CN114588846A - A kind of nanocellulose/Ti3C2TX composite aerogel and its preparation method and application - Google Patents
A kind of nanocellulose/Ti3C2TX composite aerogel and its preparation method and application Download PDFInfo
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Abstract
Description
技术领域technical field
本发明属于气凝胶技术领域，具体涉及一种纳米纤维素/Ti3C2TX复合气凝胶及其制备方法与应用。The invention belongs to the technical field of aerogel, in particular to a nanocellulose/Ti 3 C 2 T X composite aerogel and a preparation method and application thereof.
背景技术Background technique
人体皮肤不仅可以感知外部压力，还可以感知外部温度和湿度。相关研究者对传感材料进行研究期望实现电子皮肤的感知功能。导电气凝胶因其重量超轻、孔隙结构丰富、压缩性优良等优点而被广泛应用于传感器领域。其中，纤维素气凝胶因其绿色无污染、来源广泛、生物相容性好、重量轻、抗压强度好等特点而被广泛用作制备气凝胶传感器的框架材料。然而，纤维素气凝胶的导电性较差，使其难以作为唯一的材料用于制备电子皮肤。另外，一般纤维素气凝胶由于其内部结构随机，压缩恢复性能较差，难以满足电子皮肤的日常使用要求。同时，由于纤维素具有丰富的亲水性基团，吸收水分子后，纤维素气凝胶会在外力的作用下，由于强大的水张力，使其内部结构发生粘结，最终破坏气凝胶的结构，这使得纤维素气凝胶在实际应用中难以长期使用。因此，如何赋予纤维素复合气凝胶良好的压缩性能，解决吸水失效的问题使气凝胶保持压缩弹性，是纤维素基气凝胶领域的一大挑战，对于扩大纤维素基气凝胶的应用具有重要意义。Human skin can sense not only external pressure, but also external temperature and humidity. Relevant researchers conduct research on sensing materials and expect to realize the sensing function of electronic skin. Conductive aerogels have been widely used in sensors due to their ultra-light weight, rich pore structure, and excellent compressibility. Among them, cellulose aerogels are widely used as framework materials for the preparation of aerogel sensors due to their green, pollution-free, wide-ranging sources, good biocompatibility, light weight, and good compressive strength. However, the poor electrical conductivity of cellulose aerogels makes it difficult to be used as the only material for electronic skin. In addition, due to its random internal structure and poor compression recovery performance, general cellulose aerogels are difficult to meet the daily use requirements of electronic skins. At the same time, because cellulose has abundant hydrophilic groups, after absorbing water molecules, the cellulose aerogel will bond its internal structure due to the strong water tension under the action of external force, and finally destroy the aerogel The structure of cellulose aerogels makes it difficult to use cellulose aerogels in practical applications for a long time. Therefore, how to endow the cellulose composite aerogel with good compressibility, solve the problem of water absorption failure and keep the aerogel compressive elasticity is a major challenge in the field of cellulose-based aerogels. Applications are important.
发明内容SUMMARY OF THE INVENTION
本发明所要解决的技术问题是针对现有技术中存在的上述不足，提供一种纳米纤维素/Ti3C2TX复合气凝胶及其制备方法与应用，该纳米纤维素/Ti3C2TX复合气凝胶具有高压缩弹性，并具有压力传感功能，在电子皮肤领域具有潜在的应用前景。The technical problem to be solved by the present invention is to provide a nanocellulose/Ti 3 C 2 T X composite aerogel and its preparation method and application in view of the above-mentioned deficiencies in the prior art. The nano cellulose/Ti 3 C The 2TX composite aerogel has high compressive elasticity and pressure sensing function, which has potential application prospects in the field of electronic skin.
为解决上述技术问题，本发明提供的技术方案是：For solving the above-mentioned technical problems, the technical scheme provided by the present invention is:
提供一种纳米纤维素/Ti3C2TX复合气凝胶，其由多层波浪形层状材料有序密集堆叠得到，所述层状材料为纳米纤维素和Ti3C2TX均匀混合得到，并且在各层层状材料表面覆有一层甲基三甲氧基硅烷(MTMS)。 A nanocellulose / Ti3C2TX composite aerogel is provided, which is obtained by orderly and densely stacking multiple layers of wavy layered materials, and the layered materials are uniformly composed of nanocellulose and Ti3C2TX It is obtained by mixing, and a layer of methyltrimethoxysilane (MTMS) is coated on the surface of each layered material.
按上述方案，所述波浪形层状材料厚度为0.1～1μm，各层层状材料间距小于200μm。According to the above scheme, the thickness of the wavy layered material is 0.1-1 μm, and the distance between the layers of the layered material is less than 200 μm.
按上述方案，所述纳米纤维素/Ti3C2TX复合气凝胶中Ti3C2TX的质量百分含量为10～70％。According to the above scheme, the mass percentage content of Ti 3 C 2 T X in the nanocellulose/Ti 3 C 2 T X composite aerogel is 10-70%.
