CN108899207A - 一步法原位生长硒化镍太阳能电池对电极及其制备方法和应用 - Google Patents
一步法原位生长硒化镍太阳能电池对电极及其制备方法和应用 Download PDFInfo
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- -1 nickelous selenide Chemical class 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011521 glass Substances 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 229910001868 water Inorganic materials 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052697 platinum Inorganic materials 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 239000002002 slurry Substances 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000000975 dye Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 206010070834 Sensitisation Diseases 0.000 description 3
- SXGROPYLQJYUST-UHFFFAOYSA-N iron(2+);selenium(2-) Chemical compound [Fe+2].[Se-2] SXGROPYLQJYUST-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
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- 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
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- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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Abstract
本发明涉及电极材料技术领域,具体涉及一步法原位生长硒化镍用作染料敏化太阳能电池对电极。取去离子水置于烧杯中,加入NiCl2·6H2O和Se,匀速搅拌下滴加NH3·H2O、N2H4·H2O,继续搅拌。将烧杯中溶液转移到高压反应釜中,将一块的ITO玻璃置于反应釜水热反应得到黑色硒化镍对电极。本发明首次通过水热法一步制得纳米颗粒状的硒化镍对电极,用商业化的TiO2浆料作光阳极,以N719为敏化剂,组装成三明治结构的电池,注入电解液,在100mW/cm2的光强、AM1.5条件下,取得了8.25%的光电转化效率。相同条件下,铂电极的光电转换效率为8.13%。
Description
技术领域
本发明涉及电极材料技术领域,具体涉及一步法原位生长硒化镍太阳能电池对电极。
背景技术
由于其电池成本低、光电转换效率高、对环境无污染,染料敏化太阳能电池自开发出来就备受各国研究工作者的青睐,非常有可能替代硅晶电池成为下一代光伏产业的支柱产品。在目前的研究结果中,半导体材料TiO2作为光阳极在染料吸附、电荷分离及传输等方面都显示了优越的性能。通常,铂电极具有良好的电导率、电催化活性和优异的稳定性,被证明是染料敏化太阳能电池的一个较好的对电极。然而,作为一种贵金属,它的储量低价格高,特别是易被I3 -/I-电解液腐蚀,不仅使电池性能恶化,而且也限制了染料敏化太阳能电池大规模的商业应用。因此,有必要去开发更合适的电极材料,如碳化物,氮化物及氧族化合物等来有效地取代贵金属铂,以取得较好的电化学性能。目前还尚未有通过一步水热法原位生长三元化合物硒化铁镍制备有效的染料敏化太阳能电池对电极,并取得与铂电极相当的光电转换效率的相关专利报道。
发明内容
本发明提供了一步法原位生长硒化镍太阳能电池对电极。本发明首次通过水热法一步制得纳米颗粒状的硒化镍对电极,用商业化的TiO2浆料作光阳极,以N719为敏化剂,组装成三明治结构的电池,注入电解液,在100mW/cm2的光强、AM1.5条件下,取得了8.25%的光电转化效率。
为实现上述目的,本发明采用如下技术方案:
所述硒化铁镍对电极制备方法:取10mL-15mL 去离子水置于容积为50mL烧杯中,加入0.075 mmol NiCl2·6H2O和0.1 mmol Se,匀速搅拌下滴加10mL-15mL NH3·H2O、2mL-5mLN2H4·H2O,继续搅拌15min。将烧杯中溶液转移到高压反应釜中,将一块1.5*3cm的ITO玻璃导电面面朝下与反应釜的内壁成45°角放置,反应釜加盖加外壳后于100-120℃烘箱中恒温反应10-12h,自然冷却至室温,取出玻璃用去离子水和乙醇冲洗数次后晾干即可得到黑色硒化镍对电极,无需后处理。将釜内剩余黑色沉淀物离心分离,用去离子水和乙醇各洗涤3次后冷冻干燥,用于后续表征。
所述硒化镍对电极在染料敏化上的应用:本发明通过水热法一步制得纳米颗粒状的硒化镍对电极,用商业化的TiO2浆料作光阳极,以N719为敏化剂,组装成三明治结构的电池,注入电解液,在100mW/cm2的光强、AM1.5条件下,取得了8.25%的光电转化效率。
本发明的显著优点在于:过渡金属硒化物材料因其优越的电化学性能,在染料敏化太阳能电池中被广泛研究。本发明一步法原位生长硒化镍作染料敏化太阳能电池的对电极,获得了8.25%的高效率。该制备方法简便易行,原材料来源丰富价格低廉,且重现性好,对将来高效染料敏化太阳能电池的研究提供了一个新思路。
附图说明
图1、硒化镍粉末的XRD谱图;
图2、在ITO玻璃上生长的硒化镍的扫描电镜图;
图3、硒化镍的透射电镜图;
图4、硒化镍的高倍透射电镜图
图5、硒化镍与铂作对电极的的染料敏化太阳能电池的性能对比。
具体实施方式
为进一步公开而不是限制本发明,以下结合实例对本发明作进一步的详细说明。
所述硒化镍对电极制备方法:取10mL-15mL 去离子水置于容积为50mL烧杯中,加入0.075 mmol NiCl2·6H2O和0.1 mmol Se,匀速搅拌下滴加10mL-15mL NH3·H2O、2mL-5mLN2H4·H2O,继续搅拌15min。将烧杯中溶液转移到高压反应釜中,将一块1.5*3cm的ITO玻璃导电面面朝下与反应釜的内壁成45°角放置,反应釜加盖加外壳后于100-120℃烘箱中恒温反应10-12h,自然冷却至室温,取出玻璃用去离子水和乙醇冲洗数次后晾干即可得到黑色硒化镍对电极,无需后处理。将釜内剩余黑色沉淀物离心分离,用去离子水和乙醇各洗涤3次后冷冻干燥,用于后续表征。
所述硒化镍对电极在染料敏化太阳能电池上的应用:本发明通过水热法一步制得纳米颗粒状的硒化镍对电极,用商业化的TiO2浆料作光阳极,以N719为敏化剂,组装成三明治结构的电池,注入电解液,在100mW/cm2的光强、AM1.5条件下,取得了8.25%的光电转化效率。
图1为水热反应后釜内所得物质的XRD图。从图中可以看出,釜内产物为混合相,其衍射峰对应于Ni3Se4(JCPDS 89-2020)的衍射峰,匹配度较高,且无杂峰。因此,ITO玻璃上负载的产物为Ni3Se4。
图2为硒化镍对电极的扫描电镜图。从图上可以看出,硒化镍纳米颗粒均匀生长在ITO玻璃表面,形貌均一,无团聚现象。
图3及图4为硒化镍对电极的透射电镜图。从图3可以看出,硒化铁镍纳米颗粒大小为50-100 nm不等。图4中0.35nm的晶格对应于Ni3Se4的(-111)晶面。
图5及表1分别为硒化镍对电极和铂对电极制得的染料敏化太阳能电池性能对比情况。
表1 染料敏化太阳能电池性能测试数据表
由表1可见,贵金属铂作对电极时,光电转换效率为8.13%,原位生长的硒化镍对电极取得8.25%的光电转换效率,其催化活性与铂电极相当。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (4)
1.一步法原位生长硒化镍太阳能电池对电极的制备方法,其特征在于:具体步骤包括:
(1)取10mL-15mL 去离子水置于容积为50mL烧杯中,加入0.075 mmol NiCl2·6H2O和0.1 mmol Se,匀速搅拌下滴加10mL-15mL NH3·H2O、2mL-5mL N2H4·H2O,继续搅拌15min;
(2)将烧杯中溶液转移到高压反应釜中,将一块1.5*3cm的ITO玻璃导电面面朝下与反应釜的内壁成45°角放置,反应釜加盖加外壳后于烘箱中水热反应;
(3)自然冷却至室温,取出玻璃用去离子水和乙醇冲洗数次后晾干得到黑色硒化镍太阳能电池对电极。
2.根据权利要求1所述的一步法原位生长硒化镍太阳能电池对电极的制备方法,其特征在于:步骤(2)中水热反应具体条件为:100-120℃恒温反应10-12h。
3.一种如权利要求1所述方法制备得到的一步法原位生长硒化镍太阳能电池对电极。
4.一种如权利要求1所述方法制备得到的一步法原位生长硒化镍太阳能电池对电极在用于染料敏化太阳能电池上的应用。
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