CN108922784B - 染料敏化太阳能电池非铂对电极CoTe/Te纳米线及其制备方法 - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title abstract description 18
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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 claims abstract description 8
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims abstract description 6
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- VOADVZVYWFSHSM-UHFFFAOYSA-L sodium tellurite Chemical compound [Na+].[Na+].[O-][Te]([O-])=O VOADVZVYWFSHSM-UHFFFAOYSA-L 0.000 claims abstract description 5
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- CXXKWLMXEDWEJW-UHFFFAOYSA-N tellanylidenecobalt Chemical compound [Te]=[Co] CXXKWLMXEDWEJW-UHFFFAOYSA-N 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Abstract
本发明公开了一种染料敏化太阳能电池非铂对电极CoTe/Te纳米线及其制备方法，其步骤为：将六水合硝酸钴溶解在甲醇中，在剧烈搅拌下，依次加入亚碲酸钠和水合肼，一段时间后进行水热反应，待反应结束后，自然降温至室温，离心洗涤、干燥，即得到CoTe/Te纳米线。本发明采用水热法和旋涂法，所用的方法简单，仪器设备简易，可得到形貌均一的CoTe/Te纳米线，CoTe/Te纳米线表面CoTe（102）晶面的选择性生长，该晶面对I3ˉ还原表现出较高的电催化活性，单质Te是P型半导体，具有较高的空穴载流子迁移率，有利于提升复合材料的催化性能。
Description
技术领域
本发明属于太阳能电池纳米材料生产技术领域，具体涉及过渡金属碲化物的纳米线的制备方法。
背景技术
在染料敏化太阳能电池（Dye-sensitized solar cells，DSSCs）的对电极中，是采用I3ˉ和Iˉ作为氧化还原电对，在其表面发生I3ˉ的还原反应：I3ˉ+ 2 e- →3 Iˉ。因此对电极对于I3ˉ还原的催化性能好坏决定了电池的整体性能。作为对电极的Pt贵金属电极其催化效果受空气影响严重，同时存在很严重的性能衰减。且Pt在地球上的储量极少，价格昂贵，极大地限制了电池的大规模生产。因此，研发新型、高稳定性、催化性能好的非铂对电极材料是目前染料敏化太阳能电池领域的热点问题之一。
发明内容
本发明的目的在于提供一种一步水热法合成的CoTe/Te纳米线及其方法，并将其应用于DSSCs的对电极。
实现本发明目的的技术解决方案是：
CoTe/Te纳米线及其制备方法，包括如下步骤：
称取一定量的六水合硝酸钴溶解在甲醇中，在剧烈搅拌下，依次加入亚碲酸钠和水合肼，一段时间后进行水热反应，待反应结束后，自然降温至室温，离心洗涤收集并进行样品干燥，即得到CoTe/Te纳米线。
进一步的，六水合硝酸钴与亚碲酸钠质量比为5
3~1。
进一步的，甲醇与水合肼的体积比为25
3~1。
进一步的，水热反应温度100~260
，反应时间1~48h。
制成的CoTe/Te纳米线为核壳结构，在纳米线的两侧存在2~5 nm的壳层结构。
CoTe/Te纳米线的对电极的制备方法：
通过超声使CoTe/Te纳米其完全分散于乙醇中，形成墨汁状的黑色溶液，取上述溶液滴在导电玻璃上，进行旋涂，自然晾干，即得到CoTe/Te非铂对电极。
与现有技术相比，本发明获得形貌均一，分散均匀的CoTe/Te纳米线，将其应用于染料敏化太阳能电池中的对电极，可代替传统的贵金属Pt对电极，同时还在碲化钴中引入了单质Te，方法简单，价格便宜，催化效果稳定，不容易失去催化活性，同时提高了光电转化效率，具有广泛的应用前景。
附图说明
图1为实施例2制备的CoTe/Te纳米线的XRD图。
图2为实施例2制备的CoTe/Te纳米线不同放大倍数的透射电镜图。
图3为实施例2制备的CoTe/Te纳米线的EDS Mapping图。
图4为实施例2和不同对电极的DSSCs的J-V曲线图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例对本发明进行详细地说明。
理论计算表明，Te的存在，使材料的电负性增加，更有利于I3ˉ与非金属原子形成电子耦合作用，电极材料对于I3ˉ的吸附能力增强，而对于Iˉ的束缚将减弱，有利于Iˉ离子快速的离开电极表面，扩散到溶液中，提高物质的催化活性，进而影响DSSCs的光电转换性能。因此，发明人制备了CoTe/Te复合纳米材料并将其作为对电极应用到染料敏化太阳能电池中。
一、材料制备
实施例1：
