CN112458745B - Method for preparing flexible inorganic semiconductor textile composite material by padding - Google Patents

Method for preparing flexible inorganic semiconductor textile composite material by padding Download PDF

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CN112458745B
CN112458745B CN202011047309.8A CN202011047309A CN112458745B CN 112458745 B CN112458745 B CN 112458745B CN 202011047309 A CN202011047309 A CN 202011047309A CN 112458745 B CN112458745 B CN 112458745B
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solution
padding
flexible
precursor ion
inorganic semiconductor
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CN112458745A (en
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徐红
周培文
毛志平
张琳萍
马紫旋
钟毅
隋晓锋
张凯
杜立新
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Luthai Textile Co Ltd
Donghua University
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Luthai Textile Co Ltd
Donghua University
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/30—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with oxides of halogens, oxyacids of halogens or their salts, e.g. with perchlorates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B15/00—Removing liquids, gases or vapours from textile materials in association with treatment of the materials by liquids, gases or vapours
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
    • D06B3/10—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fabrics
    • D06B3/18—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fabrics combined with squeezing, e.g. in padding machines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic System; Zincates; Cadmates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • D06M11/56—Sulfates or thiosulfates other than of elements of Groups 3 or 13 of the Periodic System
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • D06M2101/36—Aromatic polyamides

Abstract

The invention relates to a method for preparing a flexible inorganic semiconductor textile composite material by padding, which comprises the following steps: (1) preparing a precursor ion A solution and a precursor ion B solution required by preparing an inorganic semiconductor; (2) sequentially and alternately padding a precursor ion A solution and a precursor ion B solution on the flexible textile material for n times in a circulating and alternating manner, wherein n is a positive integer; (3) and (3) drying the product obtained in the step (2) to obtain the flexible inorganic semiconductor textile composite material. The flexible inorganic semiconductor textile composite material consists of a flexible textile material and an inorganic semiconductor loaded on the flexible textile material; the inorganic semiconductor is nanoparticles or nanosheets, the nanoparticles have an average diameter of 100-1000 nm, and the nanosheets have an equivalent diameter of 0.5-2 μm; the inorganic semiconductor has a loading amount of 10 to 100 mg/g. The method provided by the invention is simple and easy to operate, high in production efficiency, green and environment-friendly, the waste materials are easy to recycle, and the uniform load of the inorganic semiconductor on the flexible textile material can be realized.

Description

Method for preparing flexible inorganic semiconductor textile composite material by padding
Technical Field
The invention belongs to the technical field of composite materials, and relates to a method for preparing a flexible inorganic semiconductor textile composite material by padding.
Background
A great deal of research is directed to the self-assembly of inorganic semiconductor materials on geometrically stable substrates (conductive glass) for the fields of solar energy conversion, conductive devices, batteries, etc. With the development of intelligent textiles, flexible semiconductor devices using textiles as substrates are being developed. The flexible semiconductor device is manufactured by various methods such as a solvothermal method, a hydrothermal method, a calcination method, and a SILAR (continuous ion-layer adsorption reaction method), and compared with other manufacturing methods, the SILAR is a loading method which is simple in operation, energy-saving, less in consumption, and less in damage to a substrate.
The SILAR method is a deposition process in which precursor ions (ion clusters) in a specific solution are chemically adsorbed on the surface of an active base material and chemically reacted with ions in an adsorption layer, and the reaction product is deposited on the surface of a base material to form a surface modification layer. The method is characterized in that an ion adsorption layer is formed by adsorption of ions on a substrate, the adsorbed ions react with coordination ions to generate precipitates, or the adsorbed ions undergo hydrolysis reaction to generate precipitates, the ion adsorption layer is converted into a solid film layer, the growth of the film in a nanometer scale is realized, and the thickness of the film can be controlled by controlling the concentration of anions and cations in a precursor solution and the number of times of repeating the process cycle.
The conventional SILAR method mainly includes four steps: 1) adsorbing the substrate in a precursor ion A solution; 2) washing off the precursor ions A excessively adsorbed on the surface of the substrate by using a cleaning agent; 3) putting the substrate in a precursor ion B solution for adsorption, and reacting the precursor ion A with the precursor ion B to obtain a target compound; 4) and washing off the precursor ions B excessively adsorbed on the surface by using a cleaning solvent. And (5) circulating the four steps to prepare the target compound loaded composite material.
The surface of the traditional load base material (conductive glass and metal plate) is mostly of a plane structure without a complex organizational structure, the surface is easily wetted by precursor ionic solution after chemical treatment, and the excessively adsorbed ionic solution is also easily eluted, so that the target precipitate can be uniformly loaded on the surface of the base material.
The textile is a material which is woven by yarns, has three-dimensional size, flexibility and bending and abundant surface functional groups. The yarn is mainly formed by twisting textile fibers with different lengths to a certain degree, tissue gaps exist among the yarns, capillary gaps exist among the fibers, and wetting of the gaps is influenced by hydrophilic and hydrophobic properties of textile materials.