本发明还包括上述纳米纤维素/Ti3C2TX复合气凝胶的制备方法，具体步骤如下：The present invention also includes the preparation method of the above nanocellulose/Ti 3 C 2 T X composite aerogel, and the specific steps are as follows:
1)制备TEMPO氧化纤维素纳米纤维：将TEMPO、天然纤维、NaBr和NaClO加入去离子水中并搅拌均匀，然后滴加NaOH溶液保持体系pH值为9，室温搅拌条件下进行氧化反应，然后再加入NaBH4还原未完全氧化的醛基，反应完成后抽滤至中性，将所得固体洗涤至中性并分散于去离子水中得到TEMPO氧化纤维素纳米纤维的分散液(TOCN分散液)；1) Preparation of TEMPO oxidized cellulose nanofibers: add TEMPO, natural fibers, NaBr and NaClO into deionized water and stir evenly, then dropwise add NaOH solution to keep the pH value of the system at 9, carry out the oxidation reaction under stirring conditions at room temperature, and then add NaBH 4 reduces the incompletely oxidized aldehyde group, after the reaction is completed, suction filtration to neutrality, the obtained solid is washed to neutrality and dispersed in deionized water to obtain a dispersion of TEMPO oxidized cellulose nanofibers (TOCN dispersion);
2)制备Ti3C2TX：将氟化钠加入浓盐酸中，搅拌至氟化钠完全溶解得到刻蚀溶液，然后将Ti3AlC2加入到刻蚀溶液中进行刻蚀反应，反应完成后用去离子水离心洗涤反应液，收集沉淀物重新分散于去离子水中，放入冰箱冷冻，再取出冰箱解冻，经过多次循环冻融过程后将所得分散液在氮气气氛下超声分散均匀，将所得悬浮液离心处理，收集上层分散相得到Ti3C2TX分散液；2) Preparation of Ti 3 C 2 T X : adding sodium fluoride to concentrated hydrochloric acid, stirring until the sodium fluoride is completely dissolved to obtain an etching solution, and then adding Ti 3 AlC 2 to the etching solution to carry out an etching reaction, and the reaction is completed Then, the reaction solution was washed with deionized water by centrifugation, and the precipitate was collected and re-dispersed in deionized water, put in a refrigerator to freeze, and then taken out of the refrigerator to thaw. The obtained suspension is centrifuged, and the upper dispersed phase is collected to obtain a Ti 3 C 2 T X dispersion;
3)纳米纤维素/Ti3C2TX复合气凝胶的制备：将步骤1)所得TEMPO氧化纤维素纳米纤维的分散液与步骤2)所得Ti3C2TX分散液混合并搅拌均匀，然后将所得混合液进行双向冷冻，将冷冻完成后的样品冷冻干燥得到TOCN/Ti3C2TX复合气凝胶，将得到的TOCN/Ti3C2TX复合气凝胶和甲基三甲氧基硅烷放置于真空干燥箱中加热将甲基三甲氧基硅烷沉积至TOCN/Ti3C2TX复合气凝胶表面得到表面疏水性的纳米纤维素/Ti3C2TX复合气凝胶(M-TOCN/Ti3C2TX)。3) Preparation of nanocellulose/Ti 3 C 2 T X composite aerogel: The dispersion of TEMPO oxidized cellulose nanofibers obtained in step 1) and the Ti 3 C 2 T X dispersion obtained in step 2) are mixed and stirred uniformly , and then bidirectionally freeze the obtained mixed solution, freeze-dry the frozen sample to obtain TOCN/Ti 3 C 2 T X composite aerogel, and combine the obtained TOCN/Ti 3 C 2 T X composite aerogel with methyl Trimethoxysilane was placed in a vacuum drying oven and heated to deposit methyltrimethoxysilane on the surface of TOCN/Ti 3 C 2 T X composite aerogel to obtain surface hydrophobic nanocellulose/Ti 3 C 2 T X composite gas Gel ( M - TOCN/ Ti3C2TX ).
按上述方案，步骤1)所述天然纤维素为棉花纤维素，木浆纤维素，苎麻纤维素，甘蔗渣纤维素，细菌纤维素，海鞘纤维素中的一种或多种。According to the above scheme, the natural cellulose in step 1) is one or more of cotton cellulose, wood pulp cellulose, ramie cellulose, bagasse cellulose, bacterial cellulose, and ascidian cellulose.
按上述方案，步骤1)所述TEMPO、天然纤维、NaBr、NaClO与NaBH4的质量比为1：5～100：5～100：5～100：5～100。其中天然纤维作为纤维原料，NaClO用作氧化剂，TEMPO用作催化剂，NaBr用作助催化剂，NaBH4用作还原剂。According to the above scheme, the mass ratio of TEMPO, natural fiber, NaBr, NaClO and NaBH 4 in step 1) is 1:5-100:5-100:5-100:5-100. Among them, natural fiber was used as fiber raw material, NaClO was used as oxidant, TEMPO was used as catalyst, NaBr was used as co - catalyst, and NaBH was used as reducing agent.
按上述方案，步骤1)将所得固体洗涤至中性并分散于去离子水中，分散方式为机械搅拌，高压均质处理，超声细胞破碎仪，球磨处理，高速水冲击处理中的一种。According to the above scheme, step 1) the obtained solid is washed to neutrality and dispersed in deionized water, and the dispersion mode is one of mechanical stirring, high-pressure homogenization treatment, ultrasonic cell disruptor, ball milling treatment, and high-speed water shock treatment.
按上述方案，步骤1)所述TEMPO氧化纤维素纳米纤维的分散液的浓度为0.1～2wt％。According to the above scheme, the concentration of the dispersion liquid of the TEMPO oxidized cellulose nanofibers in step 1) is 0.1-2 wt%.
按上述方案，步骤2)所述浓盐酸浓度为5～12mol/L，所述刻蚀溶液中盐酸与氟化钠的摩尔比为1～4：1。According to the above scheme, the concentration of concentrated hydrochloric acid in step 2) is 5-12 mol/L, and the molar ratio of hydrochloric acid to sodium fluoride in the etching solution is 1-4:1.
按上述方案，步骤2)所述Ti3AlC2与刻蚀溶液中氟化钠的质量比为0.2～5：1。According to the above scheme, the mass ratio of Ti 3 AlC 2 in step 2) to sodium fluoride in the etching solution is 0.2-5:1.
按上述方案，步骤2)所述刻蚀反应温度为25～36℃，刻蚀反应时间为2～24h。According to the above scheme, the etching reaction temperature in step 2) is 25-36° C., and the etching reaction time is 2-24 h.
按上述方案，步骤2)所述Ti3AlC2粒径为100～600目。According to the above scheme, the particle size of Ti 3 AlC 2 described in step 2) is 100-600 mesh.
按上述方案，步骤2)循环冻融次数为1～5次。According to the above scheme, the number of cycles of freezing and thawing in step 2) is 1 to 5 times.
按上述方案，步骤2)所述Ti3C2TX分散液的浓度为1～20mg/mL。步骤2)采用氟化钠和浓盐酸的混合溶液作为刻蚀剂刻蚀掉多层状Ti3AlC2中的铝层，从而得到更易剥离为单片层的多层Ti3C2TX，再利用冷冻解冻法和超声进一步将多层Ti3C2TX剥离为单片层的Ti3C2TX。According to the above scheme, the concentration of the Ti 3 C 2 T X dispersion in step 2) is 1-20 mg/mL. Step 2) using a mixed solution of sodium fluoride and concentrated hydrochloric acid as an etchant to etch away the aluminum layer in the multi-layer Ti 3 AlC 2 , thereby obtaining a multi-layer Ti 3 C 2 T X that is easier to peel off into a single layer, The multi-layer Ti 3 C 2 T X is further exfoliated into a single layer of Ti 3 C 2 T X by using the freeze-thaw method and ultrasound.
