CN105633266A - Preparation method for composite thermoelectric film with flexible reduced graphene oxide and tellurium nano wires - Google Patents
Preparation method for composite thermoelectric film with flexible reduced graphene oxide and tellurium nano wires Download PDFInfo
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Abstract
本发明涉及一种柔性还原石墨烯(RGO)/碲纳米线(Te？NWs)复合热电薄膜的制备方法。其特点包括以下步骤：以氧化石墨烯(GO)粉末与聚苯乙烯磺酸钠(NaPSS)为原料，通过水热法还原制备可在水中分散的RGO；以亚碲酸钠(Na2TeO3)为原料，水合肼(N2H4·H2O)为还原剂，通过水热法还原制备可在水中分散的TeNWs；将一定量RGO和Na2TeO3分别超声分散在水中后，在真空抽滤辅助下，将RGO分散液与碲纳米线分散液依次滴涂在柔性玻璃纤维膜上，真空下将玻璃纤维膜烘干。在Ar/H2混合气氛中，于200℃下将覆有复合薄膜的玻璃纤维退火一定时间，得到柔性还原石墨烯/碲纳米线复合热电薄膜。本发明具有工艺简单易控、反应时间短、能耗低、安全无污染、柔性薄膜热电性能优异等特点。
The invention relates to a method for preparing a flexible reduced graphene (RGO)/tellurium nanowire (Te?NWs) composite thermoelectric film. Its characteristics include the following steps: use graphene oxide (GO) powder and sodium polystyrene sulfonate (NaPSS) as raw materials, prepare RGO that can be dispersed in water by hydrothermal reduction; use sodium tellurite (Na 2 TeO 3 ) as the raw material and hydrazine hydrate (N 2 H 4 ·H 2 O) as the reducing agent, TeNWs that can be dispersed in water were prepared by hydrothermal reduction; after a certain amount of RGO and Na 2 TeO 3 were ultrasonically dispersed in water, the With the assistance of vacuum filtration, the RGO dispersion liquid and the tellurium nanowire dispersion liquid are sequentially drip-coated on the flexible glass fiber membrane, and the glass fiber membrane is dried under vacuum. In an Ar/ H2 mixed atmosphere, the glass fiber coated with the composite film was annealed at 200 °C for a certain period of time to obtain a flexible reduced graphene/tellurium nanowire composite thermoelectric film. The invention has the characteristics of simple and easy-to-control process, short reaction time, low energy consumption, safety and pollution-free, excellent thermoelectric performance of the flexible film, and the like.
Description
技术领域technical field
本发明属于新能源材料技术领域，具体涉及一种柔性还原石墨烯与碲纳米线复合热电薄膜的制备方法。The invention belongs to the technical field of new energy materials, and in particular relates to a method for preparing a composite thermoelectric thin film of flexible reduced graphene and tellurium nanowires.
背景技术Background technique
热电材料是能够实现热能与电能直接相互转换的材料，基于热电材料的温差发电器件及制冷器件，具有设备结构紧凑、运行时无噪音、无污染、可回收利用废弃能源等特点，在军事、医学、航天、微电子乃至家用电器等领域都有着广阔的应用前景。柔性热电材料相比商业化的块体热电材料，具有可弯曲、制备成本低、工艺简单、适用范围广等独特优势，近年来吸引了科研界及企业界越来越多的关注。Thermoelectric materials are materials that can directly convert heat energy and electric energy. Thermoelectric power generation devices and refrigeration devices based on thermoelectric materials have the characteristics of compact equipment, no noise, no pollution during operation, and waste energy can be recycled. Used in military, medical , aerospace, microelectronics and even household appliances and other fields have broad application prospects. Compared with commercial bulk thermoelectric materials, flexible thermoelectric materials have unique advantages such as bendability, low preparation cost, simple process, and wide application range. In recent years, they have attracted more and more attention from the scientific research community and the business community.