The method is characterized in that a target precipitate is grown on the surface of a flexible textile by an SILAR method, the target precipitate cannot be uniformly distributed on the surface of the textile, the target precipitate mainly grows on the surface of fibers on the surface of the textile and less grows on the surface of fibers at the interweaving position of internal fibers and yarns, meanwhile, a precursor ion A solution of the target precipitate existing on the textile in a free state is not easy to clean, the precursor ion A solution is released in the process of soaking a precursor ion B solution of another target precipitate, the released ion A and the ion B in the solution can form the target precipitate to pollute the precursor ion B solution, and part of the target precipitate is weakly adsorbed on the surface of the textile by intermolecular force. The uneven distribution of the target precipitate on the textile surface seriously affects the performance of intelligent textile devices, and therefore, the invention of a new method for realizing the uniform loading of the target precipitate on the flexible textile is urgently needed.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a method for preparing a flexible inorganic semiconductor textile composite material by padding, wherein the existing printing and dyeing production equipment is adopted, inorganic semiconductors are assembled on the surface of the flexible textile material layer by layer, compared with the traditional continuous ionic layer adsorption reaction method (SILAR), the adsorption quantity of precursor ions on the surface of the fabric is reasonably controlled by the padding equipment, the operation procedure of washing after soaking in ionic solution in the SILAR is omitted, and the uniform loading of the inorganic semiconductors on the flexible textile material and the high-efficiency mass production of the flexible inorganic semiconductor textile composite material are realized.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing a flexible inorganic semiconductor textile composite material by padding comprises the following steps:
(1) preparing a precursor ion A solution and a precursor ion B solution required by preparing an inorganic semiconductor;
(2) sequentially and alternately padding a precursor ion A solution and a precursor ion B solution on the flexible textile material for n times in a circulating and alternating manner, wherein n is a positive integer; in a single cycle, a-B, n ═ 1, i.e., a-B; n-2, i.e. a-B-a-B; n-3, i.e. a-B-a-B; n-4, i.e.,.; in the process, the precursor ions A form an ion adsorption layer on the surface of the flexible textile material in a chemical adsorption mode, and the adsorbed ions and the coordination ions (precursor ions B) perform adsorption reaction to generate target precipitates (inorganic semiconductors) and are fixed on the surface of the flexible textile material;
(3) and (3) drying the product obtained in the step (2) to obtain the flexible inorganic semiconductor textile composite material.
As a preferred technical scheme:
a method of padding producing a flexible inorganic semiconductor textile composite material as described above, the flexible inorganic semiconductor textile composite material being composed of a flexible textile material and an inorganic semiconductor supported thereon; the inorganic semiconductor is nanoparticles or nanosheets, the nanoparticles have an average diameter of 100-1000 nm, and the nanosheets have an equivalent diameter of 0.5-2 μm; the inorganic semiconductor has a loading amount of 10 to 100 mg/g.
According to the method for preparing the flexible inorganic semiconductor textile composite material by padding, in the step (1), the precursor ions A and the precursor ions B can perform adsorption reaction to form precipitates; the precursor ion a and the precursor ion B correspond to bismuth ion and halide ion respectively (i.e. the precursor ion a is bismuth ion, the precursor ion B is halide ion, and the corresponding target precipitate is bismuth oxyhalide), or correspond to copper ion and sulfide ion respectively (i.e. the precursor ion a is copper ion, the precursor ion B is sulfide ion, and the corresponding target precipitate is copper sulfide), or correspond to zinc ammine complex ion and hydroxide ion respectively (i.e. the precursor ion a is zinc ammine complex ion, the precursor ion B is hydroxide ion, and the corresponding target precipitate is zinc oxide), or correspond to cadmium ion and sulfide ion respectively (i.e. the precursor ion a is cadmium ion, the precursor ion B is sulfide ion, and the corresponding target precipitate is cadmium sulfide), or correspond to silver ion and sulfide ion respectively (i.e. the precursor ion a is silver ion, and the precursor ion B is sulfide ion, the corresponding target precipitate is silver sulfide).
According to the method for preparing the flexible inorganic semiconductor textile composite material by padding, in the step (1), the concentration of the precursor ion A solution is determined according to the solubility of a precursor substance, but the concentration of the precursor ion A solution cannot be too high, so that the condition that the adsorption quantity of the precursor ion A is too large after padding, and the precursor ion A is released in the precursor ion B solution to pollute the precursor ion B solution in the process of padding another precursor ion B solution is avoided, and similarly, the concentration of the precursor ion B solution cannot be too high, so that the concentration of the precursor ion A in the precursor ion A solution is 2-100 mmol/L; the concentration of the precursor ions B in the precursor ion B solution is 2-80 mmol/L.
In the method for preparing the flexible inorganic semiconductor textile composite material by padding, the solvents in the precursor ion A solution and the precursor ion B solution are both water.
