阅读说明：本技术 多孔TiO2/NaPSS的复合敏感材料的制备方法及其产品 (Porous TiO2Preparation method of NaPSS composite sensitive material and product thereof ) 是由 张晓宇 张楠 杨文耀 段良菊 查小婷 侯超 邓泽毅 彭清林 于 2020-08-12 设计创作，主要内容包括：本发明公开了多孔TiO<Sub>2</Sub>/NaPSS的复合敏感材料的制备方法及其产品,具体制备方法如下：制备方法如下：首先将聚苯乙烯微球和四氯化钛水溶液通过旋涂法均匀涂在清洗后的叉指电极上,烘干；其次将烘干的电极放入二氯甲烷溶液中超声溶解聚苯乙烯微球,驱溶,获得带有多孔TiO<Sub>2</Sub>膜的叉指电极；最后将带有多孔TiO<Sub>2</Sub>膜的叉指电极采用浸渍法涂敷添加有羧甲基纤维素钠的聚苯乙烯磺酸钠溶液,获得多孔TiO<Sub>2</Sub>/NaPSS的复合敏感材料；制得的材料的阻抗值和湿滞差减小、线性关系增强,其响应速度加快,且重复稳定性得到较大提高,可以在湿度传感器方面具有广阔的应用前景。(The invention discloses porous TiO 2 A preparation method of NaPSS composite sensitive material and a product thereof are specifically as follows: the preparation method comprises the following steps: firstly, uniformly coating polystyrene microspheres and a titanium tetrachloride aqueous solution on cleaned interdigital electrodes by a spin coating method, and drying; secondly, putting the dried electrode into dichloromethane solution to ultrasonically dissolve the polystyrene microspheres, and removing the solution to obtain the porous TiO 2 Interdigital electrodes of the membrane; finally, porous TiO is carried 2 Coating sodium polystyrene sulfonate solution added with sodium carboxymethylcellulose on interdigital electrode of membrane by dipping method to obtain porous TiO 2 NaPSS composite sensitive material; the impedance value and the humidity hysteresis difference of the prepared material are reduced, the linear relation is enhanced, the response speed is accelerated, the repeated stability is greatly improved, and the material has wide application prospect in the aspect of humidity sensors.)

1. Porous TiO₂The preparation method of the NaPSS composite sensitive material is characterized by comprising the following specific steps:

1) uniformly coating the polystyrene microspheres and the titanium tetrachloride aqueous solution on the cleaned interdigital electrodes by a spin coating method, and drying;

2) putting the dried electrode into dichloromethane solution to ultrasonically dissolve polystyrene microspheres, and removing the solvent to obtain porous TiO₂Interdigital electrodes of the membrane;

3) will carry porous TiO₂Coating sodium polystyrene sulfonate solution added with sodium carboxymethylcellulose on interdigital electrode of membrane by dipping method to obtain porous TiO₂NaPSS composite sensitive material.

2. The porous TiO of claim 1₂The preparation method of the NaPSS composite sensitive material is characterized in that: in the step (1), the cleaning is ultrasonic cleaning by using absolute ethyl alcohol and acetone.

3. The porous TiO of claim 1₂The preparation method of the NaPSS composite sensitive material is characterized by comprising the following steps: in the step (1), the concentration of the titanium tetrachloride in the polystyrene microspheres and the titanium tetrachloride water solution is 0.3 mol/L; the concentration of the polystyrene microsphere is 0.05-0.2 mol/L, and the dosage ratio of the polystyrene microsphere to the titanium tetrachloride is 1: 1.

4. porous TiO according to claim 3₂The preparation method of the NaPSS composite sensitive material is characterized by comprising the following steps: the diameter of the polystyrene microsphere is 1000 nm.

5. The porous TiO of claim 1₂The preparation method of the NaPSS composite sensitive material is characterized by comprising the following steps: in the step (2), the ultrasound is performed for 2-10 min.

6. The porous TiO of claim 1₂The preparation method of the NaPSS composite sensitive material is characterized by comprising the following steps: in the step (2), the flooding is performed for 1h at a constant temperature of 200 ℃.

7. The porous TiO of claim 1₂The preparation method of the NaPSS composite sensitive material is characterized by comprising the following steps: the mass fraction of the sodium polystyrene sulfonate aqueous solution is 1%.

8. Porous TiO produced by the production method according to any one of claims 1 to 7₂NaPSS composite sensitive material.

Technical Field

The invention relates to the field of materials, in particular to porous TiO₂A preparation method of NaPSS composite sensitive material and a product prepared by the method are also disclosed.

