导电浆料,所述太阳能电池用侣导电浆料的组分包括侣粉、玻璃粉、有机载体和无机添加剂粉体;所述无机添加剂粉体的中粒径馬。 [0006] The present invention provides a solar cell using the conductive paste Lu, the solar cell comprises a conductive paste component Lu Lu powder, glass frit, an organic vehicle and an inorganic additive powders; powders of the inorganic additive the particle size horse. 为0. 1-5. 0ym,且选自0 -裡霞石、鹤酸错或饥酸错的一种或多种。 To 0. 1-5 0ym, and selected from 0 - in one or more of nepheline, hunger crane acid or acid wrong wrong.

[0007] 本发明还提供了所述太阳能电池用侣导电浆料的制备方法,包括将玻璃粉和无机添加剂粉体分散于有机载体中,然后分批加入侣粉,研磨后得到所述太阳能电池用侣导电浆料;所述无机添加剂粉体的中粒径〇5。 [0007] The present invention further provides a method of preparing a solar cell of the companion conductive paste, comprising glass frit, inorganic additives and powder dispersed in an organic carrier, and then added portionwise companion powder, after trituration of the solar cell Lu with conductive paste; particle size of said inorganic additive powder 〇5. 为0. 1-5. 0ym,且选自0 -裡霞石、鹤酸错或饥酸错的一种或多种。 To 0. 1-5 0ym, and selected from 0 - in one or more of nepheline, hunger crane acid or acid wrong wrong.

[0008] 本发明提供的太阳能电池用侣导电浆料,通过对浆料配方进行改进,减少侣膜与娃基底层应力产生根源。 [0008] The present invention provides a solar cell using the conductive paste Lu, the root cause of the slurry formulation is improved by reducing the base layer baby companion film stress. 本发明中,具体通过采用中粒径〇5。 In the present invention, the specific particle size by using 〇5. 为0.l-5.0ym、且选自e-裡霞石、鹤酸错或饥酸错的一种或多种的无机添加剂粉体,从而浆料烧结后残留混合物的热膨胀系数,缩小烧结残余物与娃材料之间的热膨胀系数的差异,进而改善电池片烧结后的翅曲问题;将该侣导电浆料印刷至娃基体上烧结成膜后,电池片翅曲度小,侣膜光滑致密, 无侣珠侣瘤,光电转换效率高。 It is 0.l-5.0ym, and in selected e- nepheline, hunger crane acid or acid wrong wrong one or more inorganic additives powder mixture so that the thermal expansion coefficient of the residual slurry after sintering, the sintered residue was reduced the difference in thermal expansion coefficient between the baby and the material thereof, thereby improving the warpage problem of the battery after sintering sheet; companion after the conductive paste printed onto the sintered body forming the substrate baby, small cell plate fin curvature, smooth and compact film companion no companion beads companion tumors, high photoelectric conversion efficiency. 从实施例1-4与对比例1-4的结果比较可W看出,印刷本发明提供的太阳能电池用侣导电浆料的晶体娃太阳电池片,烧结后得到的侣膜与娃基体附着牢固,表面光滑,不起侣珠和侣瘤,电池片翅曲度很小,156X156型的多晶娃太阳电池片的平均翅曲度小于0. 5mm。 1-4 and W can be seen from the comparison of the results of Comparative Example 1-4, baby crystal solar cell sheet of the present invention provides a printed solar cell companion conductive paste, obtained after sintering companion film attached to a solid substrate doll , smooth surface, and can not afford beads Lu Lu tumors, small cell sheet fin curvature, the curvature of the average fin polycrystalline solar cell sheet 156X156 type baby less than 0. 5mm.

具体实施方式 detailed description

[0009] 本发明提供了一种太阳能电池用侣导电浆料,所述太阳能电池用侣导电浆料的组分包括侣粉、玻璃粉、有机载体和无机添加剂粉体;所述无机添加剂粉体的中粒径〇5。 [0009] The present invention provides a solar cell using the conductive paste Lu, the solar cell comprises a conductive paste component Lu Lu powder, glass frit, an organic vehicle and an inorganic additive powders; powders of the inorganic additive the particle size 〇5. 为0. 1-5.Oym,且选自0-裡霞石、鹤酸错或饥酸错的一种或多种。 It is 0. 1-5.Oym, and is selected from 0- in nepheline, crane or hunger acid wrong wrong one or more acids.

[0010] 由于目前行业通用的背场侣浆一般由侣粉、玻璃粉、有机载体揽拌研磨而成,在侣浆印刷烧结后,留在娃片背面的是侣粉及少量起粘接作用的玻璃粉。 [0010] As the current common industry generally consists of the back surface field Lu Lu pulp powder, glass frit, an organic vehicle mixed embrace grinded, after sintering companion printing paste, leaving back surface sheet is baby powder and a small amount of play companion bonding effect glass frit. 由于金属侣(膨胀系数为232X10 ,20-300°C)与娃(膨胀系数为26X10V°C,20-300°C)材料的热膨胀系数差别较大,造成背场侣膜冷却后,在娃片内产生应力,造成娃片的弯曲。 Since the metal companion (expansion coefficient 232X10, 20-300 ° C) and Wa (expansion coefficient 26X10V ° C, 20-300 ° C) thermal expansion coefficient greatly different material, resulting in the back field companion film cooling, the baby sheet internal stress, causing bending piece Wa.