In the method for preparing the flexible inorganic semiconductor textile composite material by padding, in the step (2), the flexible textile material is aramid 1313, aramid 1414, cotton or polyester fabric; the gram weight of the flexible textile material is 100-250 g/m2；
When the precursor ion A solution is padded, the padding pressure is 0.5-5 kg; most of the precursor ions A are metal oxygen ions, and the solubility and the existing state of the precursor ions with low solubility can be effectively adjusted by the temperature and the pH value, so that the temperature of the precursor ion A solution is 20-50 ℃; the pH value of the precursor ion A solution is kept at 2-10 to avoid hydrolysis of the precursor ion A to separate out a precipitate; the transmission speed can adjust the adsorption and reaction time of the ions A and the ions B, and the transmission speed cannot be too high in order to ensure that the ions A and the ions B have enough time to perform adsorption reaction, so that the transmission speed of the flexible textile material is 60-500 m/h; the padding allowance rate controls the content of ions adsorbed on the surface of the fabric, and is controlled within a reasonable range, so that the phenomena of aggregation growth or inorganic nanosheet crushing and the like caused by too much or too little are avoided, and therefore, the padding allowance rate is 50-100%;
when the precursor ion B solution is padded, the padding pressure is 0.5-5 kg, the temperature of the precursor ion B solution is 20-50 ℃, the pH value of the precursor ion B solution is kept at 6-12, the transmission speed of the flexible textile material is 60-500 m/h, and the padding residual rate is 50-100%.
According to the method for preparing the flexible inorganic semiconductor textile composite material by padding, the flexible textile material is subjected to alkali treatment, and the alkali treatment can endow the surfaces of the aramid fibers 1313, the aramid fibers 1414 and the cotton or polyester fabrics with certain roughness and ion adsorption sites, so that precursor ions can be adsorbed on the surfaces of the fabrics in an ionic bond form, and conditions are provided for uniform and efficient growth of target precipitates (inorganic semiconductors).
According to the method for preparing the flexible inorganic semiconductor textile composite material by padding, caustic soda solution with the concentration of 5-20 wt% is adopted for alkali treatment, the temperature of the alkali treatment is 80-100 ℃, the time is 1-3 hours, and after the alkali treatment, the flexible textile material needs to be fully cleaned by water to remove the residual alkaline agent on the surface.
According to the method for preparing the flexible inorganic semiconductor textile composite material by padding, in the step (2), the value range of n is 5-50.
According to the method for preparing the flexible inorganic semiconductor textile composite material by padding, in the step (3), a drying mode is adopted for drying, the drying temperature is 80-100 ℃, and the time is 0.5-1 h.
The invention mechanism is as follows:
the invention is technically characterized in that aiming at flexible textile materials (such as aramid fiber, cotton, terylene and the like), padding equipment is adopted to grow target precipitates (inorganic semiconductors) on the flexible textile materials. Aiming at the structural characteristics of the flexible textile material, the ion layer-by-layer adsorption and reaction are realized by adopting a padding mode, the process of the SILAR method is improved, the step of loading the target precipitate is shortened, and the uniform loading of the target precipitate on the flexible textile material is realized.
By combining the structural characteristics of the flexible textile material, the invention adopts the padding device to realize the uniform adsorption of ions on the surface of the flexible textile material, thereby realizing the uniform load of the target precipitate on the flexible textile material. The padding equipment is characterized in that: the two ends of the roller are pressurized by compressed air, the inside of the roller is pressurized by an oil pump, the pressure on the whole range of the roller is the same by adjustment, and the difference of the edge and the middle part of the flexible textile material is not easy to cause. After the flexible textile material is soaked in the precursor ion A solution, the precursor ion A solution on the flexible textile material exists in three forms: (1) precursor ion A solution absorbed by the flexible textile material fiber; (2) a small amount of or excessive precursor ion A solution is left in the yarn interweaving gaps and the inter-fiber capillary gaps (for hydrophilic fibers, the precursor ion A solution is easy to enter the inter-yarn gaps and the inter-fiber capillary gaps, and for hydrophobic fibers, the precursor ion A solution is not easy to enter the inter-yarn gaps and the inter-fiber capillary gaps); (3) and the precursor ion A solution is remained on the surface of the flexible textile material and is easy to flow under the action of gravity. The existence form of the precursor ion A on the flexible textile material is mainly divided into three cases: (1) exists on the surface of the fiber in a chemical adsorption form; (2) exists on the surface of the fiber in a physical adsorption form; (3) in free ionic form in a flowable solution carried on the surface of the flexible textile material.
In the padding process, the precursor ion A solution on the flexible textile material can go through two processes: the flexible textile material soaked with the precursor ion A solution is pressed into the flexible textile material when passing through a rolling point, so that fibers at different parts of the flexible textile material are wetted by the precursor ion A solution, meanwhile, the flexible textile material with rich surface functional groups is equivalent to an ion filter membrane, the pressure enables the precursor ion A in the precursor ion A solution to approach the surface of the fiber ion filter membrane and be filtered by the fiber ion filter membrane, the precursor ion A is chemically adsorbed by the functional groups on the surface of the fibers until reaching the chemical adsorption balance, meanwhile, redundant precursor ions A exist in a solvent in a free state and are rolled out of the flexible textile material under the action of pressure.
The flexible textile material padded by the precursor ion A solution is changed into a fiber filter membrane with the surface rich in the precursor ion A, and the fiber filter membrane can adsorb the precursor ion B to form a target precipitate, so that the uniform adsorption of the precursor ions on the surface of the flexible textile material can be realized by adopting a padding device and combining an SILAR method, and the uniform load of the target precipitate on the surface of the flexible textile material is further realized.