按上述方案，步骤3)所述混合液中Ti3C2TX的质量占其中固体总质量(TOCN和Ti3C2TX)的10～70％。According to the above scheme, the mass of Ti 3 C 2 T X in the mixed solution in step 3) accounts for 10-70% of the total mass of solids (TOCN and Ti 3 C 2 T X ).
按上述方案，步骤3)所述双向冷冻的方法为：将所述混合液注入双向冷冻模具中，将双向冷冻模具置于楔型块上，楔型块上端为倾斜角度为15～30°的斜面，楔型块下端与圆形铜块接触，将圆形铜块置于液氮中，使混合液完全冷冻，冷冻时间为1～4h。According to the above scheme, the method for the two-way freezing in step 3) is: injecting the mixed solution into a two-way freezing mold, placing the two-way freezing mold on a wedge block, and the upper end of the wedge block is an inclined angle of 15 to 30°. The lower end of the wedge-shaped block is in contact with the round copper block, and the round copper block is placed in liquid nitrogen to completely freeze the mixture, and the freezing time is 1 to 4 hours.
所述楔形块为聚二甲基硅氧烷(PDMS)材质。按上述方案，步骤3)所述甲基三甲氧基硅烷的体积与TOCN/Ti3C2TX复合气凝胶的质量比为1～20mL/g。The wedge-shaped block is made of polydimethylsiloxane (PDMS). According to the above scheme, the volume ratio of the methyltrimethoxysilane in step 3) to the mass ratio of the TOCN/Ti 3 C 2 T X composite aerogel is 1-20 mL/g.
按上述方案，步骤3)所述冷冻干燥温度为-10～-60℃，真空度20～40Pa，冷冻干燥时间为1～4天。According to the above scheme, the freeze-drying temperature in step 3) is -10--60°C, the vacuum degree is 20-40Pa, and the freeze-drying time is 1-4 days.
按上述方案，步骤3)将甲基三甲氧基硅烷沉积至TOCN/Ti3C2TX复合气凝胶表面，具体工艺条件为：真空条件下于25～100℃反应沉积2～24小时。According to the above scheme, step 3) depositing methyltrimethoxysilane on the surface of TOCN/Ti 3 C 2 T X composite aerogel, and the specific process conditions are: reaction deposition at 25-100° C. for 2-24 hours under vacuum conditions.
本发明还包括上述纳米纤维素/Ti3C2TX复合气凝胶在传感器领域的应用。The invention also includes the application of the above nanocellulose/Ti 3 C 2 T X composite aerogel in the field of sensors.
以及包含上述纳米纤维素/Ti3C2TX复合气凝胶的传感器。And a sensor comprising the above nanocellulose/Ti 3 C 2 T X composite aerogel.
本发明制备的TEMPO氧化纤维素纳米纤维长度在20nm～2μm，直径在1～50nm之间，与其他方法得到的纤维素纳米纤维相比，具有更易分散的优点(TOCN上带有被氧化后的羧基因而带有负电荷，其本身由于负电荷之间的静电斥力能很好地实现纳米分散)，同时还可作为二维纳米片的良好分散体。而Ti3C2TX作为一种良好的二维活性导电材料，不仅具有优异的导电性，而且也具有优异电磁屏蔽性功能，本发明制备的Ti3C2TX不仅产量提高，而且所得到的Ti3C2TX尺寸更大且分布更加集中。最后利用双向冷冻干燥法将纳米纤维素(TOCN)和Ti3C2TX的混合分散体制备成具有有序堆叠的波浪结构的压缩弹性TOCN/Ti3C2TX导电气凝胶，解决了纤维素基气凝胶弹性差的缺点。为了防止气凝胶吸水后压缩弹性损失，进一步通过热化学气相沉积在弹性气凝胶表面沉积疏水性甲基三甲氧基硅烷(MTMS)，以保持其压缩弹性。有序堆叠的波浪形层状结构可展现出良好的压缩弹性。由于纤维素材料的吸水特性使得气凝胶压缩弹性损失，通过简单地沉积疏水MTMS硅烷至气凝胶表面，改善了纤维素气凝胶吸水性使性能下降的缺点，使得复合气凝胶具有疏水性并且压缩弹性得以保存，适用于传感器的实际使用。The TEMPO oxidized cellulose nanofibers prepared by the present invention have a length of 20nm-2μm and a diameter of 1-50nm. Compared with the cellulose nanofibers obtained by other methods, they have the advantage of being easier to disperse (TOCN has oxidized cellulose nanofibers). The carboxyl gene has a negative charge, which can well achieve nano-dispersion due to the electrostatic repulsion between the negative charges), and can also be used as a good dispersion of two-dimensional nanosheets. As a good two - dimensional active conductive material, Ti 3 C 2 T X not only has excellent electrical conductivity, but also has excellent electromagnetic shielding function . The resulting Ti 3 C 2 T X is larger in size and more concentrated. Finally, the mixed dispersion of nanocellulose (TOCN) and Ti 3 C 2 T X was prepared into a compressive elastic TOCN/Ti 3 C 2 T X conductive aerogel with ordered stacked wave structure by bidirectional freeze-drying method. The disadvantage of poor elasticity of cellulose-based aerogels is eliminated. In order to prevent the loss of compressive elasticity of the aerogel after water absorption, hydrophobic methyltrimethoxysilane (MTMS) was further deposited on the surface of the elastic aerogel by thermal chemical vapor deposition to maintain its compressive elasticity. The orderly stacked wavy layered structure can exhibit good compressive elasticity. Due to the water absorption properties of cellulose materials, the compression elasticity of the aerogels is lost. By simply depositing the hydrophobic MTMS silane on the surface of the aerogels, the shortcomings of the performance degradation caused by the water absorption of the cellulose aerogels are improved, so that the composite aerogels have hydrophobic properties. The stability and compression elasticity are preserved, which is suitable for the actual use of the sensor.