[0011] 本发明的发明人通过大量实验发现,本发明中通过在侣导电浆料中添加一定量的无机粉体,该类无机粉体材料具有较大的负热膨胀系数,并具有各向同性,响应溫度范围宽;该类负热膨胀无机粉体材料与浆料中的侣粉、玻璃粉W及有机载体混合研磨后,即得到本发明的太阳能电池用侣导电浆料,通过采用本发明的太阳能电池用侣导电浆料,浆料烧结后的残余物的热膨胀系数相比金属侣大大降低,因此缩小了浆料烧结残余物与娃材料的热胀系数的差异,因此很大程度地改善了电池片烧结后的翅曲问题。 [0011] The present inventors have found through many experiments, the present invention, by adding the conductive paste companion amount of inorganic powder, an inorganic powder material having such a large negative coefficient of thermal expansion, and having an isotropic in response to a wide temperature range; Lu such a negative thermal expansion material powder inorganic powder in the slurry, after mixing and grinding glass frit and an organic vehicle W, i.e., to obtain a solar cell of the present invention companion conductive paste, by using the present invention. the solar cell is greatly reduced by Lu conductive paste, the thermal expansion coefficient of the residue after metal slurry sintering companion compared, thus reducing the difference in the thermal expansion coefficient of the residue and a slurry sintering baby material, thus largely improving warpage problems after sintering solar cells.

[0012] 本发明中,所述无机添加剂粉体选自0-裡霞石、鹤酸错或饥酸错。 [0012] In the present invention, the inorganic additive is selected from 0- in powder nepheline, hunger crane acid or acid wrong wrong. 其中,0-裡霞石在O-IOOCTC内的平均热膨胀系数为-6. 4X10V°C。 Wherein, in the nepheline 0- average thermal expansion coefficient in the O-IOOCTC to -6. 4X10V ° C. 鹤酸错在0. 3-777°C之间具有各向同性的负热膨胀效应,其负热膨胀系数最高可达-8. 7X10 6/°C,且其负热膨胀系数的溫度范围也比较广。 Crane acid wrong isotropic negative thermal expansion effect between 0. 3-777 ° C, the negative coefficient of thermal expansion up to -8. 7X10 6 / ° C, and the temperature range of negative thermal expansion coefficient is relatively broad.

[0013]因此,所述0-裡霞石、鹤酸错和饥酸错在现有技术中侣浆的常用烧结溫度范围内具有更大的负热膨胀系数。 [0013] Thus, in the 0- nepheline, and hunger crane acid wrong wrong acids having a larger negative coefficient of thermal expansion common companion sintering temperature range in the prior art slurry. 因此,本发明中通过采用0-裡霞石、鹤酸错或饥酸错作为浆料中的无机添加剂粉体,能大大降低浆料的热膨胀系数,从而改善电池片烧结后的翅曲问题。 Accordingly, by using the present invention, in the 0- nepheline, crane or hunger acid wrong wrong acid powder as the inorganic additive in the slurry can greatly reduce the thermal expansion coefficient of the slurry, thereby improving the warpage problem of the battery after sintering sheet.

[0014] 同时,本发明中,所述太阳能电池用侣导电浆料中,所采用的无机添加剂粉体的中粒径咕。 [0014] Meanwhile, in the present invention, the solar cell companion conductive paste, the particle diameter of the inorganic additive powder cushions employed. 为0. 1-5. 0ym。 As 0. 1-5. 0ym. 所述无机添加剂的中值粒径不能太大,否则不能很好的填充于侣粉和玻璃粉之间,影响烧结后侣膜的导电性能,影响电池效率。 The median particle size of the inorganic additive can not be too large, otherwise not well is filled between the powder and the glass frit Lu, Lu affect the film after sintering conductivity, impact cell efficiency. 另外,所述无机添加剂的中值粒径也不能太小,否则加工困难、且材料成本升高。 In addition, the median diameter of the inorganic additives may also not be too small, otherwise processing difficulties, and the material cost is increased. 优选情况下,所述无机添加剂的中粒径D加为0. 5_3. 0ym。 Preferably, the particle size of the inorganic additive is added to D 0. 5_3. 0ym.

[001引本发明的无机添加剂粉体中,在浆料高溫烧结过程中,0 -裡霞石(LizO•Al203 • 2Si02)可看作是氧化裡、氧化侣与氧化娃的组合物,鹤酸错(Zr02 .W03)可看作是=氧化鹤与二氧化错的组合物,而饥酸错(Zr02 可看作是五氧化二饥与二氧化错的组合物。在晶体娃太阳电池的烧结工艺下,所述无机添加剂粉体与浆料中的玻璃粉相互烙合,从而成为浆料粘结剂的一部分,增加烧结后侣膜对娃基体的附着力,同时也可减少浆料中的玻璃粉的添加量,从而保证浆料体系侣粉的含量,W避免导电物的减少而导致电池片的光电转换效率的降低。 Inorganic additive powder [001 incorporated in the present invention, a high temperature sintering process in a slurry, 0 - li nepheline (LizO • Al203 • 2Si02) can be regarded as oxide, the oxide companion baby oxide composition crane acid error (Zr02 .W03) can be regarded as oxide = crane and wrong dioxide composition, and hunger wrong acid (can be regarded as of Zr02 hunger pentaoxide or wrong dioxide composition. sintered at baby crystal solar cell under the process, the additive powder and inorganic glass frit slurry is baked together with each other, thus becoming part of the slurry binder, increase the adhesion of the film after sintering baby companion matrix, can also reduce the slurry the amount of glass frit is added, so as to ensure the content of the powder slurry system Lu, W and prevent a decrease of the conductive material results in a reduction in photoelectric conversion efficiency of solar cells.