The scheme of the invention will now be described with reference to specific cases:
in gram weight of 200g/m2The aramid fiber (1313) fabric is a flexible textile material, bismuth oxyhalide is taken as a target precipitate (bismuth oxyhalide (BiOX; X ═ I, Cl, Br, F) is paid much attention to due to a unique layered structure, high-efficiency photocatalytic efficiency and low price, meanwhile, literature reports of applying the bismuth oxyhalide to the textile field are gradually increased, but the preparation methods in the prior art mainly comprise a thermal sintering method, a sol-gel method, a magnetron sputtering method, a chemical vapor deposition method, a liquid phase deposition method and an electrochemical deposition method, the methods are mostly suitable for laboratory research, the large-batch production difficulty is high, and the production price is high, the preparation method can effectively solve the problems in the prior art, the bismuth oxyhalide ion solution is taken as an ion A solution (wherein the concentration of the precursor ion A is 2-10 mmol/L), and the halide ion solution is taken as a precursor ion B solution (wherein the concentration of the precursor ion B is 2-10 mmol/L) L).
The aramid fiber belongs to synthetic fiber and has poor hygroscopicity, a large number of amido bonds are contained on the surface of the aramid 1313 fiber (poly m-phenylene isophthalamide fiber), the surface electrostatic potential is relatively negative, and cations are easily adsorbed, therefore, after the bismuth oxygen ion solution is firstly padded, the bismuth oxygen ions mainly exist in a free state in the surface of the aramid fiber surface yarn and tissue gaps among the surface yarns after the aramid fiber is soaked in the bismuth oxygen ion solution, however, capillary gaps among the internal yarns and fibers forming the internal yarns are not easy to be wetted, the free bismuth oxygen ion solution adsorbed by the aramid fiber surface yarn can be promoted to permeate the tissue gaps among the internal yarns and the capillary gaps among the fibers forming the yarns by adjusting the padder pressure, at the moment, the bismuth oxygen ions are adsorbed by functional groups with strong electronegativity on the surface of the aramid fiber, and redundant bismuth oxygen ions exist in a free state in water, and the aramid fiber is rolled out after passing through a rolling point, bismuth oxygen radical ions exist on the surface of the aramid fiber in a chemical adsorption or physical adsorption mode, and the bismuth oxygen radical ions existing in a free ion state do not exist. The aramid fiber after being padded with the bismuth oxygen ion solution can be directly soaked in the halide ion solution, bismuth oxygen ions existing on the surface of aramid fiber through chemical and physical adsorption can not be diffused into the halide ion solution, but can quickly react with halide ions on the surface of the fiber to form a target precipitate, then the halide ion solution existing in a free state is padded, and the steps are circulated, so that the target precipitate can uniformly grow on the aramid fiber. The introduction of the padding device not only improves the distribution uniformity of the target precipitate on the flexible textile material, but also can save the cleaning step of precursor ions, greatly improves the load efficiency and saves the cleaning agent.
The experimental results show that: by regulating and controlling the pressure of a padder, the rolling residual rate of the aramid fiber is controlled to be 50-100%, when the rolling residual rate is in the range, bismuth oxide ions mainly exist on the surface of the aramid fiber in a chemical and physical adsorption mode, the aramid fiber which is padded in the bismuth oxide ion solution does not need to be washed by deionized water, another precursor ion (halide ion) solution required for preparing a target precipitate can be directly soaked, the target precipitate (bismuth oxyhalide) cannot be generated in the halide ion solution, and the surface of the fiber can be uniformly wrapped by bismuth oxyhalide nanosheets after a certain number of padding cycles (5-30 times); the padding pressure is increased to enable the rolling residual rate of the aramid fiber to be less than 50%, at the moment, bismuth oxygen radical ions and halogen ion solutions can penetrate into capillary gaps between fibers, the bismuth oxygen radical ions almost completely exist on the surface of the aramid fiber in a chemical and physical adsorption state, but due to the fact that the padding pressure is too large, inorganic nano-sheets generated on the surface of the aramid fiber can be cracked to different degrees due to the fact that the padding pressure is too large; reducing padding pressure to enable the rolling residual rate of the aramid fiber to be more than 100%, wherein at the moment, due to the fact that the padding pressure is too low, bismuth oxygen radical ion solution cannot effectively permeate capillary gaps between fibers, a large number of bismuth oxygen radical ions are adsorbed on the surfaces of the fibers on the surface of the aramid fiber and tissue gaps between the surface yarns, the surfaces of inner yarns and the fibers forming the inner yarns cannot be wetted by bismuth oxygen radical ions or halide ion solution, a large number of bismuth oxygen radical ions exist in the flowable solution in a free ion state, under the condition that deionized water is not introduced for cleaning, the bismuth oxygen radical ions adsorbed on the surface of the aramid fiber and existing in the free ion state can be released in the halide ion solution, target precipitates (bismuth oxyhalide) are generated in the halide ion solution to pollute the halide ion solution, meanwhile, part of the target precipitates can be deposited on the surface of the aramid fiber, and the acting force of the precipitates and the aramid fiber base material is weak, is easy to fall off from the aramid fiber. Therefore, the padding device is adopted, the padding pressure is reasonably adjusted, the existing state of precursor ions on the flexible textile material is adjusted, the load uniformity of the target precipitate on the flexible textile material can be improved, meanwhile, the cleaning step in the SILAR process can be omitted, the SILAR production efficiency is improved, and the introduction of the padding technology enables the rapid and efficient production of large-size functional flexible textile materials to be possible.