本发明的有益效果在于：1、本发明提供的纳米纤维素/Ti3C2TX复合气凝胶不仅质轻，同时内部具有有序堆叠的波浪形层状结构和疏水性能使其具有持久的高压缩弹性(压缩强度高达4.5KPa，300次10％压缩循环下压缩强度仍可保留92％)，而且制备的纳米纤维素/Ti3C2TX复合气凝胶还具有良好的压力传感性能，用于组装成压力传感器灵敏度高达4.05kPa-1，50ms响应时间和1Pa的压力检测极限，可用于手指弯曲、心跳、发声等生理信号的检测，解决了目前纤维素基气凝胶压缩弹性差而难以实际应用的缺点，在多功能传感器和电子皮肤领域具有极大的应用潜力。2、本发明提供的制备方法工艺简单，操作方便，对环境无污染，整个工艺对设备要求不高，有利于工业化生产。The beneficial effects of the present invention are as follows: 1. The nanocellulose/Ti 3 C 2 T X composite aerogel provided by the present invention is not only light in weight, but also has an orderly stacked wavy layered structure and hydrophobic properties inside, making it durable The high compressive elasticity (compressive strength is as high as 4.5KPa, and the compressive strength can still retain 92% under 300 10% compression cycles), and the prepared nanocellulose/Ti 3 C 2 T X composite aerogel also has good pressure transmission. It can be used to assemble a pressure sensor with a sensitivity of up to 4.05kPa -1 , a response time of 50ms and a pressure detection limit of 1Pa. It can be used for the detection of physiological signals such as finger bending, heartbeat, and vocalization. It solves the problem of the current compression of cellulose-based aerogels. Due to the disadvantage of poor elasticity and difficult practical application, it has great application potential in the fields of multifunctional sensors and electronic skin. 2. The preparation method provided by the present invention has the advantages of simple process, convenient operation, no pollution to the environment, and the whole process does not require high equipment, which is beneficial to industrialized production.
附图说明Description of drawings
图1为本发明实施例1制备的Ti3C2TX分散液的TEM图；1 is a TEM image of the Ti 3 C 2 T X dispersion prepared in Example 1 of the present invention;
图2为对比例1和2所制备的G-TOCN/Ti3C2TX-5和B-TOCN/Ti3C2TX-5气凝胶压缩弹性测试图；Fig. 2 is the compression elasticity test chart of G-TOCN/Ti 3 C 2 T X -5 and B-TOCN/Ti 3 C 2 T X -5 aerogels prepared in Comparative Examples 1 and 2;
图3为实施例1所制备的M-TOCN/Ti3C2TX-10复合气凝胶的SEM图；3 is a SEM image of the M-TOCN/Ti 3 C 2 T X -10 composite aerogel prepared in Example 1;
图4为实施例1所制备的M-TOCN/Ti3C2TX-10复合气凝胶应力-应变曲线图；4 is a stress-strain curve diagram of the M-TOCN/Ti 3 C 2 T X -10 composite aerogel prepared in Example 1;
图5为实施例1所制备的M-TOCN/Ti3C2TX-10复合气凝胶表面对水的静态接触角照片；5 is a photo of the static contact angle of the M-TOCN/Ti 3 C 2 T X -10 composite aerogel surface prepared in Example 1 with respect to water;
图6为实施例1和2所制备的M-TOCN/Ti3C2TX复合气凝胶传感器的电流(I)-时间(t)曲线图；6 is a current (I)-time (t) curve diagram of the M-TOCN/Ti 3 C 2 T X composite aerogel sensors prepared in Examples 1 and 2;
图7为实施例2制备的M-TOCN/Ti3C2TX-30复合气凝胶的应力-应变曲线图；7 is a stress-strain curve diagram of the M-TOCN/Ti 3 C 2 T X -30 composite aerogel prepared in Example 2;
图8为实施例2制备的M-TOCN/Ti3C2TX-30复合气凝胶置于狗尾草上的照片；8 is a photo of the M-TOCN/Ti 3 C 2 T X -30 composite aerogel prepared in Example 2 placed on foxtail grass;
图9为实施例1制备的传感器用于检测手指弯曲的电流(I)-时间(t)曲线图；9 is a current (I)-time (t) curve diagram of the sensor prepared in Example 1 for detecting finger bending;
图10为实施例2制备的传感器用于检测人体脉搏跳动的电流(I)-时间(t)曲线图。FIG. 10 is a current (I)-time (t) curve diagram of the sensor prepared in Example 2 for detecting human pulse beat.
具体实施方式Detailed ways
为使本领域技术人员更好地理解本发明的技术方案，下面结合附图对本发明作进一步详细描述。In order for those skilled in the art to better understand the technical solutions of the present invention, the present invention is further described in detail below with reference to the accompanying drawings.
对比例1Comparative Example 1
制备TOCN/Ti3C2TX复合气凝胶，步骤如下：To prepare TOCN/Ti 3 C 2 T X composite aerogel, the steps are as follows:
1)制备TOCN分散液：取2g木浆纤维素，0.032g TEMPO，0.2g NaBr，加入200mL去离子水中，磁力搅拌溶解，其后加入5.56mL浓度为5mmol/g的NaClO水溶液，在0.5M NaOH溶液滴定条件下，保持体系pH值为9.0进行氧化反应(反应2h)，反应完成后加入0.2g NaBH4继续进行还原反应，3h后用去离子水洗涤抽滤至中性，然后加入去离子水中分散，机械搅拌并高压均质后得到0.5wt％的TOCN分散液，其中的TOCN的直径约为3nm，长度约为1μm；1) Preparation of TOCN dispersion liquid: take 2g wood pulp cellulose, 0.032g TEMPO, 0.2g NaBr, add 200mL deionized water, magnetic stirring to dissolve, then add 5.56mL concentration of 5mmol/g NaClO aqueous solution, in 0.5M NaOH Under the condition of solution titration, keep the pH value of the system at 9.0 to carry out the oxidation reaction (reaction 2h), after the reaction is completed, add 0.2g NaBH 4 to continue the reduction reaction, wash with deionized water after 3h and filter to neutrality, and then add deionized water. After dispersion, mechanical stirring and high pressure homogenization, a 0.5wt% TOCN dispersion was obtained, in which TOCN was about 3nm in diameter and about 1μm in length;