[0016] 优选情况下,本发明中,所述无机添加剂粉体为0-裡霞石。 The [0016] Preferably, the present invention, the inorganic additive is in the range of 0 nepheline powder. 因为0-裡霞石比鹤酸错、饥酸错更易获得,且能经受急剧的溫度变化,性能不发生任何改变。 Since 0- error ratio in nepheline crane acid, hunger wrong acid more available, and can withstand rapid temperature change, any change in properties occurs. 另外,P-裡霞石相比鹤酸错、饥酸错,在相应溫度区域内具有更大的平均负热膨胀系数。 Further, P- nepheline compared crane acid in the wrong, the wrong hunger acid, having a greater average negative thermal expansion coefficient within the respective temperature range. 本发明中,所述无机添加剂粉体可通过自己制备,也可直接采用市售产品,例如可W采用天津洪腾电子陶瓷有限公司的负膨胀系数系列的裡霞石粉末。 The present invention, the inorganic powder additive may be prepared by themselves, commercially available products may be used directly, for example, using negative expansion coefficient W in series nepheline powder Hongteng Tianjin Electronic Ceramics Limited.

[0017] 本发明中,所述太阳能电池用侣导电浆料中,侣粉、玻璃粉和无机载体的含量均在本领域技术人员常用范围内即可,本发明没有特殊规定。 [0017] In the present invention, a solar cell with a conductive paste Lu, Lu powder, glass powder and the content of the inorganic carrier are used within the purview of one skilled in the art can, according to the present invention is not particularly specified. 例如,W所述太阳能电池用侣导电浆料的总重量为基准,侣粉的含量为60-85wt%,玻璃粉的含量为0. 2-8.Owt%,有机载体的含量为15-30wt〇/〇。 For example, W the total weight of the solar cell as a reference companion conductive paste, the content of companion powder is 60-85wt%, the content of glass frit is 0. 2-8.Owt%, content of the organic carrier is 15-30wt square / square.

[0018] W所述太阳能电池用侣导电浆料的总重量为基准,本发明中,所述无机添加剂粉体的含量为0. 5-5.Owt%。 [0018] The total weight W for a solar cell as a reference companion conductive paste, the present invention, the content of the inorganic additive powder is 0. 5-5.Owt%. 虽然所述无机添加剂的用量相对侣粉来说比较小,根据热膨胀系数的加和性,浆料烧结后得到的残留混合物仍然具有正热膨胀特性,但其膨胀系数相比金属侣已大大降低。 Although the additive amount of the inorganic powder is relatively small companion, from the residual mixture was added and the coefficients of thermal expansion of the slurry obtained after the sintering still having a positive thermal expansion characteristic, but its companion expansion coefficient compared to metals has been greatly reduced. 同时,本发明的发明人通过实验发现,浆料中无机添加剂粉体含量过多, 可能会影响烧结后侣膜的导电性能,而过少又起不到降低电池片翅曲度的效果。 Meanwhile, the inventors of the present invention found through experiments that, excessive inorganic additive powder content in the slurry may affect the conductivity of the film after sintering companion, and too little will not achieve the effect of reducing the cell plate fin curvature.

[0019] 本发明中,所述侣粉为现有的侣导电浆料中常用的各种侣粉。 [0019] In the present invention, the powder is Lu Lu conventional conductive paste commonly used in a variety of companion powder. 例如,所述侣粉为氮气雾化法得到的活性侣含量在98. 5%W上的球形侣粉。 For example, the content of Lu Lu obtained powder as an active nitrogen gas atomizing method companion spherical powder of a 98. 5% W. 优选情况下,所述侣粉的中粒径〇5。 Preferably, the particle size of the powder 〇5 companion. 为2.0-8.0ym。 As 2.0-8.0ym. 本发明中,所述侣粉可直接采用商购产品,例如可W采用河南远洋公司生产的中值粒径D50为2. 0~8. 0ym球状侣粉、或者湖南恒昌股份有限公司生产〇5。 In the present invention, the powder can be directly used companion commercially available products, for example, W may be produced using ocean Henan median diameter D50 of 2. 0 ~ 8. 0ym companion spherical powder, square or Hunan Hengchang Co. 5. 小于8. 0ym 的球状侣粉。 8. 0ym less than the spherical powder of Lu.