Has the advantages that:
compared with the traditional ion adsorption reaction method, the padding method for preparing the flexible inorganic semiconductor textile composite material improves the distribution uniformity of precursor ion solution on the flexible textile material, further promotes the uniform growth of the inorganic semiconductor material on the flexible textile material, shortens the operation flow of the ion adsorption reaction, has high automation degree of padding equipment and good reproducibility, and can realize the efficient preparation of large-size flexible inorganic semiconductor textile composite materials.
Drawings
FIG. 1 is a flow chart of the operation of the sequential ionic layer adsorption reaction process (a) and the padding process (b);
FIG. 2 shows respectively aramid fibers (a), BiOCl-aramid fibers (b) in example 1, BiOBr-aramid fibers (c) in example 2, BiOI-aramid fibers (d) in example 3, and BiOBr-aramid fibers (d) in example 40.5I0.5--a digital picture of aramid (e);
FIG. 3 is a scanning electron microscope image of BiOCl-aramid prepared by the padding method (a) and the dipping method (b), respectively;
FIG. 4 shows an aramid fabric, BiOCl-aramid in example 1, BiOBr-aramid in example 2, BiOI-aramid in example 3, and BiOBr in example 4, respectively0.5I0.5--XRD spectrum of aramid fiber.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A method for preparing a flexible inorganic semiconductor textile composite material by padding comprises the following steps:
(1) preparing a precursor ion A solution (specifically a bismuth nitrate aqueous solution with the bismuth ion concentration of 6 mmol/L) and a precursor ion B solution (specifically a potassium chloride aqueous solution with the chloride ion concentration of 6 mmol/L);
(2) mixing a flexible textile material (gram weight of 200 g/m)2Specifically, the aramid 1313 fabric after alkali treatment, as shown in fig. 2(a) and 4, the alkali treatment is performed by using a caustic soda solution with a concentration of 10 wt%, the temperature of the alkali treatment is 90 ℃, and the time is 3h) and the precursor ion a solution and the precursor ion B solution are alternately and cyclically padded for 20 times;
when padding the precursor ion A solution, the padding pressure is 3kg, the temperature of the precursor ion A solution is 25 ℃, the pH value of the precursor ion A solution is kept at 2.3, the transmission speed of the flexible textile material is 200m/h, and the padding allowance rate is 70%;
when padding the precursor ion B solution, the padding pressure is 3kg, the temperature of the precursor ion B solution is 25 ℃, the pH value of the precursor ion B solution is kept at 7, the transmission speed of the flexible textile material is 200m/h, and the padding allowance rate is 70%;
(3) and (4) drying (in a drying mode, the drying temperature is 80 ℃, and the drying time is 1h) to obtain the flexible inorganic semiconductor textile composite material.
The finally prepared flexible inorganic semiconductor textile composite material is composed of a flexible textile material and BiOCl nano-sheets uniformly loaded on the flexible textile material, as shown in FIG. 2(b), FIG. 3(a) and FIG. 4, wherein the size of the BiOCl nano-sheets is 1.5 μm (equivalent diameter), the thickness is 40nm, the loading amount is 45mg/g, and the coverage rate of target precipitates on the surface of the fabric is more than 90%.
According to the method for preparing the flexible inorganic semiconductor textile composite material by padding, the existing printing and dyeing production equipment is adopted, the inorganic semiconductors are assembled on the surface of the flexible textile material layer by layer, compared with the traditional continuous ionic layer adsorption reaction method (SILAR) (the specific flow is shown in figure 1 (a)), the adsorption quantity of precursor ions on the surface of the fabric is reasonably controlled by the padding equipment (the specific flow is shown in figure 1 (b)), the operation procedure that the SILAR needs washing after being soaked in an ionic solution is omitted, and uniform loading of the inorganic semiconductors on the flexible textile material and high-efficiency mass production of the flexible inorganic semiconductor textile composite material are realized.
Comparative example 1
A method for preparing a flexible inorganic semiconductor textile composite material, which is basically the same as the embodiment 1, and is different in that the padding treatment in the step (2) is changed into dipping treatment, and a bismuth ion solution, deionized water, a chloride ion solution and deionized water are sequentially dipped in a single cycle for 0.5min, 0.5min and 0.5min respectively, and the cycle time is 20 times.
The loading condition of the nano-sheet is shown in fig. 3(b), the nano-sheet prepared by the impregnation method is unevenly loaded on the surface of the aramid fiber, the size of the bismuth oxyhalide nano-sheet is 2 μm (equivalent diameter), the thickness is 40nm, the loading amount is 35mg/g, and the coverage rate of the target precipitate on the surface of the fabric is less than 50%.