2)制备Ti3C2TX：将1.6g氟化钠加入到20mL浓度为12mol/L的浓盐酸中，搅拌至氟化钠完全溶解得到刻蚀溶液，然后在5分钟内分5批加入1g Ti3AlC2原料(尺寸大小为200目)到刻蚀溶液中进行刻蚀反应，于36℃反应24小时，反应完成后用去离子水洗涤反应液，3500rpm离心至pH值约5，收集沉淀物重新分散于去离子水中，放入-20℃冰箱冷冻12小时，再取出冰箱解冻，经过五个循环的冻融过程，然后将所得分散液在氮气氛下超声分散30分钟，最后将分散液以7000rpm离心0.5小时，收集上层分散相，得到少层或单层Ti3C2TX分散液，分散液浓度配置成5mg/mL；2) Preparation of Ti 3 C 2 T X : 1.6 g of sodium fluoride was added to 20 mL of concentrated hydrochloric acid with a concentration of 12 mol/L, stirred until the sodium fluoride was completely dissolved to obtain an etching solution, and then added in 5 batches within 5 minutes. 1g of Ti 3 AlC 2 raw material (size of 200 mesh) was put into the etching solution to carry out the etching reaction, and the reaction was carried out at 36 ° C for 24 hours. The precipitate was redispersed in deionized water, placed in a -20°C refrigerator for 12 hours, and then taken out of the refrigerator to thaw. After five cycles of freezing and thawing, the resulting dispersion was ultrasonically dispersed for 30 minutes in a nitrogen atmosphere. The liquid was centrifuged at 7000 rpm for 0.5 hours, and the upper dispersed phase was collected to obtain a few-layer or single-layer Ti 3 C 2 T X dispersion, and the concentration of the dispersion was configured to be 5 mg/mL;
3)制备TOCN/Ti3C2TX复合气凝胶：取19g上述步骤1)制备的TOCN分散液和1mL步骤2)制备的Ti3C2TX分散液，混合并搅拌6小时得到均匀的混合液，混合液中TOCN和Ti3C2TX的总质量为100mg，质量比TOCN：Ti3C2TX＝95：5，密度为～5mg/cm3，然后将混合液倒入3cm×3cm×3cm的塑料小方盒模具中，将模具置于液氮中进行冷冻，最后将冷冻材料在-60℃和30Pa条件下冷冻干燥24小时，得到冷冻干燥的G-TOCN/Ti3C2TX复合气凝胶。3) Preparation of TOCN/Ti 3 C 2 T X composite aerogel: take 19 g of the TOCN dispersion prepared in the above step 1) and 1 mL of the Ti 3 C 2 T X dispersion prepared in the step 2), mix and stir for 6 hours to obtain a uniform The total mass of TOCN and Ti 3 C 2 T X in the mixed solution is 100mg, the mass ratio TOCN:Ti 3 C 2 T X =95:5, the density is ~5mg/cm 3 , and then the mixed solution is poured into 3cm×3cm×3cm plastic small square box mold, put the mold in liquid nitrogen for freezing, and finally freeze-dried the frozen material at -60°C and 30Pa for 24 hours to obtain freeze-dried G-TOCN/Ti 3 C 2 T X composite aerogel.
将本对比例制备的G-TOCN/Ti3C2TX复合气凝胶组成传感主元件，G-TOCN/Ti3C2TX复合气凝胶上下两个表面分别设置一个铜箔电极，电极与铜导线相连，最后封装制备成高压缩弹性的柔性压力传感器。The G-TOCN/Ti 3 C 2 T X composite aerogel prepared in this comparative example constitutes the main sensing element, and a copper foil electrode is set on the upper and lower surfaces of the G-TOCN/Ti 3 C 2 T X composite aerogel respectively. , the electrodes are connected with copper wires, and finally a flexible pressure sensor with high compression elasticity is packaged and prepared.
采用MTS Exceed E44(中国)机电万能试验机在室温下测量气凝胶的力学性能。G-TOCN/Ti3C2TX气凝胶表现出差的压缩弹性，受力形变后不能恢复原样，如图2a所示。主要是因为常规冷冻干燥的气凝胶内部为无序结构，受到外部压力时容易发生破坏。The mechanical properties of the aerogels were measured at room temperature using an MTS Exceed E44 (China) electromechanical universal testing machine. The G-TOCN/Ti 3 C 2 T X aerogel exhibited poor compressive elasticity and could not return to its original shape after being deformed by force, as shown in Figure 2a. The main reason is that the inside of conventional freeze-dried aerogels has a disordered structure and is easily damaged when subjected to external pressure.
利用CHI 660E型电化学工作站，在1V的直流电压下实时测量本对比例制备的G-TOCN/Ti3C2TX复合气凝胶的电流(I)-时间(t)曲线，以KH-01步进电机和测力计作为辅助设备进行一系列电信号响应测试。该传感器不能产生电信号响应，几乎没有传感性能，主要是因为气凝胶中Ti3C2TX含量太少，使复合气凝胶的导电性差，没有传感性能。Using a CHI 660E electrochemical workstation, the current (I)-time (t) curves of the G-TOCN/Ti 3 C 2 T X composite aerogels prepared in this comparative example were measured in real time at a DC voltage of 1 V, with KH- 01 A stepper motor and a dynamometer are used as auxiliary equipment for a series of electrical signal response tests. The sensor cannot generate electrical signal response and has almost no sensing performance, mainly because the content of Ti 3 C 2 T X in the aerogel is too small, so the composite aerogel has poor conductivity and no sensing performance.
对比例2Comparative Example 2
制备TOCN/Ti3C2TX复合气凝胶，步骤如下：To prepare TOCN/Ti 3 C 2 T X composite aerogel, the steps are as follows:
1)制备TOCN分散液：采用对比例1的方法制备TOCN分散液，其浓度为0.5wt％；1) Preparation of TOCN dispersion: using the method of Comparative Example 1 to prepare TOCN dispersion, the concentration of which is 0.5wt%;
2)制备Ti3C2TX：采用对比例1的方法制备浓度为5mg/mL的Ti3C2TX分散液；2) Preparation of Ti 3 C 2 T X : using the method of Comparative Example 1 to prepare a Ti 3 C 2 T X dispersion with a concentration of 5 mg/mL;
3)制备TOCN/Ti3C2TX复合气凝胶：取19g步骤1)制备的TOCN分散液和1mL步骤2)制备的Ti3C2TX分散液，混合并搅拌6小时得到均匀的混合液，混合液中TOCN和Ti3C2TX的总质量为100mg，质量比TOCN：Ti3C2TX＝95：5，密度为～5mg/cm3，然后将混合液倒入3cm×3cm×3cm的塑料小方盒模具中，将模具置于楔型块上，楔型块上端为倾斜角度为15°的斜面，楔型块下端与圆形铜块接触，将圆形铜块置于液氮中进行双向冷冻，冷冻时间为1h，最后将冷冻材料在-60℃和30Pa条件下冷冻干燥24小时，得到双向冷冻干燥的B-TOCN/Ti3C2TX复合气凝胶。3) Preparation of TOCN/Ti 3 C 2 T X composite aerogel: take 19 g of the TOCN dispersion prepared in step 1) and 1 mL of the Ti 3 C 2 T X dispersion prepared in step 2), mix and stir for 6 hours to obtain a uniform aerogel. Mixed solution, the total mass of TOCN and Ti 3 C 2 T X in the mixed solution is 100mg, the mass ratio TOCN:Ti 3 C 2 T X =95:5, the density is ~5mg/cm 3 , and then the mixed solution is poured into 3cm In the plastic small square box mold of ×3cm×3cm, place the mold on the wedge block. It was placed in liquid nitrogen for bidirectional freezing, and the freezing time was 1 h. Finally, the frozen material was freeze-dried at -60 °C and 30 Pa for 24 hours to obtain a bidirectional freeze-dried B-TOCN/Ti 3 C 2 T X composite aerogel .