[0020] 本发明中,所述玻璃粉可采用现有技术中常用的各种无铅玻璃粉,例如可W采用Bi2〇3-B2〇3-Si〇2系玻璃粉。 [0020] In the present invention, the glass frit can be commonly used in the prior art lead-free glass frit, for example using W-Si〇2 B2〇3 Bi2〇3-based glass frit. 所述Bi2〇3-B2〇3-Si〇2系玻璃粉的组成为:氧化祕(Bi2〇3)占30-70wt%,S氧化二棚(B203)占5-30wt%,二氧化娃(Si〇2)占2-15wt%,氧化巧(CaO)占1.0-5. Owt%,氧化儀(MgO)占0.2-8. Owt%,氧化侣(AI2O3)占0-5. Owt%,氧化领(BaO)占0-3. Owt%。 The composition Bi2〇3 B2〇3 Si〇2 - based glass frit is: Peru oxide (Bi2〇3) accounts for 30-70wt%, S shed oxide (B203) representing 5-30wt%, baby dioxide ( Si〇2) accounted 2-15wt%, Qiao oxide (CaO) representing 1.0-5. Owt%, instrument oxide (MgO) representing 0.2-8. Owt%, companion oxide (of AI2O3) representing 0-5. Owt%, oxide collar (BaO) accounted for 0-3. Owt%. 所述Bi2〇3-B2〇3-Si〇2系玻璃粉可直接采用商购产品,也可自己合成,合成方法为: 将W上各类氧化物粉末按比例混合均匀,烙炼、水泽、过滤、烘干,研磨至所需粒径即得到所述Bi2〇3-B2〇3-Si〇2系玻璃粉。 The Bi2〇3-B2〇3 Si〇2-based glass frit can be directly used commercially available products, but also their synthesis, the synthesis method: the various types of the W oxide powder homogeneously mixed at a ratio, branded refining, Mizusawa, filtered, dried, ground to the desired particle size to obtain the Bi2〇3-B2〇3 Si〇2-based glass frit. 优选情况下,本发明中,所述玻璃粉的中粒径D5。 Preferably, in the present invention, the glass frit of particle size D5. 为0. 2-3. 0 微米。 0. 2-3. 0 microns. 所述玻璃粉的始烙点为580-620°C。 Starting point of the glass frit is baked 580-620 ° C.

[0021] 上述无机添加剂粉体、侣粉、玻璃粉的中粒径〇5。 [0021] The inorganic powder additive, companion powder, glass powder the particle diameter 〇5. 均可通过现有的测试中粒径的方法和仪器进行测试,例如可采用BT-9300型激光粒度分析仪进行测试。 It can be tested by a conventional test method and apparatus for particle size, for example, may be employed BT-9300 laser particle size analyzer test. 阳022] 本发明的有机载体为现有技术中常用的含有乙基纤维素、助剂和溶剂的混合体系。 Male organic vehicle 022] of the present invention is a prior art conventional mixing systems containing ethyl cellulose, additives and solvent. W所述有机载体的总质量为基准,其中乙基纤维素的含量为3. 0-15wt%,助剂的含量为0. 5-5.Owt%,溶剂的含量为70-95wt%。 W total mass of the organic vehicle as a reference, wherein the content of ethyl cellulose is 3. 0-15wt%, the content of additives is 0. 5-5.Owt%, the solvent content is 70-95wt%. 其中,所述溶剂可采用现有技术中常用的多种溶剂的组合,即为混合溶剂。 Wherein the solvent composition employed in the prior art commonly used in a variety of solvents, i.e. a mixed solvent. 例如,所述混合溶剂可选自松油醇、邻苯二甲酸二下醋(DBP)、下基卡必醇、松节油、乙二醇下酸、下基卡必醇醋酸醋、乙二醇乙酸醋酸醋、巧樣酸S下醋、二乙二醇单下酸乙酸醋、邻苯二甲酸二下醋、憐酸=下醋中的两种或两种W上。 For example, the mixed solvent may be selected from terpineol, vinegar under phthalate (DBP), under carbitol, turpentine, glycol acid, vinegar under carbitol acetate, ethylene glycol acetate vinegar acetic acid S clever like vinegar, the acetic acid diethylene glycol monoethyl acetate, dibutyl phthalate, and vinegar, vinegar pity of the acid = two or W. 所述助剂选自十六醇、十八醇、聚酷胺蜡粉、氨化藍麻油中的一种或多种。 Said adjuvant is selected from cetyl alcohol, stearyl alcohol, polyethylene wax cool amines, one or more amides of sesame oil blue.

[0023] 本发明还提供了所述太阳能电池用侣导电浆料的制备方法,包括将玻璃粉和无机添加剂粉体分散于有机载体中,然后分批加入侣粉,研磨后得到所述太阳能电池用侣导电浆料;所述无机添加剂粉体的中粒径〇5。 [0023] The present invention further provides a method of preparing a solar cell of the companion conductive paste, comprising glass frit, inorganic additives and powder dispersed in an organic carrier, and then added portionwise companion powder, after trituration of the solar cell Lu with conductive paste; particle size of said inorganic additive powder 〇5. 为0. 1-5. 0ym,且选自0 -裡霞石、鹤酸错或饥酸错的一种或多种。 To 0. 1-5 0ym, and selected from 0 - in one or more of nepheline, hunger crane acid or acid wrong wrong.