Compared with the dipping method, the padding method remarkably improves the load uniformity of the nanosheets on the surface of the aramid fiber, the size of the nanosheets is uniform, the load capacity is higher than that of the dipping method, and meanwhile, the padding method omits a water washing step in an ion adsorption reaction process, so that the efficiency is improved, and the method is green and energy-saving.
Example 2
A method for preparing a flexible inorganic semiconductor textile composite material by padding comprises the following steps:
(1) preparing a precursor ion A solution (specifically a bismuth nitrate aqueous solution with bismuth ion concentration of 6 mmol/L) and a precursor ion B solution (specifically a potassium bromide aqueous solution with bromide ion concentration of 6 mmol/L);
(2) mixing a flexible textile material (gram weight of 200 g/m)2Specifically, the aramid fiber 1313 fabric is subjected to alkali treatment, wherein the alkali treatment adopts 10 wt% caustic soda solution, the temperature of the alkali treatment is 90 ℃, and the time is 3h), and the precursor ion A solution and the precursor ion B solution are subjected to alternate cyclic padding for 20 times;
when padding the precursor ion A solution, the padding pressure is 3kg, the temperature of the precursor ion A solution is 25 ℃, the pH value of the precursor ion A solution is kept at 2.3, the transmission speed of the flexible textile material is 200m/h, and the padding allowance rate is 70%;
when padding the precursor ion B solution, the padding pressure is 3kg, the temperature of the precursor ion B solution is 25 ℃, the pH value of the precursor ion B solution is kept at 7, the transmission speed of the flexible textile material is 200m/h, and the padding allowance rate is 70%;
(3) and (4) drying (in a drying mode, the drying temperature is 80 ℃, and the drying time is 1h) to obtain the flexible inorganic semiconductor textile composite material.
The finally prepared flexible inorganic semiconductor textile composite material is composed of a flexible textile material and BiOBr nano-sheets uniformly loaded on the flexible textile material, wherein the size of the BiOBr nano-sheets is 1.5 mu m (equivalent diameter), the thickness of the BiOBr nano-sheets is 45nm, the loading amount of the BiOBr nano-sheets is 50mg/g, and the coverage rate of target precipitates on the surface of the fabric is more than 90 percent, as shown in fig. 2(c) and 4.
Example 3
A method for preparing a flexible inorganic semiconductor textile composite material by padding comprises the following steps:
(1) preparing a precursor ion A solution (specifically a bismuth nitrate aqueous solution with bismuth ion concentration of 6 mmol/L) and a precursor ion B solution (specifically a potassium iodide aqueous solution with iodide ion concentration of 6 mmol/L);
(2) mixing a flexible textile material (gram weight of 200 g/m)2Specifically, the aramid fiber 1313 fabric is subjected to alkali treatment, wherein the alkali treatment adopts 10 wt% caustic soda solution, the temperature of the alkali treatment is 90 ℃, and the time is 3h), and the precursor ion A solution and the precursor ion B solution are subjected to alternate cyclic padding for 20 times;
when padding the precursor ion A solution, the padding pressure is 3kg, the temperature of the precursor ion A solution is 25 ℃, the pH value of the precursor ion A solution is kept at 2, the transmission speed of the flexible textile material is 200m/h, and the padding allowance rate is 70%;
when padding the precursor ion B solution, the padding pressure is 3kg, the temperature of the precursor ion B solution is 25 ℃, the pH value of the precursor ion B solution is kept at 7, the transmission speed of the flexible textile material is 200m/h, and the padding allowance rate is 70%;
(3) and (4) drying (in a drying mode, the drying temperature is 80 ℃, and the drying time is 1h) to obtain the flexible inorganic semiconductor textile composite material.
The finally prepared flexible inorganic semiconductor textile composite material is composed of a flexible textile material and BiOI nano-sheets uniformly loaded on the flexible textile material, wherein the size of the BiOI nano-sheets is 1 mu m (equivalent diameter), the thickness is 50nm, the loading amount is 50mg/g, and the coverage rate of target precipitates on the surface of the fabric is more than 90%, as shown in fig. 2(d) and fig. 4.
Example 4
A method for preparing a flexible inorganic semiconductor textile composite material by padding comprises the following steps:
(1) preparing a precursor ion A solution (specifically a bismuth nitrate aqueous solution with bismuth ion concentration of 6 mmol/L) and a precursor ion B solution (specifically a potassium bromide and potassium iodide aqueous solution with bromide ion and iodide ion (molar ratio of 1:1) concentration of 6 mmol/L);
(2) mixing a flexible textile material (gram weight200g/m2Specifically, the aramid fiber 1313 fabric is subjected to alkali treatment, wherein the alkali treatment adopts 10 wt% caustic soda solution, the temperature of the alkali treatment is 90 ℃, and the time is 3h), and the precursor ion A solution and the precursor ion B solution are subjected to alternate cyclic padding for 25 times;
when padding the precursor ion A solution, the padding pressure is 3kg, the temperature of the precursor ion A solution is 25 ℃, the pH value of the precursor ion A solution is kept at 2.3, the transmission speed of the flexible textile material is 200m/h, and the padding allowance rate is 70%;
when padding the precursor ion B solution, the padding pressure is 3kg, the temperature of the precursor ion B solution is 25 ℃, the pH value of the precursor ion B solution is kept at 7, the transmission speed of the flexible textile material is 200m/h, and the padding allowance rate is 70%;
(3) and (4) drying (in a drying mode, the drying temperature is 80 ℃, and the drying time is 1h) to obtain the flexible inorganic semiconductor textile composite material.
