CN104078245A - Nanowire array device capable of simultaneously achieving photoelectric conversion and optical energy storage and manufacturing method and application thereof - Google Patents
Nanowire array device capable of simultaneously achieving photoelectric conversion and optical energy storage and manufacturing method and application thereof Download PDFInfo
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Abstract
本发明属于太阳能电池技术领域,具体为一种可同时光电转化与光能存储的纳米线阵列器件及其制备方法和应用。本发明包括:在光电材料上复合电容材料制成的光阳极;光阴极;电解液;光阳极和光阴极短路连接后置于电解液中。如在TiO2纳米线阵列上负载NiO纳米片作为光阳极,以硅纳米线阵列作为光阴极,光生电子在硅纳米上还原H+产生H2,光生空穴将TiO2纳米线上的NiO氧化成NiOOH,将光生空穴的能量储存成NiOOH的化学能,实现了同时光电转换与光能储存,提高了太阳能电池对光的利用效率。进一步通过NiOOH将葡萄糖氧化成葡萄糖酮,将NiOOH中储存的化学能作为一个自驱动的化学传感器释放。本发明原材料来源广泛,制备方法简单、环保、价格低廉。
The invention belongs to the technical field of solar cells, in particular to a nanowire array device capable of simultaneous photoelectric conversion and light energy storage, a preparation method and application thereof. The invention comprises: a photoanode made of a composite capacitance material on a photoelectric material; a photocathode; an electrolyte; For example, NiO nanosheets are loaded on the TiO2 nanowire array as a photoanode, and the silicon nanowire array is used as a photocathode. The photogenerated electrons reduce H + on the silicon nanowires to generate H2 , and the photogenerated holes oxidize NiO on the TiO2 nanowires. NiOOH, the energy of photogenerated holes is stored into the chemical energy of NiOOH, which realizes simultaneous photoelectric conversion and light energy storage, and improves the utilization efficiency of solar cells for light. Glucose was further oxidized to glucosone by NiOOH, and the chemical energy stored in NiOOH was released as a self-driven chemical sensor. The invention has wide sources of raw materials, simple preparation method, environmental protection and low price.
Description
技术领域 technical field
本发明属于太阳能电池技术领域,具体涉及一种纳米线阵列器件及其制备方法和应用。 The invention belongs to the technical field of solar cells, and in particular relates to a nanowire array device and its preparation method and application.
背景技术 Background technique
能源危机作为本世纪急需解决的重大问题,发展新能源技术是解决能源危机的关键,而太阳能的利用作为新能源中重要一员。一般利用太阳能资源可分为两大类:一类是太阳能电池,将太阳能转换为电能利用,但由于太阳能电池的电能需及时使用,不能长期储存,因而在实际使用中会存在并网、储能等问题;另一类是光化学电池,将太阳能转换为化学能利用,如太阳能分解水制氢,此种能源无需进一步转换,可直接储存长期使用。 The energy crisis is a major problem that needs to be solved urgently in this century. The development of new energy technology is the key to solving the energy crisis, and the utilization of solar energy is an important part of new energy. Generally, the use of solar energy resources can be divided into two categories: one is solar cells, which convert solar energy into electric energy, but because the electric energy of solar cells needs to be used in time and cannot be stored for a long time, there will be grid connection and energy storage in actual use. and other issues; the other is photochemical cells, which convert solar energy into chemical energy, such as solar energy splitting water to produce hydrogen, which can be directly stored for long-term use without further conversion.
传统的光解水制氢气,是用太阳光照射半导体材料产生光生电子和空穴将水分解,光生电子还原水产生氢气,光生空穴氧化水产生氧气,氢气是重要的能源物质,但氧气在能源上却没有多少实用价值,因而此部分包含的光生空穴的能量即被浪费。本发明利用在半导体光阳极上负载赝电容材料,将光生空穴的能量储存在电容器中。并可以通过电容器放电和化学传感器将此部分储存的电容能量进一步释放出来。本发明可以有效提高光解水的能量利用效率,且制作步骤简单,方便大规模利用。 The traditional photolysis of water to produce hydrogen is to use sunlight to irradiate semiconductor materials to generate photogenerated electrons and holes to decompose water. Photogenerated electrons reduce water to generate hydrogen, and photogenerated holes oxidize water to generate oxygen. Hydrogen is an important energy substance, but oxygen is in the There is not much practical value in energy, so the energy of the photogenerated holes contained in this part is wasted. The invention utilizes the pseudocapacitive material loaded on the semiconductor photoanode to store the energy of photogenerated holes in the capacitor. And the capacitor energy stored in this part can be further released through capacitor discharge and chemical sensor. The invention can effectively improve the energy utilization efficiency of photolyzed water, has simple manufacturing steps, and is convenient for large-scale utilization.