[0024] 具体地,所述无机载体的配制方法为:将乙基纤维素与助剂溶解加入混合溶剂中, 在20-70°C下使乙基纤维素、助剂充分溶解并揽拌均匀,即得到透明的有机载体。 [0024] In particular, the method of preparation of the inorganic carrier: ethyl cellulose mixed with the adjuvants dissolved by adding solvent, at 20-70 ° C ethylcellulose, adjuvants sufficiently dissolved and mixed uniformly embrace , to obtain a transparent organic vehicle.

[0025] 本发明中,为保证侣粉与玻璃粉、无机添加剂粉体均匀分散,所述侣粉为分批加入。 [0025] The present invention, in order to ensure that the glass frit powder and Lu, the inorganic additive is uniformly dispersed powder, said powder is a companion added portionwise. 优选情况下,侣粉的分批次数为2-3次,每次加入后揽拌均匀,再加入下一批次;全部加完后,高速揽拌均匀。 Preferably, the batch number was 2-3 times companion powder, uniform mixing after each addition embrace, then adding the next batch; after all was added, uniformly mixed high-speed embrace. 所述研磨可采用=漉研磨机进行,研磨次数为10-15次,研磨至浆料细度至< 20ym,即得到本发明提供的太阳能电池用导电浆料。 The grinding can be Luk = grinder, grinding times of 10-15 times, milled to a fineness of the slurry to <20ym, i.e., to obtain a solar cell of the present invention provides a conductive paste.

[0026] 下面通过实施例对本发明作进一步的说明。 [0026] The following examples further illustrate the present invention. 实施例及对比例中所采用原料均通过商购得到。 Examples and Comparative employed raw materials are obtained by a commercially available embodiment. 阳〇27] 实施例1 Male 〇27] Example 1

[002引本实施例用于说明本发明公开的太阳能电池导电浆料及其制备方法。 [002 solar cell lead according to the present embodiment the conductive paste and preparation method described embodiments of the present invention is disclosed for.

[0029] (1)玻璃粉的制备 Preparation of [0029] (1) glass frit

[0030] 取55wt% 的氧化祕(Bi2〇3),25wt% 的;氧化二棚化〇3),15wt% 二氧化娃(Si〇2), 3. 5wt%的氧化巧(CaO),1. 5wt%的氧化儀(MgO),采用V型混合机将各组分混合均匀,装入瓷相蜗中,放入娃碳棒炉,升溫预热到550°C,保溫0.化,再升至1250°C,烙炼0.化,水泽过滤,将得到的玻璃珠装入球磨罐,控制质量比氧化错球:玻璃珠:去离子水=4 :1 :0. 6,转速250转/分钟,球磨化,过滤后烘干,再干磨0.化,干磨时氧化错球与玻璃粉的质量比为1 : 2,得到中粒径〇5。 [0030] 55wt% of the oxidation takes secret (Bi2〇3), 25wt%; the rasterized 〇3 oxide), 15wt% baby dioxide (Si〇2), 3. 5wt% Qiao oxide (CaO), 1 . 5wt% instrument oxide (MgO), a V-type mixer for mixing the components are homogeneously charged with a worm in the porcelain, baby carbon rod into a furnace heated preheated to 550 ° C, heat of 0.5, then was raised to 1250 ° C, 0. branded refining of Mizusawa was filtered, and the resulting glass beads mill pot was charged, the control oxide wrong ball mass ratio: glass beads: deionized water = 4: 1: 06, a speed of 250 rpm / min, a ball mill, filtered after drying, grinding 0. do it again, oxidation wrong ball mass ratio of the glass frit is dry milling is 1: 2 to give the particle size 〇5. 为1. 5 ym的玻璃粉,备用。 To 1. 5 ym glass frit, spare.

[0031] (2)有机载体的配制 [0031] (2) Preparation of organic vehicle

[0032] 按照质量比下基卡必醇:松油醇:下基卡必醇醋酸醋:邻苯二甲酸二下醋(DBP) =75 :10 :10 :5,将各有机溶剂混合均匀,得到混合溶剂。 [0032] The mass ratio carbitol: terpineol: the vinegar carbitol acetate: vinegar under phthalate (DBP) = 75: 10: 10: 5, each of the mixed organic solvent, to give a mixed solvent. 取90重量份的混合溶剂,加入7. 5 重量份乙基纤维素STD-4 (陶氏产,粘度为4),2重量份氨化藍麻油,0. 5重量份十六醇,加热至7(TC使充分溶解,揽拌均匀得到均一澄清的有机载体。 Take 90 parts by weight of a mixed solvent, was added 7.5 parts by weight of ethyl cellulose STD-4 (Dow yield, viscosity 4), 2 parts by weight of ammoniated blue oil, 0.5 parts by weight cetyl alcohol and heated to 7 (TC so fully dissolved, mix well to obtain a uniform embrace clear organic vehicle.