还原石墨烯拥有较高的载流子浓度和载流子迁移率，经表面活性剂处理后可分散在水中，适合于制备柔性热电材料。但由于还原石墨烯的电子及空穴的迁移率几乎相同，导致其Seebeck系数很低。许多研究结果表明，复合热电材料中的能量过滤效应及界面散射能够有效地降低材料的热导率，同时在保持电导率不变的情况下，提高材料的Seebeck系数，使得材料的ZT值大幅地增加。通过调节还原石墨烯的还原程度能够调控还原石墨烯的功函数及电子结构，使其能够与各种半导体材料进行有效地复合。但目前为止，基于还原石墨烯的复合热电材料均是由导电高分子或无机半导体与还原石墨烯简单复合组成的块体材料，并没有实现复合组分的有效匹配，有赛贝克系数较低，适用温度范围较窄，无柔性等缺点。Reduced graphene has a high carrier concentration and carrier mobility, and can be dispersed in water after being treated with a surfactant, which is suitable for the preparation of flexible thermoelectric materials. However, the mobility of electrons and holes in reduced graphene is almost the same, resulting in a very low Seebeck coefficient. Many research results show that the energy filtering effect and interface scattering in composite thermoelectric materials can effectively reduce the thermal conductivity of the material, and at the same time keep the electrical conductivity constant, increase the Seebeck coefficient of the material, so that the ZT value of the material can be greatly improved. Increase. By adjusting the degree of reduction of the reduced graphene, the work function and electronic structure of the reduced graphene can be regulated, so that it can be effectively combined with various semiconductor materials. But so far, composite thermoelectric materials based on reduced graphene are all bulk materials composed of conductive polymers or inorganic semiconductors and reduced graphene, which have not achieved effective matching of composite components, and have low Seebeck coefficients. The applicable temperature range is narrow, and there are no shortcomings such as flexibility.
发明内容Contents of the invention
本发明的目的是提供一种柔性还原石墨烯与碲纳米线复合热电薄膜的制备方法，该方法工艺简单，制备周期短，得到的薄膜热电性能好。The purpose of the present invention is to provide a method for preparing a flexible reduced graphene and tellurium nanowire composite thermoelectric thin film. The method has simple process, short preparation period, and the obtained thin film has good thermoelectric performance.
为了实现上述目的，本发明采用以下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
一种柔性还原石墨烯与碲纳米线复合热电薄膜的制备方法，包括以下步骤：A method for preparing a flexible reduced graphene and tellurium nanowire composite thermoelectric film, comprising the following steps:
(1)将一定量的氧化石墨烯与表面活性剂超声分散在水中，再向分散液中加入2—4倍分散液的酸，混合液于120—150℃下水热反应2—6小时自然冷却后抽滤得到沉淀；(1) Ultrasonic disperse a certain amount of graphene oxide and surfactant in water, then add 2-4 times the acid of the dispersion liquid to the dispersion liquid, and the mixed liquid reacts hydrothermally at 120-150 ° C for 2-6 hours and naturally cools Suction filtration obtains precipitation afterward;
(2)步骤(1)中得到的沉淀用去离子水洗至中性，沉淀于60℃下真空干燥3—5小时得到可分散的还原石墨烯；(2) The precipitate obtained in step (1) is washed with deionized water to neutrality, and the precipitate is vacuum-dried at 60° C. for 3-5 hours to obtain dispersible reduced graphene;