发明内容 Contents of the invention
本发明的目的是提供一种可利用太阳能同时实现光电转换、光能储存与利用的多功能纳米线阵列器件及其制备方法和应用。 The object of the present invention is to provide a multifunctional nanowire array device capable of utilizing solar energy to simultaneously realize photoelectric conversion, storage and utilization of light energy, and its preparation method and application.
本发明提供的同时实现光电转换、光能储存与利用的纳米线阵器件,包括:一在光电材料上复合电容材料制成的光阳极;一光阴极;电解液;上述光阳极和光阴极短路连接后置于电解液中。 The nanowire array device that simultaneously realizes photoelectric conversion, light energy storage and utilization provided by the present invention includes: a photoanode made of a composite capacitor material on a photoelectric material; a photocathode; an electrolyte; the photoanode and photocathode are short-circuited Then placed in the electrolyte.
本发明提供的同时实现光电转换、光能储存与利用的纳米线阵器件的制备方法,具体步骤为: The method for preparing a nanowire array device that simultaneously realizes photoelectric conversion, light energy storage and utilization provided by the present invention, the specific steps are:
(1) 在光电材料上复合电容材料,作为光阳极; (1) Composite capacitor material on the photoelectric material as photoanode;
(2) 提供一光阴极; (2) providing a photocathode;
(3) 将上述光阳极和光阴极短路连接置于电解液中。 (3) Put the photoanode and photocathode short-circuit connection in the electrolyte.
用光照给纳米线阵列电容器件充电,在充电过程中,加入不同浓度化学检测物溶液,通过电流变化反应化学检测物浓度。 Light is used to charge the nanowire array capacitive device. During the charging process, chemical detection solutions with different concentrations are added, and the concentration of chemical detection substances is reflected by the change of current.
放电过程中加入不同浓度化学检测物溶液,通过光阳极电势变化反应化学检测物浓度。 During the discharge process, different concentrations of chemical detection substance solutions are added, and the concentration of the chemical detection substance is reflected by the change of the photoanode potential.
所述的光电材料是TiO2、ZnO、WO3、Fe2O3中的一种或多种。 The photoelectric material is one or more of TiO 2 , ZnO, WO 3 , Fe 2 O 3 .
所述的电容材料是NiO、Ni(OH)2、Co3O4、CoO、Co(OH)2、MnOx、Mn(OH)2中的一种或多种。 The capacitor material is one or more of NiO, Ni(OH) 2 , Co 3 O 4 , CoO, Co(OH) 2 , MnO x , Mn(OH) 2 .
所述的光阴极光电材料是Si、Cu2O、GaP、InP中的一种或多种。 The photocathode optoelectronic material is one or more of Si, Cu 2 O, GaP, InP.
所述的电解液是Na2SO4、NaCl、K2SO4之一种。 The electrolyte is one of Na 2 SO 4 , NaCl, K 2 SO 4 .
所述的化学检测物为葡萄糖、H2O2、H2S之一种。 The chemical detection substance is one of glucose, H 2 O 2 , and H 2 S.
本发明的纳米线阵列器件能利用太阳能光解水制氢,同时将光阳极的空穴能量作为赝电容电容器的化学能储存起来,再可以通过电容器放电或者化学传感器将改电容器能量释放出来。 The nanowire array device of the present invention can use solar energy to photolyze water to produce hydrogen, and at the same time store the hole energy of the photoanode as the chemical energy of a pseudocapacitive capacitor, and then release the capacitor energy through capacitor discharge or chemical sensors.