[0033] (3)侣导电浆料的制备 Preparation of [0033] (3) The conductive paste companion

[0034] 取22重量份的由步骤(2)制得的有机载体,置于高速分散机的不诱钢罐中,揽拌状态下加入1. 5重量份步骤(1)制得的玻璃粉和2. 5重量份0 -裡霞石粉(天津洪腾电子陶瓷有限公司,中粒径〇5。为1. 5ym),揽拌均匀。 [0034] 22 parts by weight taken from step (2) an organic vehicle prepared, placed in high-speed disperser steel can not trap, was added 1.5 parts by weight of mixed state embrace the step (1) made of glass frit and 2.5 parts by weight 0 - in Xia powder (Tianjin Hongteng electronic ceramics Co., Ltd., particle size of 〇5 1. 5ym), embrace mix well. 再分2批次加入74重量份球形侣粉(河南远洋公司生产的超纯侣粉,中粒径〇5。为4. 5ym),每批次侣粉加入后先揽拌均匀,再加入下一批次;全部加完后,高速揽拌均匀;最后用0150的=漉研磨机研磨15次,研磨至浆料细度< 20帕,得到本实施例的太阳能电池用侣导电浆料,记为S1。 Was added in 2 batches and then 74 parts by weight of spherical powder Lu (Henan offshore produced ultrapure companion powder, particle size 〇5 For 4. 5ym), companion powder was added after each batch to embrace uniformly mix, then add the a batch; after all was added, uniformly mixed high-speed embrace; Luk Finally = 0150 polishing mill 15 for grinding to a fine paste of <20 Pa, to obtain a solar cell according to the present embodiment with companion conductive paste, denoted as S1. 阳0对实施例2 0 cases of male Embodiment 2

[0036] 采用与实施例1相同的步骤制备本实施例的太阳能电池用侣导电浆料S2,不同之处在于:步骤(3)中,0 -裡霞石粉的用量由2. 5重量份改为5重量份,玻璃粉的用量由1. 5 重量份改为0. 5重量份,侣粉的用量由74重量份改为72. 5重量份。 [0036] Prepared using the same procedure as in Example 1 of the present embodiment, a solar cell with a conductive paste companion S2, except that: in step (3), 0 - Xia powder in an amount of 2.5 parts by weight of a modified 5 parts by weight, the amount of the glass powder was changed to 1.5 parts by weight 0.5 parts by weight, the amount of powder companion changed from 74 parts by weight 72.5 parts by weight.

[0037] 实施例3 [0037] Example 3

[003引采用与实施例I相同的步骤制备本实施例的太阳能电池用侣导电浆料S2,不同之处在于:步骤(3)中,0-裡霞石粉的中粒径05。 [003 using primers with the same procedures as in Example I for preparing a solar cell of the present embodiment is a conductive paste companion S2, except that: in step (3), in 0- Xia powder particle size of 05. 由LSiim改成5.0ym。 By the LSiim into 5.0ym.

[0039]实施例4 W40] 采用与实施例1相同的步骤制备本实施例的太阳能电池用侣导电浆料S2,不同之处在于:步骤(3)中,采用鹤酸错替代实施例1中的0-裡霞石粉。 [0039] Example 4 W40] using the same procedure was prepared a solar cell 1 according to the present embodiment with the companion conductive paste S2 embodiment, except that: in step (3), the use of alternative error crane acid Example 1 0-Xia powder inside. 阳OW 对比例1 Yang OW Comparative Example 1

[0042] 采用与实施例1相同的步骤制备本对比例的太阳能电池用侣导电浆料DS1,不同之处在于:步骤(3)中,不加入0 -裡霞石粉,同时玻璃粉的用量由1. 5重量份改为4重量份。 [0042] The same procedure as in Example 1. Comparative Example solar cell conductive paste companion DS1, except that the present preparation: Step (3) was not added 0 - Xia powder in, while an amount of a glass frit 1.5 parts by weight to 4 parts by weight. W43] 对比例2 W44] 采用与实施例1相同的步骤制备本对比例的太阳能电池用侣导电浆料DS2,不同之处在于:步骤(3)中,不加入0 -裡霞石粉,同时璃粉的用量由1. 5重量份改为2. 5重量份,侣粉的用量由74重量份改为75. 5重量份。 W43] Comparative Example 2 W44] using the same procedures as in Example 1. Comparative Example solar cell conductive paste companion DS2, except that this Preparation: Step (3) was not added 0 - in Xia powder, glass while the amount of powder by 1.5 parts by weight to 2.5 parts by weight, the amount of powder companion changed from 74 parts by weight 75.5 parts by weight. W45] 对比例3 W45] Comparative Example 3

[0046] 采用与实施例1相同的步骤制备本对比例的太阳能电池用侣导电浆料DS3,不同之处在于:步骤(3)中,0-裡霞石粉的中粒径〇5。 [0046] The same procedure as in Example 1 to prepare the comparative solar cell by the conductive paste companion DS3, except that: in step (3), in 0- Xia powder of particle size 〇5. 由1.5ym改成6.0ym。 By the 1.5ym into 6.0ym. W47] 对比例4 W4引采用CN101728439A的方法制备本对比例的太阳能电池侣导电浆料DS4,具体步骤与实施例1相同,不同之处在于:步骤(3)中,采用2. 5重量份的中粒径〇5。 W47] The solar cell of the present comparative companion conductive paste is prepared DS4 method of Comparative Example 4 W4 CN101728439A primers employed, and the specific steps the same as in Example 1, except that: in step (3), the use of 2.5 parts by weight particle size 〇5. 为3. 5微米的棚粉取代实施例1中的2. 5重量份0 -裡霞石粉。 To shed powder 3.5 microns 2.5 parts by weight of 0-substituted in Example 1 - in Xia powder. W例性能测试 Performance Test Example W