(3)将亚碲酸钠与络合剂搅拌溶解于水中，再向前述溶液中加入25％的氨水及98％的水合肼，混合液于180℃下水热反应一定时间后冷却；(3) stirring and dissolving sodium tellurite and complexing agent in water, then adding 25% ammonia water and 98% hydrazine hydrate to the aforementioned solution, and cooling the mixed solution after hydrothermal reaction at 180° C. for a certain period of time;
(4)向步骤(3)中得到的液体中加入一定量的丙酮得到絮状沉淀，离心后弃去上层清液得到可分散的碲纳米线；(4) adding a certain amount of acetone to the liquid obtained in step (3) to obtain a flocculent precipitate, discarding the supernatant after centrifugation to obtain dispersible tellurium nanowires;
(5)分别配置一定浓度的还原石墨烯和碲纳米线分散液；(5) Respectively configure a certain concentration of reduced graphene and tellurium nanowire dispersions;
(6)在真空抽滤辅助下，将一定量的还原石墨烯分散液滴涂在一定面积大小的柔性基底上，将液体抽干；(6) With the assistance of vacuum filtration, a certain amount of reduced graphene dispersion liquid is drop-coated on a flexible substrate with a certain area size, and the liquid is drained;
(7)在真空抽滤辅助下，将一定量的碲纳米线分散液滴涂在步骤(6)中还原石墨烯覆盖的区域，将液体抽干；(7) With the assistance of vacuum filtration, a certain amount of tellurium nanowire dispersion liquid is drop-coated on the area covered by the reduced graphene in step (6), and the liquid is drained;
(8)将步骤(7)中覆盖有复合薄膜的柔性基底于30—60℃下真空烘干；(8) vacuum-drying the flexible substrate covered with the composite film in step (7) at 30-60°C;
(9)将步骤(8)中覆盖有复合薄膜的玻璃纤维膜转移到管式炉中，在Ar/H2混合气氛(氢气含量8％)中于200℃下退火一定时间。(9) Transfer the glass fiber membrane covered with the composite film in step (8) to a tube furnace, and anneal at 200° C. for a certain period of time in an Ar/H mixed atmosphere ( hydrogen content 8%).
所用的表面活性剂为聚乙烯苯磺酸钠(NaPSS),所用的酸为氢溴酸或氢碘酸，所用的氧化石墨烯与聚苯乙烯磺酸钠质量比为2:1—1:2；The surfactant used is sodium polystyrene sulfonate (NaPSS), the acid used is hydrobromic acid or hydroiodic acid, and the mass ratio of graphene oxide and sodium polystyrene sulfonate used is 2:1—1:2 ;
制备碲纳米线的水热反应时间为1.5—3小时，冷却方式为水冷；The hydrothermal reaction time for preparing tellurium nanowires is 1.5-3 hours, and the cooling method is water cooling;
所用的丙酮与水热反应混合液的体积比为2—4；The volume ratio of the acetone used and the hydrothermal reaction mixture is 2-4;
所用的柔性基底为常温至500℃下稳定的玻璃纤维膜；The flexible substrate used is a glass fiber membrane stable at room temperature to 500°C;
所述的还原石墨烯的浓度为1mg/ml；碲纳米线为2mg/ml。The concentration of the reduced graphene is 1 mg/ml; the concentration of the tellurium nanowires is 2 mg/ml.
所述的还原石墨烯的滴涂量0.15—0.5mg/cm2，碲纳米线的滴涂量0.1—2mg/cm2；The dispensing amount of the reduced graphene is 0.15-0.5 mg/cm 2 , and the dispensing amount of the tellurium nanowire is 0.1-2 mg/cm 2 ;
退火气氛为Ar/H2,退火时间为0.5—2小时。The annealing atmosphere is Ar/H 2 , and the annealing time is 0.5-2 hours.
