CN108878153A - 一种硒化铁镍染料敏化太阳能电池对电极 - Google Patents
一种硒化铁镍染料敏化太阳能电池对电极 Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 49
- SXGROPYLQJYUST-UHFFFAOYSA-N iron(2+);selenium(2-) Chemical compound [Fe+2].[Se-2] SXGROPYLQJYUST-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000011521 glass Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052697 platinum Inorganic materials 0.000 abstract description 12
- 239000011669 selenium Substances 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 229910052711 selenium Inorganic materials 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000006467 substitution reaction Methods 0.000 abstract description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 abstract description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 206010070834 Sensitisation Diseases 0.000 description 3
- -1 Transition metal selenide Chemical class 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- 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 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003346 selenoethers Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910003609 H2PtCl4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- UHVZOSVJPDWNHJ-UHFFFAOYSA-N [Se].[Fe].[Ni] Chemical compound [Se].[Fe].[Ni] UHVZOSVJPDWNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 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
- 238000010586 diagram Methods 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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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
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
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Abstract
本发明公开了一种硒化铁镍染料敏化太阳能电池对电极，其是将氯化镍、氯化铁和硒为原料，经一步法原位合成，其原料易得、制备方法简单，且所得硒化铁镍染料敏化太阳能电池对电极具有较好的光电转换效率，有望用于替代铂电极。
Description
技术领域
本发明属于电极材料领域，具体涉及一种硒化铁镍染料敏化太阳能电池对电极。
背景技术
由于具有电池成本低、光电转换效率高、对环境无污染等优势，染料敏化太阳能电池自开发以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。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，铂的储量低、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，有必要开发更合适的电极材料，如碳化物、氮化物及氧族化合物等。本发明通过一步水热法原位合成三元化合物——硒化铁镍染料敏化太阳能电池对电极，并可取得与铂电极相当的光电转换效率，而目前尚未有相关文献报道。
发明内容
本发明的目的在于提供一种硒化铁镍染料敏化太阳能电池对电极，其制备方法简便易行，具有较好的光电转换效率，有望用于替代铂电极。
为实现上述目的，本发明采用如下技术方案：
一种硒化铁镍染料敏化太阳能电池对电极，其是将0.025 mmol NiCl2·6H2O、0.05mmol FeCl3·6H2O和0.1 mmol Se加入到10mL-15mL去离子水中，匀速搅拌下滴加10mL-15mLNH3·H2O、2mL-5mL N2H4·H2O，继续搅拌15min后，将溶液转移到高压反应釜中，并将ITO玻璃导电面朝下、以45°角置于溶液中，100-120℃恒温反应10-12h，自然冷却至室温后洗涤即得。
本发明的显著优点在于：