The finally obtained flexible inorganic semiconductor textile composite material is shown in fig. 2(e) and fig. 4, and is composed of a flexible textile material and BiOBr uniformly loaded on the flexible textile material0.5I0.5Nanosheet composition, BiOBr0.5I0.5The size of the nano-sheet is 1.2 mu m (equivalent diameter), the thickness is 55nm, the loading capacity is 60mg/g, and the coverage rate of the target precipitate on the surface of the fabric>90％。
Example 5
A method for preparing a flexible inorganic semiconductor textile composite material by padding comprises the following steps:
(1) preparing a precursor ion A solution (specifically a bismuth nitrate aqueous solution with bismuth ion concentration of 10mmol/L) and a precursor ion B solution (specifically a potassium iodide aqueous solution with iodide ion concentration of 10 mmol/L);
(2) mixing a flexible textile material (gram weight of 200 g/m)2Specifically, the aramid fiber 1313 fabric is subjected to alkali treatment, wherein the alkali treatment adopts 10 wt% caustic soda solution, the temperature of the alkali treatment is 90 ℃, and the time is 3h), and the precursor ion A solution and the precursor ion B solution are subjected to alternate cyclic padding for 5 times;
when padding the precursor ion A solution, the padding pressure is 5kg, the temperature of the precursor ion A solution is 25 ℃, the pH value of the precursor ion A solution is kept at 2, the transmission speed of the flexible textile material is 500m/h, and the padding allowance rate is 50%;
when padding the precursor ion B solution, the padding pressure is 5kg, the temperature of the precursor ion B solution is 25 ℃, the pH value of the precursor ion B solution is kept at 7, the transmission speed of the flexible textile material is 500m/h, and the padding allowance is 50%;
(3) and (4) drying (in a drying mode, the drying temperature is 80 ℃, and the drying time is 1h) to obtain the flexible inorganic semiconductor textile composite material.
The finally prepared flexible inorganic semiconductor textile composite material consists of a flexible textile material and BiOI nanosheets uniformly loaded on the flexible textile material, the size of the BiOI nanosheets is 0.5 mu m (equivalent diameter), the thickness of the BiOI nanosheets is 30nm, the loading capacity of the BiOI nanosheets is 20mg/g, and the coverage rate of target precipitates on the surface of the fabric is greater than 90%.
Example 6
A method for preparing a flexible inorganic semiconductor textile composite material by padding comprises the following steps:
(1) preparing a precursor ion A solution (specifically a bismuth nitrate aqueous solution with bismuth ion concentration of 2 mmol/L) and a precursor ion B solution (specifically a potassium iodide aqueous solution with iodide ion concentration of 2 mmol/L);
(2) mixing a flexible textile material (gram weight of 200 g/m)2Specifically, the aramid fiber 1313 fabric is subjected to alkali treatment, wherein the alkali treatment adopts 10 wt% caustic soda solution, the temperature of the alkali treatment is 90 ℃, and the time is 3h), and the precursor ion A solution and the precursor ion B solution are subjected to alternate cyclic padding for 50 times;
when padding the precursor ion A solution, the padding pressure is 1kg, the temperature of the precursor ion A solution is 25 ℃, the pH value of the precursor ion A solution is kept at 2.8, the transmission speed of the flexible textile material is 60m/h, and the padding allowance rate of padding is 100%;
when padding the precursor ion B solution, the padding pressure is 1kg, the temperature of the precursor ion B solution is 25 ℃, the pH value of the precursor ion B solution is kept at 7, the transmission speed of the flexible textile material is 60m/h, and the padding allowance rate is 100%;
(3) and (4) drying (in a drying mode, the drying temperature is 80 ℃, and the drying time is 1h) to obtain the flexible inorganic semiconductor textile composite material.
The finally prepared flexible inorganic semiconductor textile composite material consists of a flexible textile material and BiOI nanosheets uniformly loaded on the flexible textile material, the size of the BiOI nanosheets is 1.3 mu m (equivalent diameter), the thickness of the BiOI nanosheets is 45nm, the loading amount of the BiOI nanosheets is 47mg/g, and the coverage rate of target precipitates on the surface of the fabric is greater than 90%.