本发明的有益效果是：加入聚苯乙烯磺酸钠来使得还原石墨烯能分散在水中，从而可以将还原石墨烯与碲纳米线制成分散液；通过控制还原石墨烯及碲纳米线的水热合成条件，调控了还原石墨烯及碲纳米线为电子结构，使两者能够相互匹配；通过控制还原石墨烯与碲纳米线在复合薄膜中不同的质量比例以及退火条件，优化了复合热电薄膜的电导率及Seebeck系数。本发明具有制备周期短、工艺简单可控、安全无污染、能耗低、产物具有柔性且性能优良等特点，根据实际生产要求，该工艺可以灵活地根据玻璃纤维膜的大小制备出不同大小的复合热电薄膜，具有广阔的工业应用前景。The beneficial effects of the present invention are: adding sodium polystyrene sulfonate to make the reduced graphene disperse in water, so that the reduced graphene and tellurium nanowires can be made into a dispersion liquid; The thermal synthesis conditions adjusted the electronic structure of reduced graphene and tellurium nanowires so that the two could match each other; by controlling the different mass ratios of reduced graphene and tellurium nanowires in the composite film and the annealing conditions, the composite thermoelectric film was optimized Conductivity and Seebeck coefficient. The invention has the characteristics of short preparation period, simple and controllable process, safety and pollution-free, low energy consumption, flexible product and excellent performance. According to actual production requirements, the process can flexibly prepare glass fiber membranes of different sizes The composite thermoelectric thin film has broad industrial application prospects.
附图说明Description of drawings
图1为本发明实施例1的制备工艺流程图。Figure 1 is a flow chart of the preparation process of Example 1 of the present invention.
图2为本发明实施例1的可分散还原石墨烯的扫描电子显微镜照片。Fig. 2 is a scanning electron micrograph of the dispersible reduced graphene of Example 1 of the present invention.
图3为本发明实施例1的可分散碲纳米线的扫描电子显微镜照片。FIG. 3 is a scanning electron micrograph of the dispersible tellurium nanowires in Example 1 of the present invention.
图4为本发明实施例1的复合薄膜的扫描电子显微镜照片。Fig. 4 is a scanning electron micrograph of the composite thin film of Example 1 of the present invention.
图5为本发明实施例1的复合薄膜的电导率及Seebeck系数Fig. 5 is the electrical conductivity and the Seebeck coefficient of the composite thin film of the embodiment of the present invention 1
具体实施方式detailed description
下面通过实施例进一步阐述本发明的实质性特点和显著的进步,但本发明并不仅仅局限于下面的实施例：Further set forth substantive characteristics and remarkable progress of the present invention below by embodiment, but the present invention is not limited to following embodiment:
实施例1：Example 1:
如图1所示，一种柔性还原石墨烯/碲纳米线复合热电薄膜的制备方法，它包括以下步骤：As shown in Figure 1, a kind of preparation method of flexible reduced graphene/tellurium nanowire composite thermoelectric film, it comprises the following steps:
(1)将25mg氧化石墨烯(GO)与12.5mg聚苯乙烯磺酸钠(NaPSS)超声分散在12.5mL的去离子水中，再向分散液中加入25mL饱和氢溴酸溶液，将混合液转移至50mL的反应釜中于120℃下水热反应2小时后自然冷却得到沉淀；用去离子水将沉淀冲洗3—5次后，于60℃下真空干燥沉淀3小时得到可分散的还原石墨烯，可分散还原石墨烯的扫描电子显微镜照片如图2所示；(1) Ultrasonic disperse 25 mg graphene oxide (GO) and 12.5 mg sodium polystyrene sulfonate (NaPSS) in 12.5 mL of deionized water, then add 25 mL of saturated hydrobromic acid solution to the dispersion, and transfer the mixture to Into a 50mL reactor, hydrothermally reacted at 120°C for 2 hours, then cooled naturally to obtain a precipitate; rinsed the precipitate with deionized water for 3-5 times, and vacuum-dried the precipitate at 60°C for 3 hours to obtain dispersible reduced graphene. The scanning electron micrograph of dispersible reduced graphene is shown in Figure 2;