Background

The humidity sensor plays an important role in environmental detection in the fields of biological pharmacy, scientific research, meteorology, industrial production and the like. In recent years, a great deal of research has been conducted on high performance humidity sensors: sensitivity, linearity, wet hysteresis and response speed are main parameters for evaluating the performance of the humidity sensor, and the key influencing the performance lies in the research of humidity sensitive materials such as polymers, carbon nano tubes, inorganic oxides, porous silicon, graphene and nano composite materials thereof. The polymer humidity sensitive material has the excellent performances of high sensitivity, moderate impedance change range, quick response time and the like, is deeply favored by scientific researchers and paid attention to the outside, but has poor linearity and low repeatability, and is not suitable for being used in high-temperature and high-humidity environments. The inorganic oxide has good stability and repeatability, and quick response time, but has small impedance change range, low sensitivity and poor long-term stability, and needs to be calibrated or cleaned by heating frequently. Therefore, a single inorganic oxide or polymer humidity sensitive material is often difficult to meet the requirements of the humidity sensor application field on high sensitivity, quick response, long-term stability, excellent repeatability and other excellent comprehensive properties, and therefore, numerous researchers research the organic-inorganic composite humidity sensitive material with the advantages. The cadmium sulfide/polyaniline (CdS/PANI) composite humidity-sensitive material prepared by Niemei and the like has small humidity stagnation, good repeatability and moderate impedance change range, but the PANI rapidly expands after moisture absorption and is easy to agglomerate with CdS to prevent water molecules from being dispersed in the dehumidification process, so that the response speed is reduced. Preparation of zirconium oxide/sodium polystyrene sulfonate (ZrO) by Taozhou et al₂NaPSS) composite humidity sensitive material has the advantages of fast response, small impedance and the like. Preparation of titanium oxide/sodium polystyrene sulfonate (Ti)O₂NaPSS) composite humidity sensitive material, research TiO₂The influence of the pore diameter of (a) on the humidity sensitivity of the polymer to obtain TiO when the pore diameter is 1000nm₂The NaPSS composite material has the excellent performances of fast response, small wet retardation and the like. The research on the humidity-sensitive characteristics of the NaPSS-based composite material, such as sensitivity, linearity, repeatability and the like, is rarely reported.

Disclosure of Invention

In view of the above, an object of the present invention is to provide a porous TiO₂A preparation method of NaPSS composite sensitive material; the second purpose of the invention is to provide porous TiO prepared by the preparation method₂NaPSS composite sensitive material.

In order to achieve the purpose, the invention provides the following technical scheme:

1. porous TiO₂The preparation method of the NaPSS composite sensitive material comprises the following specific steps:

1) uniformly coating the polystyrene microspheres and a titanium tetrachloride aqueous solution on the cleaned interdigital electrodes by a spin coating method, and drying;

2) putting the dried electrode into dichloromethane solution to ultrasonically dissolve polystyrene microspheres, and removing the solvent to obtain porous TiO₂Interdigital electrodes of the membrane;

3) will carry porous TiO₂Coating sodium polystyrene sulfonate solution added with sodium carboxymethylcellulose on interdigital electrode of membrane by dipping method to obtain porous TiO₂NaPSS composite sensitive material.

Preferably, in the step (1), the cleaning is ultrasonic cleaning using absolute ethyl alcohol and acetone.

In the step (1), the concentration of titanium tetrachloride in the polystyrene microspheres and the titanium tetrachloride water solution is 0.3 mol/L; the concentration of the polystyrene microsphere is 0.05-0.2 mol/L, and the dosage ratio of the polystyrene microsphere to the titanium tetrachloride is 1: 1.

preferably, the polystyrene microspheres have a diameter of 1000 nm.

Preferably, in the step (2), the ultrasound is performed for 2-10 min.

Preferably, in the step (2), the dissolving-out is carried out at a constant temperature of 200 ℃ for 1 h.

Preferably, the mass fraction of the sodium polystyrene sulfonate aqueous solution is 1%.

2. Porous TiO prepared by the preparation method₂NaPSS composite sensitive material.

The invention has the beneficial effects that: the invention discloses porous TiO₂The preparation method of the NaPSS composite sensitive material comprises the steps of coating electrodes with mixed solution of polystyrene microspheres and titanium tetrachloride aqueous solution, dissolving the polystyrene microspheres to enable porous titanium oxide to be orderly arranged on the copper interdigital electrodes, and then arranging porous TiO₂Prepare uniform sodium polystyrene sulfonate (NaPSS) film to obtain porous titanium oxide/sodium polystyrene sulfonate (porous TiO)₂NaPSS) composite humidity sensitive material. The porous TiO obtained₂The impedance value and the humidity retardation difference of the/NaPSS composite humidity sensitive material are reduced, the linear relation is enhanced, the response speed is accelerated (the moisture absorption time is 1-2 s, the moisture removal time is 25s), and the porous TiO is₂The repeated stability of the NaPSS humidity sensitive material is greatly improved. Thus, porous TiO₂The NaPSS composite humidity sensitive material has wide application prospect in the aspect of humidity sensors.

Drawings

In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:

FIG. 1 is an SEM image of a sample (a: TiO)₂A film; b: TiO2₂A NaPSS film; c: porous TiO₂A film; d: porous TiO₂NaPSS film).

FIG. 2 is a graph showing the humidity-sensitive characteristics of porous TiO2/NaPSS (a: frequency characteristic; b: voltage characteristic).

FIG. 3 shows the sensitivity results of the humidity sensitive material (a: sample humidity sensitivity curve; b: simple linear regression fitting of NaPSS).

FIG. 4 is a graph showing the response curves of the samples (a: moisture absorption response time of three moisture-sensitive materials; b: moisture desorption response time of three moisture-sensitive materials).

FIG. 5 is a graph of the cyclic response of the sample.

FIG. 6 is a wet hysteresis chart of a sample (a: NaPSS film; b: TiO)₂A NaPSS film; c: porous TiO₂NaPSS film).

Detailed Description

The present invention is further described with reference to the following drawings and specific examples so that those skilled in the art can better understand the present invention and can practice the present invention, but the examples are not intended to limit the present invention.