[0050] 将上述太阳能电池用侣导电浆料S1-S4和DS1-DS4分别在生产线试用。 [0050] The above conductive paste for a solar cell companion S1-S4, respectively, and DS1-DS4 tested in the production line. 多晶娃片规格:156156mm,厚度为200ym(腐蚀前),印刷前厚度为ISOiim。 Baby polycrystalline sheet size: 156156mm, thickness 200ym (before etching), the pre-press thickness ISOiim. 先采用200目的丝网印刷背面银电极浆料(杜邦PV505),烘干,再采用280目的丝网目数印刷太阳能电池用侣导电浆料S1-S4和DS1-DS4,印刷重量为每片用浆1. 5克,烘干溫度均为125°C,烘干时间为4min, 再采用200目的丝网印刷正面银电极浆料(杜邦16C),过隧道炉烘干烧结,隧道炉溫度梯度分布,过隧道炉的时间为2min,烧结峰值溫度为89010°C,时间为2s,出炉后测试各电池片S10-S40和DS10-DS40的各项性能。 Using 200-mesh screen printing to the rear surface silver electrode paste (DuPont PV505), dried, then using 280-mesh screen printing mesh companion conductive paste for a solar cell S1-S4, and DS1-DS4, the printed sheet with a weight per 1.5 g slurry, drying temperatures are 125 ° C, the drying time is 4min, then using 200-mesh screen printing a front electrode silver paste (DuPont 16C), drying over sintering tunnel furnace, the tunnel furnace temperature gradient profile , through the tunnel furnace time 2min, the sintering peak temperature of 89010 ° C, time of 2s, each of the batteries after the test pieces baked S10-S40 and the performance of the DS10-DS40.

[005U(1)表面状况:目测背场表面状况,光滑、无侣珠或侣瘤,记为0K,否则为NG。 [005U (1) surface condition: Visual back field surface condition, smooth, no beads or companion companion tumors, referred to as 0K, otherwise NG.

[0052] (2)附着力:室溫下用自来水浸泡各电池片7天,背场金属膜不脱落或用纯器轻刮不脱落,记为0K,否则为NG。 [0052] (2) Adhesion: with tap water at room temperature for 7 days soaking pieces of each battery, the metal film is not back off the field or do not fall off with pure scuffing is referred to as 0K, or as NG.

[0053] (3)翅曲度:将电池片的弯曲程度用游标卡尺测量,单位为mm。 [0053] (3) the curvature wings: the degree of bending of the cell sheets with calipers measured in mm. 重复100次,记录翅曲度的平均值。 Was repeated 100 times, recording the average fin curvature.

[0054] (4)光电转化效率:采用单次闪光模拟器按照IEC904-1公开的方法对各电池片进行测试。 [0054] (4) the photoelectric conversion efficiency: single flash simulator test pieces of each battery according to the method disclosed IEC904-1. 测试条件为标准测试条件(STC):光强:1000W/m2;光谱:AM1. 5 ;溫度:25°C。 Test conditions for standard test conditions (STC): light intensity: 1000W / m2; Spectrum:. AM1 5; Temperature: 25 ° C. 重复100次,记录光电转化效率的平均值。 Was repeated 100 times, recording the average value of the photoelectric conversion efficiency.

[0055] 测试结果如表1和表2所示。 [0055] The test results are shown in Tables 1 and 2. 阳化6] 表1 Yang 6] Table 1

[0057] [0057]

Figure CN103177791BD00081

阳化8] 表2 Yang 8] Table 2

[0059] [0059]

Figure CN103177791BD00082

[0060] 从上表1与表2的结果比较可W看出,采用本发明提供的太阳能电池用侣导电浆料丝网印刷到晶体娃太阳电池上并烧结成膜后,得到侣膜光滑致密,无侣珠、侣瘤,光电转换效率高,电池片翅曲度小,156X156型多晶娃太阳电池片的平均翅曲度小于0. 50mm。 [0060] W can be seen from comparing the results of Table 1 and Table 2, the present invention provides a solar cell using the conductive paste with companion screen printed onto the baby crystal solar cell deposition and sintering, to obtain smooth dense film companion , no companion beads, Lu tumors, high photoelectric conversion efficiency, small solar cells fin curvature, the mean curvature of the wing 156X156 polymorph baby solar cell sheet is less than 0. 50mm.

[0061] W上所述仅为本发明的较佳实施例而已,并不用W限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。 [0061] W the embodiments of the invention only the preferred embodiments only, not to limit the invention by W, any modifications within the spirit and principle of the present invention, equivalent substitutions and improvements should be included in the within the scope of the present invention.