（1）本发明结合硒化物材料内在的优越催化性能，及原位生长增强硒化物与ITO导电玻璃基底的接触力，减小界面阻抗，从而使所得硒化铁镍对电极制得的染料敏化太阳能电池具有较高光电转化效率。同时，所得材料的二维结构给电极与电解液提供了更多的接触面积，从而使其电化学性能得到显著改善。
（2）本发明以氯化镍、氯化铁和硒为原料，水合肼作为还原剂，首次通过水热法一步制得形貌均一的纳米颗粒状硒化铁镍。反应体系中添加的氨水不仅可维持合成反应的碱性环境，还可减少水合肼用量，以降低生产成本，且更加绿色环保。
（3）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。本发明以硒化铁镍作为染料敏化太阳能电池对电极制备的染料敏化太阳能电池在100mW/cm2的光强、AM1.5条件下可取得8.43%的光电转化效率，与相同条件下铂电极相当（相同条件下，以铂电极作对电极的电池效率为8.13%），为高效染料敏化太阳能电池的进一步研究提供了一个新思路。
附图说明
图1为实施例1水热反应后釜内所得物质的XRD谱图；
图2为实施例1所得硒化铁镍对电极的扫描电镜图；
图3为实施例1所得硒化铁镍对电极的透射电镜图；
图4为硒化铁镍对电极与铂对电极制得的染料敏化太阳能电池性能对比情况。
具体实施方式
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。
实施例1
取12mL去离子水，置于容积为50mL烧杯中，加入0.025 mmol NiCl2·6H2O、0.05 mmolFeCl3·6H2O和0.1 mmol Se，匀速搅拌下滴加10mL NH3·H2O、3mL N2H4·H2O，继续搅拌15min后将烧杯中的溶液转移到高压反应釜中，将一块1.5×3cm的ITO玻璃导电面朝下并与反应釜的内壁成45°角放置，反应釜加盖加外壳后于120℃烘箱中恒温反应12h，自然冷却至室温，取出后用去离子水和乙醇冲洗数次后晾干，即得到黑色硒化铁镍对电极。
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。
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，其衍射峰分别对应于Fe2NiSe4（JCPDS 65-2338）和Ni3Se4（JCPDS 89-2020）的衍射峰。由此推断，该反应的主要生成物为铁镍硒化合物，匹配度较高，且无杂峰，无其它物质生成。因此，ITO玻璃上负载的产物为Fe-NiSe。
图2为硒化铁镍对电极的扫描电镜图。从图上可以看出，硒化铁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为硒化铁镍对电极的透射电镜图。从图上可以看出，硒化铁镍纳米颗粒大小约为50 nm。
实施例2
取10mL去离子水，置于容积为50mL烧杯中，加入0.025 mmol NiCl2·6H2O、0.05 mmolFeCl3·6H2O和0.1 mmol Se，匀速搅拌下滴加10mL NH3·H2O、2mL N2H4·H2O，继续搅拌15min后将烧杯中的溶液转移到高压反应釜中，将一块1.5×3cm的ITO玻璃导电面朝下并与反应釜的内壁成45°角放置，反应釜加盖加外壳后于120℃烘箱中恒温反应12h，自然冷却至室温，取出后用去离子水和乙醇冲洗数次后晾干，即得到黑色硒化铁镍对电极。
实施例3
取15mL去离子水，置于容积为50mL烧杯中，加入0.025 mmol NiCl2·6H2O、0.05 mmolFeCl3·6H2O和0.1 mmol Se，匀速搅拌下滴加10 mL NH3·H2O、5mL N2H4·H2O，继续搅拌15min后将烧杯中的溶液转移到高压反应釜中，将一块1.5×3cm的ITO玻璃导电面朝下并与反应釜的内壁成45°角放置，反应釜加盖加外壳后于100℃烘箱中恒温反应12h，自然冷却至室温，取出后用去离子水和乙醇冲洗数次后晾干，即得到黑色硒化铁镍对电极。
用商业化的TiO2浆料作为光阳极、N719为敏化剂，与实施例1制得的硒化铁镍对电极组装成三明治结构的电池，注入电解液后在100mW/cm2的光强、AM1.5条件下进行电池性能测试。采用未加入铁盐制备的硒化镍对电极及热解氯铂酸制备的铂电极作为对照。所述铂电极的制备方法为：取5mmol H2PtCl4滴涂在1.5cm×1.5cm的FTO玻璃上，移置加热板上450℃加热20 min，自然降温后制得。
图4及表1分别为硒化铁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，原位生长的硒化镍对电极取得8.14%的光电转换效率，原位生长的硒化铁镍对电极取得8.43%的光电转换效率，其与铂电极相比分别提高了0.12%、3.69%。
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 (1)
1. 一种硒化铁镍染料敏化太阳能电池对电极，其特征在于：将0.025 mmol NiCl2·6H2O、0.05 mmol FeCl3·6H2O和0.1 mmol Se加入到10mL-15mL去离子水中，匀速搅拌下滴加10mL-15mL NH3·H2O、2mL-5mL N2H4·H2O，继续搅拌15min后，将溶液转移到高压反应釜中，并将ITO玻璃导电面朝下、以45°角置于溶液中，100-120℃恒温反应10-12h，自然冷却至室温后洗涤即得。
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| CN112678784B (zh) * | 2020-12-28 | 2023-11-21 | 天目湖先进储能技术研究院有限公司 | 一种钠离子电池复合负极材料的制备方法及应用 |
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