称取0.15 g 的Co(NO3)2·6H2O溶解在25 mL的甲醇中，搅拌10 min，溶液呈现粉色，加入0.09g Na2TeO3固体粉末，剧烈搅拌30 min，加入3 mL水合肼，将其置于40 mL的水热反应釜中，100℃反应48 h，自然降温至室温，离心洗涤收集并进行样品干燥，即得到CoTe/Te纳米线。
实施例2：
称取0.15 g 的Co(NO3)2·6H2O溶解在25 mL的甲醇中，搅拌10 min，加入0.06gNa2TeO3固体粉末，剧烈搅拌30 min，加入2 mL水合肼，将其置于40 mL的水热反应釜中，200℃反应24 h，自然降温至室温，离心洗涤收集并进行样品干燥，即得到CoTe/Te纳米线。
实施例3：
称取0.15 g 的Co(NO3)2·6H2O溶解在25 mL的甲醇中，搅拌10 min，加入0.03gNa2TeO3固体粉末，剧烈搅拌30 min，加入1 mL水合肼，将其置于40 mL的水热反应釜中，260℃反应1 h，自然降温至室温，离心洗涤收集并进行样品干燥，即得到CoTe/Te纳米线。
将上述实施例中不同条件下制备得到的CoTe/Te固体粉末，分别称取0.1 g分散在1 mL 的乙醇中，超声使其完全分散，得到墨汁状的黑色溶液。取上述溶液滴在导电玻璃上，2000 rpm旋涂30s，自然晾干，得到CoTe/Te非铂对电极。
二、产物验证
在实施例2的条件下，可以获得最优的光电转换性能的染料敏化太阳能电池的对电极材料，以下是选取的实施例2的材料表征：
图1为制备的CoTe/Te纳米线的XRD图。从图分析可知：位于31.3°、43.1°、46.7°、58.3° 的峰对应于（101）、（102）、（110）和（103）晶面，与六方相CoTe的JCPDS标准卡片（PDF#34-0420）相匹配，即有CoTe的存在；图中位于27.6°左右的衍射峰归属于单质Te的（101）晶面，证明了这个物质包含了单质Te的存在。
图2分别为制备的不同放大倍数的CoTe/Te纳米线的透射电镜图。从图可见：该纳米线直径≈25 nm，对纳米线局部放大，发现其为核壳结构，壳层厚度≈5 nm。
图3为制备的CoTe/Te纳米线的EDS Mapping图，从左到右依次是元素Co、元素Te以及Co和Te的组合图。从图可见，Te的分布主要集中在纳米线衬度较暗的中间部分，与TEM得到的结果相一致。
图4为不同对电极的DSSCs的J-V曲线图。在标准1.5 G（100 mW cm-2）模拟太阳光照射下，测定其光电转化效率。从图4和表1可见：当采用Pt为对电极时，DSSCs的短路电流为13.99 mA cm-2，开路电压为0.76 V，光电转换效率为6.65%；当对电极为CoTe/Te时，DSSCs短路电流为17.28 mA cm-2，开路电压为0.74 V，光电转换效率为8.06%；当采用CoTe为对电极材料时，DSSCs短路电流为16.14 mA cm-2，开路电压为0.73 V，光电转换效率为6.92%；当DSSCs的对电极为CoTe2时，其光电转换效率为6.40%。由CoTe/Te作为对电极组装的DSSCs具有最高的光电转换效率。
表1对电极为Pt，CoTe/Te，CoTe，CoTe2的DSSCs的主要性能参数
| CEs | <i>V</i><sub>oc</sub>(V) | <i>J</i><sub>sc</sub>(mA cm<sup>-2</sup>) | FF | <i>η</i>(%) |
| Pt | 0.76 | 13.99 | 0.63 | 6.65 |
| CoTe/Te | 0.74 | 17.28 | 0.63 | 8.06 |
| CoTe | 0.73 | 16.14 | 0.58 | 6.92 |
| CoTe<sub>2</sub> | 0.70 | 15.19 | 0.60 | 6.40 |
本发明采用水热法和旋涂法，所用的方法简单，仪器设备简易，可得到形貌均一的CoTe/Te纳米线。CoTe/Te纳米线表面CoTe（102）晶面的选择性生长，该晶面对I3ˉ还原表现出较高的电催化活性。单质Te是P型半导体，具有较高的空穴载流子迁移率，有利于提升复合材料的催化性能。Te在CoTe纳米线中的分布呈现中间高、边缘低，即有利于I3ˉ的吸附，同时便于Iˉ快速的从电极材料表面解吸，释放出更多的活性位点，加速催化反应的进行。CoTe/Te纳米线作为对电极材料代替传统的贵金属Pt对电极，制备方法简单，价格便宜，CoTe与Te之间的协同作用，增强了复合材料的催化性能，催化效果稳定，不易失活。
Claims (2)
1.CoTe/Te纳米线的制备方法，其特征在于，包括如下步骤：
将六水合硝酸钴溶解在甲醇中，在剧烈搅拌下，依次加入亚碲酸钠和水合肼，一段时间后进行水热反应，待反应结束后，自然降温至室温，离心洗涤、干燥，即得到CoTe/Te纳米线，其中，
六水合硝酸钴与亚碲酸钠质量比为5
3~1；
甲醇与水合肼的体积比为25
3~1；
水热反应温度100~260
，反应时间1~48h；
所述的CoTe/Te纳米线为核壳结构，单质Te在纳米线分布呈现中部高、边缘低的微观结构，该纳米线总的直径为15~35 nm，壳层厚度为2~5nm。
2.如权利要求1所述的方法制备的CoTe/Te纳米线。
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