Claims (11)

  1. 1. 一种太阳能电池用铝导电浆料,其特征在于,所述太阳能电池用铝导电浆料的组分包括铝粉、玻璃粉、有机载体和无机添加剂粉体;以所述太阳能电池用铝导电浆料的总重量为基准,所述无机添加剂粉体的含量为0. 5-5. Owt %,所述无机添加剂粉体的中粒径D5。 A solar cell aluminum electroconductive paste, wherein the aluminum component of the solar cell conductive paste comprises aluminum powder, glass frit, an organic vehicle and an inorganic additive powder; aluminum in the solar cell the total weight of the conductive paste as a reference, the content of the inorganic additive powder is 0. 5-5. Owt%, the inorganic additive powder particle size D5. 为0. 1-5. Oy m,且选自(6-锂霞石、钨酸锆或钒酸锆的一种或多种。 As 0. 1-5. Oy m, and selected from (one or more 6--eucryptite, zirconium tungstate or vanadate zirconium.
  2. 2. 根据权利要求1所述的太阳能电池用铝导电浆料,其特征在于,所述无机添加剂粉体为(6-锂霞石。 The solar cell aluminum electroconductive paste according to claim 1, wherein said inorganic powder as additive (6-eucryptite.
  3. 3. 根据权利要求1所述的太阳能电池用铝导电浆料,其特征在于,所述无机添加剂粉体的中粒径D5。 The solar cell aluminum electroconductive paste according to claim 1, wherein said inorganic additive powder particle size D5. 为0. 5-3. 0 ym。 To 0. 5-3. 0 ym.
  4. 4. 根据权利要求1-3中任一项所述的太阳能电池用铝导电浆料,其特征在于,以所述太阳能电池用铝导电浆料的总重量为基准,铝粉的含量为60-85wt %,玻璃粉的含量为0• 2-8. Owt %,有机载体的含量为15-30wt %。 The solar cell aluminum conductive paste according to any one of the preceding claims, characterized in that the total weight of the aluminum conductive paste solar cell as a reference, the content of aluminum is 60 85wt%, the content of glass frit is 0 • 2-8. Owt%, content of the organic carrier is 15-30wt%.
  5. 5. 根据权利要求1所述的太阳能电池用铝导电浆料,其特征在于,所述铝粉为活性铝含量在98. 5%以上的雾化球形铝粉。 The solar cell aluminum electroconductive paste according to claim 1, wherein said aluminum powder is atomized spherical aluminum powder active aluminum content of more than 98.5% of.
  6. 6. 根据权利要求1所述的太阳能电池用铝导电浆料,其特征在于,所述玻璃粉为Bi2O3-B 2O3-SiO2 系玻璃粉。 The solar cell aluminum electroconductive paste according to claim 1, wherein said glass frit is a Bi2O3-B 2O3-SiO2-based glass frit.
  7. 7. 根据权利要求1、5、6任一项所述的太阳能电池用铝导电浆料,其特征在于,所述铝粉的中粒径D5。 The solar cell aluminum electroconductive paste according to any one of claims 1,5,6, wherein said aluminum powder particle size D5. 为2. 0-8. 0 ym,玻璃粉的中粒径D 5。 Of 2. 0-8. 0 ym, the diameter D 5 of the glass frit. 为0. 2-3. 0 ym。 To 0. 2-3. 0 ym.
  8. 8. 根据权利要求1所述的太阳能电池用铝导电浆料,其特征在于,所述有机载体含有3. 0-15wt%的乙基纤维素,0• 5-5. Owt%的助剂和占70-95wt%的混合溶剂。 The solar cell aluminum electroconductive paste according to claim 1, wherein said organic vehicle contains 3. 0-15wt% of ethylcellulose, 0 • 5-5. Owt% auxiliaries and accounting for 70-95wt% of the mixed solvent.
  9. 9. 根据权利要求8所述的太阳能电池用铝导电浆料,其特征在于,所述混合溶剂选自松油醇、邻苯二甲酸二丁酯、丁基卡必醇、松节油、乙二醇丁醚、丁基卡必醇醋酸酯、乙二醇乙醚醋酸酯、柠檬酸三丁酯、二乙二醇单丁醚乙酸酯、磷酸三丁酯中的两种或两种以上。 The solar cell according to claim aluminum electroconductive paste according to claim 8, characterized in that, in the mixed solvent is selected from terpineol, dibutyl phthalate, butyl carbitol, turpentine, ethylene glycol tributyl ether, butyl carbitol acetate, ethylene glycol ethyl ether acetate, tributyl citrate, diethylene glycol monobutyl ether acetate, phosphoric two or more.
  10. 10. 权利要求1所述的太阳能电池用铝导电浆料的制备方法,其特征在于,包括将玻璃粉和无机添加剂粉体分散于有机载体中,然后分批加入铝粉,研磨后得到所述太阳能电池用铝导电浆料;所述无机添加剂粉体的中粒径D 5。 10. A method of preparing a solar cell as claimed in claim aluminum conductive paste, characterized by comprising a glass frit powder and an inorganic additive dispersed in an organic carrier, and then added portionwise aluminum powder, after grinding to give the aluminum electroconductive paste of the solar cell; said inorganic additive powder particle size D 5. 为0. 1-5. 0 ym,自P -锂霞石、钨酸锆或钒酸锆的一种或多种。 Is 0. 1-5 0 ym, since the P -. One or more eucryptite, zirconium tungstate or vanadate zirconium.
  11. 11. 根据权利要求10所述的制备方法,其特征在于,所述研磨的次数为10-15次,至浆料细度< 20ym。 The production method according to claim 10, wherein the number of polishing is 10-15 times, to the slurry fineness <20ym.
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CN104751939B (en) * 2013-12-31 2017-05-31 比亚迪股份有限公司 A crystalline silicon solar cell with aluminum conductive paste
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