将本对比例制备的B-TOCN/Ti3C2TX复合气凝胶组成传感主元件，B-TOCN/Ti3C2TX复合气凝胶上下两个表面分别设置一个铜箔电极，电极上与铜导线相连，最后封装制备成高压缩弹性的柔性压力传感器。The B-TOCN/Ti 3 C 2 T X composite aerogel prepared in this comparative example constitutes the main sensing element, and a copper foil electrode is set on the upper and lower surfaces of the B-TOCN/Ti 3 C 2 T X composite aerogel respectively. , the electrodes are connected with copper wires, and finally a flexible pressure sensor with high compressive elasticity is packaged and prepared.
采用MTS Exceed E44(中国)机电万能试验机在室温下测量复合气凝胶的力学性能，本对比例制备的B-TOCN/Ti3C2TX气凝胶表现出良好的压缩弹性，受力形变后能恢复原样，如图2b所示，主要是因为采用双向冷冻干燥制备气凝胶具有有序堆叠的波浪形层状结构，具有优异的压缩弹性，但是随着在空气中放置时间延长，气凝胶压缩弹性逐渐下降，主要是因为纤维素强烈的吸水性，使气凝胶结构被破环。 The mechanical properties of the composite aerogels were measured by MTS Exceed E44 (China) electromechanical universal testing machine at room temperature. After deformation, it can be restored to its original state, as shown in Figure 2b, mainly because the aerogels prepared by bidirectional freeze-drying have an ordered stacked wavy layered structure with excellent compressive elasticity, but with prolonged exposure in air, The compressive elasticity of aerogels gradually decreased, mainly because the strong water absorption of cellulose resulted in the destruction of the aerogel structure.
利用CHI 660E型电化学工作站，在1V的直流电压下实时测量本对比例制备的TOCN/Ti3C2TX复合气凝胶的电流(I)-时间(t)曲线，该传感器不能产生电信号响应，几乎没有传感性能，主要是因为气凝胶中Ti3C2TX含量太少，使复合气凝胶的导电性差，没有传感性能。Using a CHI 660E electrochemical workstation, the current (I)-time (t) curve of the TOCN/Ti 3 C 2 T X composite aerogel prepared in this comparative example was measured in real time at a DC voltage of 1 V. The sensor cannot generate electricity. Signal response, almost no sensing performance, mainly because the content of Ti 3 C 2 T X in the aerogel is too small, so that the composite aerogel has poor conductivity and no sensing performance.
实施例1Example 1
制备TOCN/Ti3C2TX复合气凝胶，步骤如下：To prepare TOCN/Ti 3 C 2 T X composite aerogel, the steps are as follows:
1)制备TOCN分散液：取2g木浆纤维素，0.032g TEMPO，0.2g NaBr，加入200mL去离子水中，磁力搅拌溶解，其后加入5.56mL浓度为5mmol/g的NaClO水溶液，在0.5M NaOH溶液滴定条件下，保持体系pH值为9.0进行氧化反应(反应2h)，反应完成后加入0.2g NaBH4继续进行还原反应，3h后用去离子水洗涤抽滤至中性，然后加入去离子水中分散，机械搅拌并高压均质后得到0.5wt％的TOCN分散液，其中的TOCN的直径约为3nm，长度约为1μm；1) Preparation of TOCN dispersion liquid: take 2g wood pulp cellulose, 0.032g TEMPO, 0.2g NaBr, add 200mL deionized water, magnetic stirring to dissolve, then add 5.56mL concentration of 5mmol/g NaClO aqueous solution, in 0.5M NaOH Under the condition of solution titration, keep the pH value of the system at 9.0 to carry out the oxidation reaction (reaction 2h), after the reaction is completed, add 0.2g NaBH 4 to continue the reduction reaction, wash with deionized water after 3h and filter to neutrality, and then add deionized water. After dispersion, mechanical stirring and high pressure homogenization, a 0.5wt% TOCN dispersion was obtained, in which TOCN was about 3nm in diameter and about 1μm in length;
2)制备Ti3C2TX：将1.6g氟化钠加入到20mL浓度为12mol/L的浓盐酸中，搅拌至氟化钠完全溶解得到刻蚀溶液，然后在5分钟内分5批加入1g Ti3AlC2原料(尺寸大小为200目)到刻蚀溶液中进行刻蚀反应，于36℃反应24小时，反应完成后用去离子水洗涤反应液，3500rpm离心至pH值约5，收集沉淀物重新分散于去离子水中，放入-20℃冰箱冷冻12小时，再取出冰箱解冻，经过五个循环的冻融过程，然后将所得分散液在氮气氛下超声分散30分钟，最后将分散液以7000rpm离心0.5小时，收集上层分散相，得到Ti3C2TX分散液，分散液浓度配置成5mg/mL；2) Preparation of Ti 3 C 2 T X : 1.6 g of sodium fluoride was added to 20 mL of concentrated hydrochloric acid with a concentration of 12 mol/L, stirred until the sodium fluoride was completely dissolved to obtain an etching solution, and then added in 5 batches within 5 minutes. 1g of Ti 3 AlC 2 raw material (size of 200 mesh) was put into the etching solution to carry out the etching reaction, and the reaction was carried out at 36 ° C for 24 hours. The precipitate was redispersed in deionized water, placed in a -20°C refrigerator for 12 hours, and then taken out of the refrigerator to thaw. After five cycles of freezing and thawing, the resulting dispersion was ultrasonically dispersed for 30 minutes in a nitrogen atmosphere. The liquid was centrifuged at 7000 rpm for 0.5 hours, and the upper layer dispersed phase was collected to obtain a Ti 3 C 2 T X dispersion, and the concentration of the dispersion was configured to be 5 mg/mL;