本发明的纳米线阵列器件可应用于太阳能电池和化学传感器。例如,以二氧化钛复合氧化镍纳米线阵列为光阳极,硅纳米线阵列为光阴极,0.5 M的硫酸钠溶液为反应溶液,照射光强度为一个太阳光,照射截面积为可根据工作电极的面积大小调节。 The nanowire array device of the present invention can be applied to solar cells and chemical sensors. For example, the titanium dioxide composite nickel oxide nanowire array is used as the photoanode, the silicon nanowire array is used as the photocathode, the 0.5 M sodium sulfate solution is used as the reaction solution, the irradiation light intensity is one sunlight, and the irradiation cross-sectional area can be determined according to the area of the working electrode Size adjustment.
本发明通过在光电材料上沉积赝电容材料,实现高效光解水制氢同时将光生空穴的能量储存在赝电容电容器中。该纳米线阵列器件具有制作工艺简单,成本低,稳定性好,光电转化效率高并对环境友好的特点,适合大面积生产,对于太阳能电池研究上具有重要意义,在新能源领域也具有很好的应用前景。 The invention realizes high-efficiency photolysis of water to produce hydrogen by depositing a pseudocapacitive material on the photoelectric material, and at the same time stores the energy of photogenerated holes in a pseudocapacitive capacitor. The nanowire array device has the characteristics of simple manufacturing process, low cost, good stability, high photoelectric conversion efficiency and environmental friendliness, is suitable for large-area production, is of great significance for solar cell research, and has a good potential in the field of new energy. application prospects.
附图说明 Description of drawings
图1:a–c为TiO2纳米线阵列上负载NiO纳米片的电镜照片;d为f图为硅纳米线阵列上负载铂纳米颗粒的电镜照片。 Figure 1: a–c are electron micrographs of NiO nanosheets loaded on TiO 2 nanowire arrays; d is an electron micrograph of platinum nanoparticles loaded on silicon nanowire arrays.
图2:为纯TiO2纳米线阵列、纯NiO纳米片、TiO2纳米线阵列上负载氧化镍纳米片随光照时间变化开路电势的变化。 Figure 2: Changes in the open circuit potential of pure TiO 2 nanowire arrays, pure NiO nanosheets, and NiO nanosheets loaded on TiO 2 nanowire arrays with light time.
图3:依次为纯TiO2纳米线阵列、TiO2纳米线阵列负载NiO纳米片光阳极、此光阳极光照充完电后状态、此光阳极放电后状态的照片,充电完之后光阳极变黑,放电后又恢复到原始颜色。 Figure 3: Photos of pure TiO 2 nanowire arrays, TiO 2 nanowire arrays loaded with NiO nanosheet photoanodes, the state of the photoanode after being illuminated and charged, and the state of the photoanode after being discharged, and the photoanode turns black after charging , and return to the original color after discharge.
图4:a–b为光照充电时用光电流检测葡萄糖浓度的原理及性能。 Figure 4: a–b are the principle and performance of using photocurrent to detect glucose concentration during light charging.
图5:a–b为暗场放电条件下用开路电势检测葡萄糖浓度的原理及性能。 Figure 5: a–b are the principle and performance of using open circuit potential to detect glucose concentration under dark field discharge conditions.
图6:本发明用于检测的系统图示。 Figure 6: Schematic representation of the system of the present invention for detection.
具体实施方式 Detailed ways
下面,通过以下实施例对本发明作进一步说明,它将有助于理解本发明,但并不限制本发明的内容。 Below, the present invention will be further described by the following examples, which will help to understand the present invention, but do not limit the content of the present invention.