(2)将0.369g亚碲酸钠与2g聚乙烯吡咯烷酮搅拌溶解于70mL去离子水中，再向溶液中加入6.6mL25％的氨水及3.4mL98％的水合肼，将混合液转移至100mL的反应釜中于180℃下水热反应3小时后用流动的自来水冷却反应釜；向冷却后的混合液中加入160mL的丙酮后，将混合物离心并弃去上清液得到可分散的碲纳米线，可分散碲纳米线的扫描电子显微镜照片如图3所示；(2) Stir and dissolve 0.369g of sodium tellurite and 2g of polyvinylpyrrolidone in 70mL of deionized water, then add 6.6mL of 25% ammonia water and 3.4mL of 98% hydrazine hydrate to the solution, and transfer the mixture to a 100mL reactor After hydrothermal reaction at 180°C for 3 hours, cool the reactor with flowing tap water; add 160 mL of acetone to the cooled mixture, centrifuge the mixture and discard the supernatant to obtain dispersible tellurium nanowires, which can be dispersed The scanning electron microscope photo of tellurium nanowires is shown in Figure 3;
(3)分别配置1mg/mL的还原石墨烯分散液和2mg/mL的碲纳米线分散液；在真空抽滤辅助下，将0.15mL的还原石墨烯分散液均匀滴涂在2cm×0.5cm的玻璃纤维膜上，将液体抽干；再在真空抽滤辅助下，将0.1mL的碲纳米线分散液均匀滴涂还原石墨烯覆盖的区域，等液体抽干后，将覆盖有复合薄膜的玻璃纤维膜于60℃下真空烘干；(3) Prepare 1mg/mL reduced graphene dispersion and 2mg/mL tellurium nanowire dispersion respectively; with the assistance of vacuum filtration, evenly drop-coat 0.15mL reduced graphene dispersion on a 2cm×0.5cm On the glass fiber membrane, drain the liquid; then, with the aid of vacuum filtration, evenly drop 0.1mL of tellurium nanowire dispersion onto the area covered by the reduced graphene. After the liquid is drained, place the glass covered with the composite film The fiber membrane was vacuum dried at 60°C;
(4)烘干了的玻璃纤维膜转移到管式炉中，在Ar/H2混合气氛(氢气含量8％)中于200℃下退火2小时，复合薄膜的扫描电子显微镜照片如图4所示，电导率及Seebeck系数如图5所示。(4) The dried glass fiber membrane is transferred to a tube furnace and annealed at 200°C for 2 hours in an Ar/H mixed atmosphere (8% hydrogen content). The scanning electron micrograph of the composite film is shown in Figure 4. The electrical conductivity and Seebeck coefficient are shown in Figure 5.
实施例2：Example 2:
(1)将25mg氧化石墨烯(GO)与50mg聚苯乙烯磺酸钠(NaPSS)超声分散在12.5mL的去离子水中，再向分散液中加入50mL饱和氢溴酸溶液，将混合液转移至100mL的反应釜中于150℃下水热反应2小时后自然冷却得到沉淀；用去离子水将沉淀冲洗3—5次后，于60℃下真空干燥沉淀3小时得到可分散的还原石墨烯；(1) ultrasonically disperse 25mg graphene oxide (GO) and 50mg sodium polystyrene sulfonate (NaPSS) in 12.5mL deionized water, then add 50mL saturated hydrobromic acid solution to the dispersion, and transfer the mixture to In a 100mL reactor, hydrothermally react at 150°C for 2 hours, then naturally cool to obtain a precipitate; rinse the precipitate with deionized water for 3-5 times, then vacuum dry the precipitate at 60°C for 3 hours to obtain dispersible reduced graphene;
(2)将0.369g亚碲酸钠与2g聚乙烯吡咯烷酮搅拌溶解于70mL去离子水中，再向溶液中加入6.6mL25％的氨水及3.4mL98％的水合肼，将混合液转移至100mL的反应釜中于180℃下水热反应1.5小时后用流动的自来水冷却反应釜；向冷却后的混合液中加入320mL的丙酮后，将混合物离心并弃去上清液得到可分散的碲纳米线；(2) Stir and dissolve 0.369g of sodium tellurite and 2g of polyvinylpyrrolidone in 70mL of deionized water, then add 6.6mL of 25% ammonia water and 3.4mL of 98% hydrazine hydrate to the solution, and transfer the mixture to a 100mL reactor After hydrothermal reaction at 180°C for 1.5 hours, cool the reactor with flowing tap water; add 320 mL of acetone to the cooled mixture, centrifuge the mixture and discard the supernatant to obtain dispersible tellurium nanowires;
