CN100463233C - 一种核壳结构杂化电极的制备方法 - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims description 4
- 239000011258 core-shell material Substances 0.000 title abstract description 20
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000000084 colloidal system Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000000151 deposition Methods 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims 2
- 238000009396 hybridization Methods 0.000 claims 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 16
- 238000001755 magnetron sputter deposition Methods 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 12
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 238000005215 recombination Methods 0.000 abstract description 5
- 230000006798 recombination Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- TXWBZNOXADEHRQ-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1.CC(C)(C)C1=CC=NC=C1 TXWBZNOXADEHRQ-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical group CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- RWSFHVICTKYFLP-UHFFFAOYSA-N [I].CC1=NC=CN1CCC Chemical compound [I].CC1=NC=CN1CCC RWSFHVICTKYFLP-UHFFFAOYSA-N 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 101100001678 Emericella variicolor andM gene Proteins 0.000 description 1
- IGPWZTRYGDSBRC-UHFFFAOYSA-N [I+].C(CC)[N+]1=CN(C=C1)C Chemical compound [I+].C(CC)[N+]1=CN(C=C1)C IGPWZTRYGDSBRC-UHFFFAOYSA-N 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
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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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- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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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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Abstract
本发明公开了一种用于染料敏化纳米晶太阳能电池的核壳结构杂化电极的制备方法，以TiO2胶体为原料采用粉末涂覆法制备TiO2纳米晶膜。在TiO2纳米晶膜上反应直流磁控溅射沉积MgO，制备TiO2(MgO)核壳结构的杂化电极。本发明的有益效果在于：解决了染料敏化太阳能电池中TiO2/电解质界面电荷复合大的缺点，有利于提高染料敏化太阳能电池的光电转换效率。该方法制备的染料敏化太阳能电池的各项光电参数均有提高，是一种提高太阳能电池光电转换效率的有效方法。此外，该方法生产工艺简单、成本低廉。