通过在TiO2纳米线阵列上负载NiO纳米片作为光阳极,以硅纳米线阵列作为光阴极,光生电子在硅纳米上还原H+产生H2,光生空穴将TiO2纳米线上的NiO氧化成NiOOH,将光生空穴的能量储存成NiOOH的化学能,实现了同时光电转换与光能储存,提高了太阳能电池对光的利用效率。进一步通过NiOOH将葡萄糖氧化成葡萄糖酮,将NiOOH中储存的化学能作为一个自驱动的化学传感器释放。具体说来: By loading NiO nanosheets on the TiO2 nanowire array as a photoanode and using the silicon nanowire array as a photocathode, the photogenerated electrons reduce H + on the silicon nanowires to generate H2 , and the photogenerated holes oxidize NiO on the TiO2 nanowires NiOOH, the energy of photogenerated holes is stored into the chemical energy of NiOOH, which realizes simultaneous photoelectric conversion and light energy storage, and improves the utilization efficiency of solar cells for light. Glucose was further oxidized to glucosone by NiOOH, and the chemical energy stored in NiOOH was released as a self-driven chemical sensor. Specifically:
首先用水热法在FTO基底上制备TiO2纳米线阵列,再用化学浴沉积法在TiO2纳米线阵列上沉积NiO纳米片。反应结束后,将基片取出洗净并吹干。接着,将基片置于管式炉内在氩气下200℃条件下焙烧2小时。最后,在氩气保护下,降至室温。所得到的TiO2纳米线阵列上负载NiO纳米片做为光阳极,如图1a-c所示。 Firstly, TiO2 nanowire arrays were prepared on the FTO substrate by hydrothermal method, and then NiO nanosheets were deposited on the TiO2 nanowire arrays by chemical bath deposition. After the reaction, the substrate was taken out, washed and dried. Next, the substrate was placed in a tube furnace and fired at 200° C. under argon for 2 hours. Finally, it was cooled to room temperature under the protection of argon. The obtained TiO2 nanowire arrays were loaded with NiO nanosheets as photoanodes, as shown in Fig. 1a–c.
用金属辅助刻蚀法制备硅纳米线阵列作为光阴极,再沉积铂纳米颗粒作为产氢催化剂,如图1b-d所示。 Silicon nanowire arrays were prepared by metal-assisted etching as photocathode, and then platinum nanoparticles were deposited as hydrogen-producing catalysts, as shown in Fig. 1b–d.
将上述光阳极和光阴极短路连接置于电解液中,用光照给电容器充电,不同光照时间光阳极的开路电势变化如图2所示。 The above-mentioned photoanode and photocathode were short-circuited and placed in the electrolyte, and the capacitor was charged with light. The open-circuit potential changes of the photoanode with different light time are shown in Fig. 2 .
图3依次为纯TiO2纳米线阵列、TiO2纳米线阵列负载NiO纳米片光阳极、此光阳极光照充完电后状态、此光阳极放电后状态的照片,充电完之后光阳极变黑,放电后又恢复到原始颜色。 Figure 3 is the photos of the pure TiO2 nanowire array, the TiO2 nanowire array loaded NiO nanosheet photoanode, the state of the photoanode after it is illuminated and charged, and the state of the photoanode after it is discharged. After charging, the photoanode turns black. It returns to its original color after discharge.
充电过程中加入不同浓度化学检测物溶液,通过电流变化反应化学检测物浓度,如图4a,b所示。 During the charging process, different concentrations of chemical detection substance solutions are added, and the concentration of chemical detection substances is reflected by the change of current, as shown in Figure 4a, b.
放电过程中加入不同浓度化学检测物溶液,通过光阳极电势变化反应化学检测物浓度,图5a,b所示。 During the discharge process, different concentrations of chemical detector solutions are added, and the concentration of chemical detectors is reflected by the change of photoanode potential, as shown in Figure 5a,b.
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CN105839139A (en) * | 2015-02-03 | 2016-08-10 | 松下知识产权经营株式会社 | Water splitting method |
CN106238081A (en) * | 2015-12-29 | 2016-12-21 | 中国特种飞行器研究所 | Preparation has the WO of high activity photoelectrocatalysis decomposition water performance3the method of nanometer thorn/CoPi complex light anode |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105839139A (en) * | 2015-02-03 | 2016-08-10 | 松下知识产权经营株式会社 | Water splitting method |
CN106238081A (en) * | 2015-12-29 | 2016-12-21 | 中国特种飞行器研究所 | Preparation has the WO of high activity photoelectrocatalysis decomposition water performance3the method of nanometer thorn/CoPi complex light anode |
CN108597879A (en) * | 2018-03-19 | 2018-09-28 | 西北师范大学 | A kind of TiO2The preparation method of nano wire/NiO nanometer sheets/porphyrin composite material |
CN108597879B (en) * | 2018-03-19 | 2020-09-22 | 西北师范大学 | TiO 22Preparation method of nanowire/NiO nanosheet/porphyrin composite material |
CN111593353A (en) * | 2020-05-29 | 2020-08-28 | 深圳大学 | Photoelectrochemistry anti-corrosion protection composite photo-anode and preparation method and application thereof |
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