(3)分别配置1mg/mL的还原石墨烯分散液和2mg/mL的碲纳米线分散液；在真空抽滤辅助下，将0.15mL的还原石墨烯分散液均匀滴涂在2cm×0.5cm的玻璃纤维膜上，将液体抽干；再在真空抽滤辅助下，将0.1mL的碲纳米线分散液均匀滴涂还原石墨烯覆盖的区域，等液体抽干后，将覆盖有复合薄膜的玻璃纤维膜于60℃下真空烘干；(3) Prepare 1mg/mL reduced graphene dispersion and 2mg/mL tellurium nanowire dispersion respectively; with the assistance of vacuum filtration, evenly drop-coat 0.15mL reduced graphene dispersion on a 2cm×0.5cm On the glass fiber membrane, drain the liquid; then, with the aid of vacuum filtration, evenly drop 0.1mL of tellurium nanowire dispersion onto the area covered by the reduced graphene. After the liquid is drained, place the glass covered with the composite film The fiber membrane was vacuum dried at 60°C;
(4)烘干了的玻璃纤维膜转移到管式炉中，在Ar/H2混合气氛(氢气含量8％)中于200℃下退火2小时。(4) The dried glass fiber membrane was transferred to a tube furnace, and annealed at 200° C. for 2 hours in an Ar/H 2 mixed atmosphere (8% hydrogen content).
实施例3：Example 3:
(1)将25mg氧化石墨烯(GO)与25mg聚苯乙烯磺酸钠(NaPSS)超声分散在12.5mL的去离子水中，再向分散液中加入25mL饱和氢溴酸溶液，将混合液转移至50mL的反应釜中于120℃下水热反应2小时后自然冷却得到沉淀；用去离子水将沉淀冲洗3—5次后，于60℃下真空干燥沉淀3小时得到可分散的还原石墨烯；(1) ultrasonically disperse 25mg graphene oxide (GO) and 25mg sodium polystyrene sulfonate (NaPSS) in 12.5mL deionized water, then add 25mL saturated hydrobromic acid solution to the dispersion, and transfer the mixture to In a 50mL reactor, hydrothermally react at 120°C for 2 hours, then naturally cool to obtain a precipitate; rinse the precipitate with deionized water for 3-5 times, and vacuum dry the precipitate at 60°C for 3 hours to obtain dispersible reduced graphene;
(2)将0.369g亚碲酸钠与2g聚乙烯吡咯烷酮搅拌溶解于70mL去离子水中，再向溶液中加入6.6mL25％的氨水及3.4mL98％的水合肼，将混合液转移至100mL的反应釜中于180℃下水热反应3小时后用流动的自来水冷却反应釜；向冷却后的混合液中加入160mL的丙酮后，将混合物离心并弃去上清液得到可分散的碲纳米线；(2) Stir and dissolve 0.369g of sodium tellurite and 2g of polyvinylpyrrolidone in 70mL of deionized water, then add 6.6mL of 25% ammonia water and 3.4mL of 98% hydrazine hydrate to the solution, and transfer the mixture to a 100mL reactor After hydrothermal reaction at 180°C for 3 hours, cool the reactor with flowing tap water; add 160 mL of acetone to the cooled mixture, centrifuge the mixture and discard the supernatant to obtain dispersible tellurium nanowires;
(3)分别配置1mg/mL的还原石墨烯分散液和2mg/mL的碲纳米线分散液；在真空抽滤辅助下，将0.5mL的还原石墨烯分散液均匀滴涂在2cm×0.5cm的玻璃纤维膜上，将液体抽干；再在真空抽滤辅助下，将1mL的碲纳米线分散液均匀滴涂还原石墨烯覆盖的区域，等液体抽干后，将覆盖有复合薄膜的玻璃纤维膜于60℃下真空烘干；(3) Prepare 1mg/mL reduced graphene dispersion and 2mg/mL tellurium nanowire dispersion respectively; with the assistance of vacuum filtration, evenly drop-coat 0.5mL reduced graphene dispersion on a 2cm×0.5cm On the glass fiber membrane, drain the liquid; then, with the aid of vacuum filtration, evenly drop 1mL of the tellurium nanowire dispersion onto the area covered by the reduced graphene, and after the liquid is drained, place the glass fiber covered with the composite film The film was vacuum dried at 60°C;
(4)烘干了的玻璃纤维膜转移到管式炉中，在Ar/H2混合气氛(氢气含量8％)中于200℃下退火0.5小时。(4) The dried glass fiber membrane was transferred to a tube furnace, and annealed at 200° C. for 0.5 hours in an Ar/H 2 mixed atmosphere (8% hydrogen content).