Description
技术领域
本发明属于染料敏化太阳能电池纳米晶膜的研究领域，涉及在TiO2纳米晶膜上反应直流磁控溅射沉积MgO层，制备MgO修饰的核壳结构杂化电极应用于染料敏化太阳能电池。
背景技术
N719敏化的液态电解质染料敏化纳米晶太阳能电池的理论光电转换效率是14％，而目前报道的最高值只有11％左右。这是由于染料敏化纳米晶太阳能电池内存在大量的电荷复合，限制了光电转换效率的提高。经实际研究可知：采用反应直流磁控溅射在TiO2纳米晶膜上沉积MgO层，制备TiO2(核)—MgO(壳)(以下简称(TiO2(MgO))核壳结构的杂化电极有利于提高染料敏化太阳能电池的光电转换效率。
染料敏化纳米晶太阳能电池在光照条件下，TiO2/电解质界面的电荷复合在整个电池内占主导，限制光电转换效率的提高。国内外研究者尝试引入大量的宽禁带氧化物，修饰TiO2纳米晶膜，以减小界面复合、提高光电转换效率，取得了一定的成效。但采用反应直流磁控溅射制备TiO2(MgO)核壳结构的杂化电极，通过提高太阳能电池的短路电流、开路电压以及填充因子来提高光电转换效率的报道还未见。
发明内容
本发明所要解决的问题是针对上述现有技术提出采用金属Mg靶，在TiO2纳米晶膜上反应直流磁控溅射沉积MgO层，制备TiO2(MgO)核壳结构的杂化电极应用于染料敏化太阳能电池，该方法有利于提高染料敏化纳米晶太阳能电池的短路电流、开路电压和填充因子，是一种提高染料敏化纳米晶太阳能电池光电效率的有效方法。
本发明为解决上述提出问题采用的解决方案为：一种核壳结构杂化电极的制备方法，该方法的包括以下步骤：
1.以TiO2胶体为原料采用粉末涂覆法制备TiO2纳米晶膜。
2.在TiO2纳米晶膜上反应直流磁控溅射沉积MgO得到TiO2(MgO)核壳结构杂化电极。
本发明所述TiO2胶体可以是水热法合成的也可以由购买的P25粉(从Degussa AGof Germany公司购买)配制成。
对本发明制得的核壳结构杂化电极敏化，并滴加氧化还原电解质于敏化后的纳米晶膜上，加盖对电极，可组装成染料敏化纳米晶太阳能电池。
按上述方案中，所述的氧化还原电解质配比为：0.1MLiI，0.05MI2，0.6M1，2-dimethyl-3-n-propylimidazolium(1，2甲基-3-n-丙基咪唑碘)，0.5M4-tertbutylpyridine(4-叔丁基吡啶)，溶剂为碳酸丙烯脂。所用的染料为N719。
本发明上述核壳结构杂化电极包括磁控溅射沉积MgO层(壳层)和TiO2(核层)纳米晶膜层两层，MgO层通过反应直流磁控溅射沉积于TiO2纳米晶膜上，制得的TiO2(MgO)核壳结构杂化电极具有良好的粗糙度。
本发明的有益效果在于：
1.本发明提出了反应直流磁控溅射制备TiO2(MgO)核壳结构杂化电极的制备方法。较好的解决了染料敏化太阳能电池中TiO2/电解质界面电荷复合大的缺点，提高了染料敏化太阳能电池的光电转换效率。
2.TiO2(MgO)核壳结构杂化电极具有良好的粗糙度，MgO的修饰提高了染料敏化纳米晶太阳能电池的短路电流、开路电压和填充因子，使得光电转换效率大幅度提高。该方法生产工艺简单、成本低廉。
具体实施方式
以下结合具体的实施例对本发明的技术方案作进一步的说明。
实施例1 在6μm的TiO2纳米晶膜上反应直流磁控溅射沉积5-20nm的MgO层，制备成TiO2(MgO)核壳结构杂化电极。
采用水热法合成TiO2胶体(参见C.J.Barbe，F.Arendse，P.Comte，M.Jirousek，F.Lenzmann，V.Shklover and M.Gratzel，J.Am.Ceram.Soc 80(12)3157(1997).)，采用粉末涂覆法(参见A.Kay and M.Gratzel Chem.Mater.，2002，14，2930.)制备6μm的TiO2纳米晶膜。采用金属Mg靶，以1-10nm/min的溅射速度在TiO2纳米晶膜上反应直流磁控溅射沉积5-20nm的MgO，制备成TiO2(MgO)核壳结构杂化电极。敏化TiO2(MgO)杂化电极，滴加氧化还原电解质，其配比为：0.1MLiI，0.05MI2，0.6M1，2-dimethyl-3-n-propylimidazolium(1，2甲基-3-n-丙基咪唑碘)，0.5M4-tertbutylpyridine(4-叔丁基吡啶)，溶剂为碳酸丙烯脂。盖上电极，组装成染料敏化纳米晶太阳能电池。
在室温环境，使用500W氙灯并配以GG420，Prinz Optics IR-3滤光片模拟太阳光，光强为75mW/cm2(辐照计：北京师范大学，型号：FZ-A)条件下，测得沉积5-20nmMgO膜制备的染料敏化纳米晶太阳能电池(有效光照面积为0.5cm2)的光电转换效率为6.59％，比未经MgO修饰的染料敏化纳米晶太阳能电池的光电效率(5.18％)提高1.41％。
