CN110590167B - 杂化玻璃粉的制备方法及应用 - Google Patents
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- 229910021389 graphene Inorganic materials 0.000 claims abstract description 48
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052709 silver Inorganic materials 0.000 claims abstract description 20
- 239000004332 silver Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 30
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
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- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
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- 230000008569 process Effects 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
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- 229910003069 TeO2 Inorganic materials 0.000 description 1
- XNRNVYYTHRPBDD-UHFFFAOYSA-N [Si][Ag] Chemical compound [Si][Ag] XNRNVYYTHRPBDD-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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- C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
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Abstract
本申请公开了一种杂化玻璃粉的制备方法及应用,先将石墨烯包覆在玻璃粉上,然后沉积银,得到包覆有石墨烯及银的玻璃粉,在高温烧结过程中,石墨烯能在界面形成良好的欧姆接触,同时石墨烯表面包覆的银层能提高对银粉的浸润性,减少银粉烧结过程中界面孔洞的产生,提高太阳能电池片的电性能。
Description
技术领域
本申请涉及电子材料技术领域,具体涉及一种杂化玻璃粉的制备方法及应用。
背景技术
导电银浆是晶体硅太阳能电池的关键材料,直接影响电池的性能。导电银浆主要由3部分组成:导电银粉、玻璃粉和有机相。银粉为导电相,玻璃粉在烧结过程中起粘结、促进银粉熔融以及形成银硅欧姆接触的媒介物质的作用,有机相起分散和赋予浆料流动性的作用。
玻璃粉在银浆中只占较小比例,但却是影响银粉烧结效果、硅表面腐蚀程度、接触电阻等性能的重要因素,特别是烧结后能否与硅形成良好的欧姆接触是提高太阳能电池光电转换效率的关键。为此,现有技术大多在玻璃粉中添加一定的氧化物,来提高烧结过程中对银的润湿能力,以获得更为致密的电极结构。但是玻璃粉中各组分膨胀系数不同,且银粉在烧结过程中也会收缩,导致Ag/Si界面易产生孔隙,限制了电池性能的提高。
石墨烯具有优异的电学性能,其电阻比银更低,部分技术使用石墨烯替代部分银粉,以获得更低的并联电阻。但是,这种方式主要考虑了导电相性能的改善,对界面接触电阻的改善作用有限。
发明内容
本申请具体实施例提供一种杂化玻璃粉的制备方法及应用,在玻璃粉表面附着石墨烯和银,降低界面接触电阻,提高对银粉的浸润性。所采用的技术方案如下:
一方面,提供一种杂化玻璃粉的制备方法,包括:
将石墨烯分散在水中,制成石墨烯混悬液;
配置水和异丙醇的混合溶剂,加入玻璃粉分散均匀,依次加入硅烷偶联剂及上一步骤制得的石墨烯混悬液,超声分散,加热,再经洗涤干燥,制得石墨烯包覆玻璃粉;
在超声及搅拌作用下将制得的石墨烯包覆玻璃粉加入硝酸银溶液中,分散均匀,维持超声搅拌作用不变,加入还原剂,使银沉积在粉体表面,经洗涤干燥,制得杂化玻璃粉。
优选的,所述还原剂为抗坏血酸。
优选的,所述玻璃粉、石墨烯、硝酸银的重量比为1:0.005~0.05:0.5~1。
优选的,所述石墨烯片径为0.1~0.5μm,玻璃粉粒径为1~4μm。
优选的,所述硝酸银溶液浓度为0.5~2mol/L。
优选的,所述硅烷偶联剂用量为玻璃粉重量的0.5~5%。
另一方面,提供一种导电银浆,其含有上述方法制得的杂化玻璃粉。
本申请具体实施例提供的技术方案至少具有以下有益效果:
石墨烯具有优异的电学性能,先将石墨烯包覆在玻璃粉上,然后沉积银,得到包覆有石墨烯及银的玻璃粉,在高温烧结过程中,石墨烯能在界面形成良好的欧姆接触,同时石墨烯表面包覆的银层能提高对银粉的浸润性,减少银粉烧结过程中界面孔洞的产生,提高太阳能电池片的电性能。
具体实施方式
为使本申请的目的、技术方案和优点更加清楚,下面将结合具体实施例作进一步地详细描述。此处所描述的实施例仅是本申请一部分实施例,不能理解为对本申请保护范围的限制。
本申请具体实施例提供的杂化玻璃粉的制备方法,包括:
步骤1,将石墨烯分散在水中,制成石墨烯混悬液。配置水和异丙醇的混合溶剂,加入玻璃粉分散均匀,依次加入硅烷偶联剂及所制得的石墨烯混悬液,超声分散,加热,再经洗涤干燥,制得石墨烯包覆玻璃粉。
目前,玻璃粉主要以含铅玻璃粉为主,组分中含有一定量的PbO。为减少危害,满足环保需求,优选为无铅玻璃粉,可选原料包括SiO2、Bi2O3、B2O3、SnO2、Fe2O3、TeO2、ZnO、Al2O3、TiO2等,粒径优选为1~4μm。石墨烯片径优选为0.1~0.5μm,硅烷偶联剂用于使石墨烯片层更好地包覆在玻璃粉表面,用量优选为玻璃粉重量的0.5~5%,在示例性实施例中,采用KH550,用量为玻璃粉重量的3%。
步骤2,在超声及搅拌作用下将步骤1制得的石墨烯包覆玻璃粉加入硝酸银溶液中,混合均匀,并在该条件下加入还原剂,使银沉积在粉体表面,完成银沉积后,经洗涤干燥,制得杂化玻璃粉。硝酸银溶液浓度可以为0.5~2mol/L,为获得性能较好的杂化玻璃粉,玻璃粉、石墨烯、硝酸银的最佳重量比为1:0.005~0.05:0.5~1。还原剂可以是抗坏血酸、水合肼等,优选为抗坏血酸,还原剂可过量。
本方法先将石墨烯包覆在玻璃粉上,在高温烧结过程中,起分散作用的偶联剂挥发,分散在界面的石墨烯能形成良好的欧姆接触,同时,石墨烯表面包覆的银能提高其对银粉的浸润性,使银粉更好地附着在界面,减少界面孔洞的产生,提高太阳能电池片的电性能。
实施例1
杂化玻璃粉的制备方法,包括:
将石墨烯分散在水中,制成石墨烯混悬液;
配置水和异丙醇的混合溶剂(体积比1:9),加入玻璃粉(无铅玻璃粉,粒径1~4μm)分散均匀,然后加入硅烷偶联剂KH550,用量为玻璃粉重量的3%,再加入上一步骤制得的石墨烯混悬液,超声分散,加热至60~70℃,维持60min,再过滤、洗涤、干燥,制得石墨烯包覆玻璃粉;
在超声及搅拌作用下将制得的石墨烯包覆玻璃粉加入1mol/L硝酸银溶液中,分散均匀,维持超声搅拌作用不变,加入抗坏血酸,使银沉积在粉体表面,经洗涤干燥,制得杂化玻璃粉。
其中,玻璃粉、石墨烯、硝酸银的重量比为1:0.05:1。
实施例2
与实施例1相比,区别在于,硝酸银溶液浓度为0.5mol/L,玻璃粉、石墨烯、硝酸银的重量比为1:0.01:0.5。
对比例1
在超声及搅拌作用下将玻璃粉(与实施例1同类型)加入1mol/L硝酸银溶液中,玻璃粉、硝酸银的重量比为1:1,分散均匀,维持超声搅拌作用不变,加入抗坏血酸,使银沉积在玻璃粉表面,经洗涤干燥,制得杂化玻璃粉。
将各实施例和对比例制得的玻璃粉按以下重量比配制成太阳能电池正面银浆:粒径1~3μm的银粉90份、粒径50~100nm的纳米银粉10份,有机载体10份,杂化玻璃粉5份,石墨烯1份。浆料制备方法:将各组分混合均匀,研磨至细度10μm以下。
将制得的正面银浆印刷于厚度为180~190μ的156mm×156mm的硅片上,经烘干、烧结,冷却得到太阳能电池片,测试电性能参数,测试两次,取平均值,结果如表1所示,其中,Uoc为开路电压,Isc为短路电流,Eff为转换效率。可见,实施例1和2采用石墨烯和银包覆的杂化玻璃粉,电池的电性能参数均高于对比例1。
表1
玻璃粉类型 | Uoc(V) | Isc(A) | Eff(%) |
实施例1 | 0.6305 | 8.9901 | 18.5137 |
实施例2 | 0.6300 | 8.9035 | 18.4259 |
对比例1 | 0.6297 | 8.8783 | 18.2516 |
Claims (5)
1.一种杂化玻璃粉的制备方法,其特征在于,包括:
将石墨烯分散在水中,制成石墨烯混悬液;
配置水和异丙醇的混合溶剂,加入玻璃粉分散均匀,依次加入硅烷偶联剂及上一步骤制得的石墨烯混悬液,超声分散,加热,再经洗涤干燥,制得石墨烯包覆玻璃粉;
在超声及搅拌作用下将制得的石墨烯包覆玻璃粉加入硝酸银溶液中,分散均匀,维持超声搅拌作用不变,加入还原剂,使银沉积在粉体表面,经洗涤干燥,制得杂化玻璃粉;
所述玻璃粉、石墨烯、硝酸银的重量比为1:0.005~0.05:0.5~1;
所述石墨烯片径为0.1~0.5μm,玻璃粉粒径为1~4μm。
2.根据权利要求1所述的杂化玻璃粉的制备方法,其特征在于,所述还原剂为抗坏血酸。
3.根据权利要求1所述的杂化玻璃粉的制备方法,其特征在于,所述硝酸银溶液浓度为0.5~2mol/L。
4.根据权利要求1所述的杂化玻璃粉的制备方法,其特征在于,所述硅烷偶联剂用量为玻璃粉重量的0.5~5%。
5.一种导电银浆,其特征在于,其含有权利要求1-4任一项所述的制备方法制得的杂化玻璃粉。
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