3)制备TOCN/Ti3C2TX复合气凝胶：取19g上述步骤1)制备的TOCN分散液和1mL步骤2)制备的Ti3C2TX分散液，混合并搅拌6小时得到均匀的混合液，混合液中TOCN和Ti3C2TX的总质量为100mg，质量比TOCN：Ti3C2TX＝90：10，密度为～5mg/cm3，然后将混合液倒入3cm×3cm×3cm的塑料模具中，将模具置于双向冷冻装置上进行双向冷冻，将模具置于楔型块上，楔型块上端为倾斜角度为15°的斜面，楔型块下端与圆形铜块接触，将圆形铜块置于液氮中，冷冻时间为1h，最后将冷冻材料在-60℃和30Pa真空度条件下冷冻干燥24小时，得到双向冷冻干燥的B-TOCN/Ti3C2TX复合气凝胶，最后将双向冷冻干燥的B-TOCN/Ti3C2TX复合气凝胶与2mL的MTMS同时置于真空干燥箱中，于75℃反应沉积12小时，得到疏水M-TOCN/Ti3C2TX-10复合气凝胶。3) Preparation of TOCN/Ti 3 C 2 T X composite aerogel: take 19 g of the TOCN dispersion prepared in the above step 1) and 1 mL of the Ti 3 C 2 T X dispersion prepared in the step 2), mix and stir for 6 hours to obtain a uniform The total mass of TOCN and Ti 3 C 2 T X in the mixed liquid is 100mg, the mass ratio TOCN:Ti 3 C 2 T X =90:10, the density is ~5mg/cm 3 , and then the mixed liquid is poured into In a 3cm×3cm×3cm plastic mold, place the mold on a two-way freezing device for two-way freezing, and place the mold on a wedge block. The circular copper block was placed in liquid nitrogen for 1 h, and finally the frozen material was freeze-dried at -60 °C and 30 Pa vacuum for 24 hours to obtain bidirectional freeze-dried B-TOCN/Ti 3 C 2 T X composite aerogel, and finally the bidirectional freeze-dried B-TOCN/Ti 3 C 2 T X composite aerogel and 2 mL of MTMS were placed in a vacuum drying box at the same time, and the reaction was deposited at 75 °C for 12 hours. The hydrophobic M-TOCN/Ti 3 C 2 T X -10 composite aerogel was obtained.
本实施例步骤2)制备的Ti3C2TX分散液的TEM图如图1所示，可见其中Ti3C2TX为少层或单层结构，单层厚度约为1nm，横向尺寸约为600nm。The TEM image of the Ti 3 C 2 T X dispersion prepared in step 2) of this example is shown in FIG. 1 , it can be seen that Ti 3 C 2 T X is a few-layer or single-layer structure, the thickness of the single layer is about 1 nm, and the lateral size is about 1 nm. about 600nm.
如图3所示为本实施例制备的M-TOCN/Ti3C2TX-10复合气凝胶的SEM图，可看出该气凝胶具有有序堆叠的波浪形层状结构，各层厚度约1μm，各层间距小于200μm。Figure 3 shows the SEM image of the M-TOCN/Ti 3 C 2 T X -10 composite aerogel prepared in this example. It can be seen that the aerogel has an orderly stacked wavy layered structure. The layer thickness is about 1 μm, and the distance between the layers is less than 200 μm.
采用MTS Exceed E44(中国)机电万能试验机在室温下测量M-TOCN/Ti3C2TX-10复合气凝胶的力学性能和压缩性能。该气凝胶表现出良好的压缩弹性，受力形变后能恢复原样，这是因为均匀复合的TOCN/Ti3C2TX微观结构展现出波浪形片层结构，导致复合气凝胶具有优异的压缩弹性，并且疏水改性后，在空气中放置不会对压缩弹性造成损失。如图4所示为本实施例制备的M-TOCN/Ti3C2TX-10复合气凝胶应力-应变曲线，由图可知该气凝胶具有4.5KPa的高压缩强度。The mechanical and compressive properties of M-TOCN/Ti 3 C 2 T X -10 composite aerogels were measured at room temperature by MTS Exceed E44 (China) electromechanical universal testing machine. The aerogel exhibits good compressive elasticity and can be restored to its original shape after being deformed by force. This is because the uniformly composite TOCN/Ti 3 C 2 T X microstructure exhibits a wavy lamellar structure, which leads to the excellent composite aerogel. compressive elasticity, and after hydrophobic modification, placing in air will not cause loss of compressive elasticity. FIG. 4 shows the stress-strain curve of the M-TOCN/Ti 3 C 2 T X -10 composite aerogel prepared in this example. It can be seen from the figure that the aerogel has a high compressive strength of 4.5KPa.
如图5所示为本实施例制备的M-TOCN/Ti3C2TX-10复合气凝胶表面对水的静态接触角照片，由图5看出，该气凝胶的疏水角为120°。Figure 5 shows the photo of the static contact angle of the M-TOCN/Ti 3 C 2 T X -10 composite aerogel surface prepared in this example to water. It can be seen from Figure 5 that the hydrophobic angle of the aerogel is 120°.
将本实施例制备的M-TOCN/Ti3C2TX-10复合气凝胶组成传感主元件，M-TOCN/Ti3C2TX-10复合气凝胶上下两个表面分别设置一个铜箔电极，电极与铜导线相连，最后封装制备成高压缩弹性的柔性压力传感器。利用CHI 660E型电化学工作站在1V的直流电压下实时测量该传感器的电流(I)-时间(t)曲线，如图6所示，基于M-TOCN/Ti3C2TX-10复合气凝胶制备的传感器表现出1.01kPa-1的灵敏度。The M-TOCN/Ti 3 C 2 T X -10 composite aerogel prepared in this example constitutes the main sensing element, and the upper and lower surfaces of the M-TOCN/Ti 3 C 2 T X -10 composite aerogel are respectively arranged A copper foil electrode, the electrode is connected with a copper wire, and finally packaged to prepare a flexible pressure sensor with high compression elasticity. The current (I)-time (t) curve of the sensor was measured in real time at a DC voltage of 1V using a CHI 660E electrochemical workstation, as shown in Figure 6. Based on the M-TOCN/Ti 3 C 2 T X -10 composite gas The gel-fabricated sensor exhibited a sensitivity of 1.01 kPa -1 .
将本实施例制备的传感器紧贴手指，利用CHI 660E型电化学工作站在1V的直流电压下实时测量该传感器的电流(I)-时间(t)曲线，如图9所示，随着手指弯曲角度的增大，电流信号也随之变大，表明该传感器可用于检测手指弯曲运动。The sensor prepared in this example was placed close to the finger, and the current (I)-time (t) curve of the sensor was measured in real time under a DC voltage of 1V using a CHI 660E electrochemical workstation, as shown in Figure 9, with the bending of the finger. As the angle increases, the current signal also increases, indicating that the sensor can be used to detect finger bending motion.