实施例4：Example 4:
(1)将25mg氧化石墨烯(GO)与12.5mg聚苯乙烯磺酸钠(NaPSS)超声分散在12.5mL的去离子水中，再向分散液中加入25mL饱和氢碘酸溶液，将混合液转移至50mL的反应釜中于150℃下水热反应6小时后自然冷却得到沉淀；用去离子水将沉淀冲洗3—5次后，于60℃下真空干燥沉淀3小时得到可分散的还原石墨烯；(1) Ultrasonic disperse 25 mg graphene oxide (GO) and 12.5 mg sodium polystyrene sulfonate (NaPSS) in 12.5 mL deionized water, then add 25 mL saturated hydroiodic acid solution to the dispersion, and transfer the mixture Into a 50mL reactor, hydrothermally reacted at 150°C for 6 hours, then cooled naturally to obtain a precipitate; rinsed the precipitate with deionized water for 3-5 times, and vacuum-dried the precipitate at 60°C for 3 hours to obtain dispersible reduced graphene;
(2)将0.178g亚碲酸钠与1g聚乙烯吡咯烷酮搅拌溶解于35mL去离子水中，再向溶液中加入3.3mL25％的氨水及1.7mL98％的水合肼，将混合液转移至50mL的反应釜中于180℃下水热反应3小时后用流动的自来水冷却反应釜；向冷却后的混合液中加入80mL的丙酮后，将混合物离心并弃去上清液得到可分散的碲纳米线；(2) Stir and dissolve 0.178g of sodium tellurite and 1g of polyvinylpyrrolidone in 35mL of deionized water, then add 3.3mL of 25% ammonia water and 1.7mL of 98% hydrazine hydrate to the solution, and transfer the mixture to a 50mL reaction kettle After hydrothermal reaction at 180°C for 3 hours, cool the reactor with flowing tap water; add 80 mL of acetone to the cooled mixture, centrifuge the mixture and discard the supernatant to obtain dispersible tellurium nanowires;
(3)分别配置1mg/mL的还原石墨烯分散液和2mg/mL的碲纳米线分散液；在真空抽滤辅助下，将0.5mL的还原石墨烯分散液均匀滴涂在1cm×1cm的玻璃纤维膜上，将液体抽干；再在真空抽滤辅助下，将1mL的碲纳米线分散液均匀滴涂还原石墨烯覆盖的区域，等液体抽干后，将覆盖有复合薄膜的玻璃纤维膜于60℃下真空烘干；(3) Prepare 1mg/mL reduced graphene dispersion and 2mg/mL tellurium nanowire dispersion respectively; with the assistance of vacuum filtration, evenly drop-coat 0.5mL reduced graphene dispersion on 1cm×1cm glass On the fiber membrane, drain the liquid; then, with the assistance of vacuum filtration, evenly drop 1mL of tellurium nanowire dispersion onto the area covered by the reduced graphene, and after the liquid is drained, place the glass fiber membrane covered with the composite film Vacuum drying at 60°C;
(4)烘干了的玻璃纤维膜转移到管式炉中，在Ar/H2混合气氛(氢气含量8％)中于200℃下退火2小时。(4) The dried glass fiber membrane was transferred to a tube furnace, and annealed at 200° C. for 2 hours in an Ar/H 2 mixed atmosphere (8% hydrogen content).