实施例2 在10μm的TiO2纳米晶膜上反应直流磁控溅射沉积5-20nm的MgO膜，制备TiO2(MgO)核壳结构杂化电极。
水热合成TiO2胶体(参见C.J.Barbe，F.Arendse，P.Comte，M.Jirousek，F.Lenzmann，V.Shklover and M.Gratzel，J.Am.Ceram.Soc 80(12)3157(1997).)，采用粉末涂覆法(参见A.Kay and M.Gratzel Chem.Mater.，2002，14，2930.)制备10μm TiO2纳米晶膜。在TiO2纳米晶膜上反应直流磁控溅射沉积5-20nm的MgO，制备TiO2(MgO)核壳结构杂化电极。敏化TiO2(MgO)杂化电极，滴加氧化还原电解质，其配比为：0.1MLiI，0.05MI2，0.6M1，2-dimethyl-3-n-propylimidazolium(1，2甲基-3-n-丙基咪唑碘)，0.5M4-tertbutylpyridine(4-叔丁基吡啶)，溶剂为碳酸丙烯脂。盖上对电极，组装成染料敏化纳米晶太阳能电池。
在室温环境，使用500W氙灯并配以GG420，Prinz Optics IR-3滤光片模拟太阳光，光强为75mW/cm2(辐照计：北京师范大学，型号：FZ-A)条件下，测得经沉积5-20nmMgO膜制备的染料敏化纳米晶太阳能电池(有效光照面积为0.5cm2)的光电转换效率为8.26％，比未经MgO修饰的染料敏化纳米晶太阳能电池效率(7.18％)提高1.08％。
实施例3 在6μm的TiO2纳米晶膜上反应直流磁控溅射沉积5-20nm的MgO层，制备成TiO2(MgO)核壳结构杂化电极。
采用P25粉(从Degussa AG of Germany公司购买)配制成胶体(参见M.K.Nazeeruddin，A.Kay，I.Rodicio，R.Humphry-Baker，E.Mu¨ller，P.Liska，N.Vlachopoulos，and M.Gratzel，J.Am.Chem.Soc.，115，6382(1993).)，采用粉末涂覆法(参见A.Kay andM.Gratzel Chem.Mater.，2002，14，2930.)制备6μm的TiO2纳米晶膜。采用高纯金属Mg靶，以1-10nm/min的溅射速度在TiO2纳米晶膜上反应直流磁控溅射沉积5-20nm的MgO，制备成TiO2(MgO)核壳结构杂化电极。敏化TiO2(MgO)杂化电极，滴加氧化还原电解质，其配比为：0.1MLiI，0.05MI2，0.6M1，2-dimethyl-3-n-propylimidazolium(1，2甲基-3-n-丙基咪唑碘)，0.5M4-tertbutylpyridine(4-叔丁基吡啶)，溶剂为碳酸丙烯脂。盖上电极，组装成染料敏化纳米晶太阳能电池。
在室温环境，使用500W氙灯并配以GG420，Prinz Optics IR-3滤光片模拟太阳光，光强为75mW/cm2(辐照计：北京师范大学，型号：FZ-A)条件下，测得沉积5-20nmMgO膜制备的染料敏化纳米晶太阳能电池(有效光照面积为0.5cm2)的光电转换效率为5.3％，比未经MgO修饰的染料敏化纳米晶太阳能电池的光电效率(4.5％)提高0.8％。
Claims (2)
1.一种核壳结构杂化电极的制备方法，其特征在于包括以下步骤：
1)以TiO2胶体为原料采用粉末涂覆法制备TiO2纳米晶膜；
2)在TiO2纳米晶膜上反应直流磁控溅射沉积MgO得到核壳结构杂化电极。
2.根据权利要求1所述的制备方法，其特征是：所述TiO2胶体为水热法合成的TiO2胶体。
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| CN103205887A (zh) * | 2013-03-19 | 2013-07-17 | 浙江理工大学 | 基于二氧化钛/氧化镁核壳纳米棒的光伏智能织物的制备方法 |
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| Dye-sensitized solid-statesolar cellsmadefrommagnesiumoxide-coated nanocrystallinetitaniumdioxidefilms:enhancement of the efficiency. G.R.A.Kumara,et al.Journal of Photochemistry and Photobiology A: Chemistry,Vol.164 No.1-3. 2004 * |
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