实施例2Example 2
制备TOCN/Ti3C2TX复合气凝胶，步骤如下：To prepare TOCN/Ti 3 C 2 T X composite aerogel, the steps are as follows:
1)制备TOCN分散液：采用实施例1的方法制备0.5wt％的TOCN分散液；1) Preparation of TOCN dispersion: using the method of Example 1 to prepare 0.5wt% TOCN dispersion;
2)制备Ti3C2TX：采用实施例1的方法制备浓度为5mg/mL的Ti3C2TX分散液；2) Preparation of Ti 3 C 2 T X : using the method of Example 1 to prepare a Ti 3 C 2 T X dispersion with a concentration of 5 mg/mL;
3)制备TOCN/Ti3C2TX复合气凝胶：取14g上述步骤1)制备的TOCN分散液和6mL步骤2)制备的Ti3C2TX分散液，混合并搅拌6小时得到均匀的混合液，混合液中TOCN和Ti3C2TX的总质量为100mg，质量比TOCN：Ti3C2TX＝70：30，密度为～5mg/cm3，然后将混合液倒入3cm×3cm×3cm的塑料模具中，将模具置于双向冷冻装置上进行双向冷冻，将模具置于楔型块上，楔型块上端为倾斜角度为15°的斜面，楔型块下端与圆形铜块接触，将圆形铜块置于液氮中，冷冻时间为1h，最后将冷冻材料在-60℃和30Pa真空度条件下冷冻干燥24小时，得到双向冷冻干燥的B-TOCN/Ti3C2TX复合气凝胶，最后将双向冷冻干燥的B-TOCN/Ti3C2TX复合气凝胶与2mL的MTMS同时置于真空干燥箱中，于75℃反应沉积12小时，得到M-TOCN/Ti3C2TX-30复合气凝胶。3) Preparation of TOCN/Ti 3 C 2 T X composite aerogel: take 14 g of the TOCN dispersion prepared in the above step 1) and 6 mL of the Ti 3 C 2 T X dispersion prepared in the step 2), mix and stir for 6 hours to obtain a uniform The total mass of TOCN and Ti 3 C 2 T X in the mixed solution is 100mg, the mass ratio TOCN:Ti 3 C 2 T X =70:30, the density is ~5mg/cm 3 , and then the mixed solution is poured into In a 3cm×3cm×3cm plastic mold, place the mold on a two-way freezing device for two-way freezing, and place the mold on a wedge block. The circular copper block was placed in liquid nitrogen for 1 h, and finally the frozen material was freeze-dried at -60 °C and 30 Pa vacuum for 24 hours to obtain bidirectional freeze-dried B-TOCN/Ti 3 C 2 T X composite aerogel, and finally the bidirectional freeze-dried B-TOCN/Ti 3 C 2 T X composite aerogel and 2 mL of MTMS were placed in a vacuum drying box at the same time, and the reaction was deposited at 75 °C for 12 hours. The M-TOCN/Ti 3 C 2 T X -30 composite aerogel was obtained.
本实施例制备的B-TOCN/Ti3C2TX复合气凝胶可放置于狗尾草上不掉落，照片如图8所示，表明该复合气凝胶具有质量轻的优点，密度约为5mg/cm3。The B-TOCN/Ti 3 C 2 T X composite aerogel prepared in this example can be placed on foxtail grass without falling off. 5mg/cm 3 .
采用MTS Exceed E44(中国)机电万能试验机在室温下测量本实施例制备的M-TOCN/Ti3C2TX-30复合气凝胶的力学性能和压缩性能。该M-TOCN/Ti3C2TX-30复合气凝胶表现出良好的压缩弹性，受力形变后能恢复原样，具有优异的压缩弹性，在空气中放置不会对压缩弹性造成损失。如图7所示为本实施例制备的M-TOCN/Ti3C2TX-30复合气凝胶在10％压缩应变下的应力-应变曲线，该复合气凝胶重复压缩300次，压缩强度仍能保留92％。The mechanical properties and compressive properties of the M-TOCN/Ti 3 C 2 T X -30 composite aerogel prepared in this example were measured at room temperature by MTS Exceed E44 (China) electromechanical universal testing machine. The M-TOCN/Ti 3 C 2 T X -30 composite aerogel exhibits good compressive elasticity, can return to its original shape after being deformed by force, and has excellent compressive elasticity, which will not cause loss of compressive elasticity when placed in air. Figure 7 shows the stress-strain curve of the M-TOCN/Ti 3 C 2 T X -30 composite aerogel prepared in this example under 10% compressive strain. Strength still retains 92%.
将本实施例制备的M-TOCN/Ti3C2TX-30复合气凝胶组成传感主元件，M-TOCN/Ti3C2TX-30复合气凝胶上下两个表面分别设置一个铜箔电极，电极与铜导线相连，最后封装制备成高压缩弹性的柔性压力传感器。利用CHI 660E型电化学工作站在1V的直流电压下实时测量该传感器的电流(I)-时间(t)曲线，如图6所示，该传感器表现出4.05kPa-1的灵敏度，50ms的响应时间和1Pa的检测极限。The M-TOCN/Ti 3 C 2 T X -30 composite aerogel prepared in this example constitutes the main sensing element, and the upper and lower surfaces of the M-TOCN/Ti 3 C 2 T X -30 composite aerogel are respectively arranged A copper foil electrode, the electrode is connected with a copper wire, and finally packaged to prepare a flexible pressure sensor with high compression elasticity. Using a CHI 660E electrochemical workstation to measure the current (I)-time (t) curve of the sensor in real time at a DC voltage of 1V, as shown in Figure 6, the sensor exhibits a sensitivity of 4.05kPa -1 and a response time of 50ms and a detection limit of 1Pa.
将本实施例制备的传感器紧贴于手臂脉搏处，利用CHI 660E型电化学工作站在1V的直流电压下实时测量该传感器的电流(I)-时间(t)曲线，如图10所示，传感器可产生明显的信号峰，表明该传感器可用于检测脉搏跳动。The sensor prepared in this example is closely attached to the pulse of the arm, and the current (I)-time (t) curve of the sensor is measured in real time under a DC voltage of 1V using a CHI 660E electrochemical workstation, as shown in Figure 10. Distinct signal peaks are produced, indicating that the sensor can be used to detect pulse beats.
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