实施例5：Example 5:
(1)将25mg氧化石墨烯(GO)与12.5mg聚苯乙烯磺酸钠(NaPSS)超声分散在12.5mL的去离子水中，再向分散液中加入50mL饱和氢碘酸溶液，将混合液转移至100mL的反应釜中于150℃下水热反应2小时后自然冷却得到沉淀；用去离子水将沉淀冲洗3—5次后，于60℃下真空干燥沉淀3小时得到可分散的还原石墨烯；(1) Ultrasonic disperse 25 mg graphene oxide (GO) and 12.5 mg sodium polystyrene sulfonate (NaPSS) in 12.5 mL deionized water, then add 50 mL saturated hydroiodic acid solution to the dispersion, and transfer the mixture Into a 100mL reactor, hydrothermally reacted at 150°C for 2 hours, then cooled naturally to obtain a precipitate; rinsed the precipitate with deionized water for 3-5 times, and vacuum-dried the precipitate at 60°C for 3 hours to obtain dispersible reduced graphene;
(2)将0.178g亚碲酸钠与1g聚乙烯吡咯烷酮搅拌溶解于35mL去离子水中，再向溶液中加入3.3mL25％的氨水及1.7mL98％的水合肼，将混合液转移至50mL的反应釜中于180℃下水热反应1.5小时后用流动的自来水冷却反应釜；向冷却后的混合液中加入80mL的丙酮后，将混合物离心并弃去上清液得到可分散的碲纳米线；(2) Stir and dissolve 0.178g of sodium tellurite and 1g of polyvinylpyrrolidone in 35mL of deionized water, then add 3.3mL of 25% ammonia water and 1.7mL of 98% hydrazine hydrate to the solution, and transfer the mixture to a 50mL reaction kettle After hydrothermal reaction at 180°C for 1.5 hours, cool the reactor with flowing tap water; add 80 mL of acetone to the cooled mixture, centrifuge the mixture and discard the supernatant to obtain dispersible tellurium nanowires;
(3)分别配置1mg/mL的还原石墨烯分散液和2mg/mL的碲纳米线分散液；在真空抽滤辅助下，将0.15mL的还原石墨烯分散液均匀滴涂在1cm×1cm的玻璃纤维膜上，将液体抽干；再在真空抽滤辅助下，将1mL的碲纳米线分散液均匀滴涂还原石墨烯覆盖的区域，等液体抽干后，将覆盖有复合薄膜的玻璃纤维膜于60℃下真空烘干；(3) Prepare 1mg/mL reduced graphene dispersion and 2mg/mL tellurium nanowire dispersion respectively; with the assistance of vacuum filtration, evenly drop-coat 0.15mL reduced graphene dispersion on 1cm×1cm glass On the fiber membrane, drain the liquid; then, with the assistance of vacuum filtration, evenly drop 1mL of tellurium nanowire dispersion onto the area covered by the reduced graphene, and after the liquid is drained, place the glass fiber membrane covered with the composite film Vacuum drying at 60°C;
(4)烘干了的玻璃纤维膜转移到管式炉中，在Ar/H2混合气氛(氢气含量8％)中于200℃下退火0.5小时。(4) The dried glass fiber membrane was transferred to a tube furnace, and annealed at 200° C. for 0.5 hours in an Ar/H 2 mixed atmosphere (8% hydrogen content).
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