Example 7
A method for preparing a flexible inorganic semiconductor textile composite material by padding comprises the following steps:
(1) preparing a precursor ion A solution (specifically a copper sulfate aqueous solution with copper ion concentration of 20 mmol/L) and a precursor ion B solution (specifically a thiourea aqueous solution with sulfur ion concentration of 20 mmol/L);
(2) mixing a flexible textile material (with a gram weight of 100 g/m)2Specifically, the cotton fabric is subjected to alkali treatment, wherein the alkali treatment adopts 5 wt% caustic soda solution, the temperature of the alkali treatment is 80 ℃, and the time is 2h), and the precursor ion A solution and the precursor ion B solution are alternately and circularly padded for 30 times;
when padding the precursor ion A solution, the padding pressure is 4kg, the temperature of the precursor ion A solution is 50 ℃, the pH value of the precursor ion A solution is kept at 10, the transmission speed of the flexible textile material is 100m/h, and the padding allowance rate is 65%;
when padding the precursor ion B solution, the padding pressure is 4kg, the temperature of the precursor ion B solution is 50 ℃, the pH value of the precursor ion B solution is kept at 6, the transmission speed of the flexible textile material is 100m/h, and the padding allowance rate is 65%;
(3) and (5) drying (in a drying mode, the drying temperature is 90 ℃ and the drying time is 0.5h) to obtain the flexible inorganic semiconductor textile composite material.
The finally prepared flexible inorganic semiconductor textile composite material consists of a flexible textile material and a copper sulfide nano-film uniformly loaded on the flexible textile material, wherein the thickness of the copper sulfide nano-film is 200nm, the loading amount is 100mg/g, and the coverage rate of a target precipitate on the surface of a fabric is more than 90%.
Example 8
A method for preparing a flexible inorganic semiconductor textile composite material by padding comprises the following steps:
(1) preparing a precursor ion A solution (specifically, a zinc chloride and ammonia water solution with zinc-ammonia complex ion concentration of 100 mmol/L) and a precursor ion B solution (specifically, a sodium hydroxide water solution with hydroxide ion concentration of 10 mmol/L);
(2) mixing a flexible textile material (with a gram weight of 180 g/m)2Specifically, the polyester fabric is subjected to alkali treatment, wherein the alkali treatment adopts 15 wt% caustic soda solution, the temperature of the alkali treatment is 85 ℃, and the time is 1h), and the precursor ion A solution and the precursor ion B solution are alternately and circularly padded for 32 times;
when padding the precursor ion A solution, the padding pressure is 2.5kg, the temperature of the precursor ion A solution is 38 ℃, the pH value of the precursor ion A solution is kept to be 5, the transmission speed of the flexible textile material is 280m/h, and the padding allowance rate is 65%;
when padding the precursor ion B solution, the padding pressure is 2.5kg, the temperature of the precursor ion B solution is 38 ℃, the pH value of the precursor ion B solution is kept to be 9, the transmission speed of the flexible textile material is 280m/h, and the padding allowance rate is 65%;
(3) and (4) drying (in a drying mode, the drying temperature is 85 ℃, and the drying time is 0.8h) to obtain the flexible inorganic semiconductor textile composite material.
The finally prepared flexible inorganic semiconductor textile composite material consists of a flexible textile material and zinc oxide nano-particles uniformly loaded on the flexible textile material, wherein the size of the zinc oxide nano-particles is 100nm (average diameter), the loading amount is 55mg/g, and the coverage rate of target precipitates on the surface of a fabric is more than 90%.
Example 9
A method for preparing a flexible inorganic semiconductor textile composite material by padding comprises the following steps:
(1) preparing a precursor ion A solution (specifically a cadmium acetate aqueous solution with cadmium ion concentration of 30 mmol/L) and a precursor ion B solution (specifically a sodium sulfide aqueous solution with sulfur ion concentration of 30 mmol/L);
(2) mixing a flexible textile material (with a gram weight of 250 g/m)2In particular to polyester fabric after alkali treatment, the alkali treatment adopts caustic soda solution with the concentration of 18 wt%, the temperature of the alkali treatment is 100 ℃, and the time is 1.5h), and the precursor ion A solution and the precursor ion B solution are alternately and circularly padded for 50 times;
when padding the precursor ion A solution, the padding pressure is 4kg, the temperature of the precursor ion A solution is 20 ℃, the pH value of the precursor ion A solution is kept at 5, the transmission speed of the flexible textile material is 320m/h, and the padding allowance rate is 60%;
when padding the precursor ion B solution, the padding pressure is 4kg, the temperature of the precursor ion B solution is 20 ℃, the pH value of the precursor ion B solution is kept at 12, the transmission speed of the flexible textile material is 320m/h, and the padding allowance rate is 60%;
(3) and (4) drying (in a drying mode, the drying temperature is 95 ℃ and the drying time is 0.7h) to obtain the flexible inorganic semiconductor textile composite material.
The finally prepared flexible inorganic semiconductor textile composite material consists of a flexible textile material and cadmium sulfide nano-particles uniformly loaded on the flexible textile material, wherein the size of the cadmium sulfide nano-particles is 60nm (average diameter), the loading amount is 40mg/g, and the coverage rate of target precipitates on the surface of the fabric is more than 90%.
Example 10
A method for preparing a flexible inorganic semiconductor textile composite material by padding comprises the following steps:
(1) preparing a precursor ion A solution (specifically a silver nitrate aqueous solution with silver ion concentration of 80 mmol/L) and a precursor ion B solution (specifically a thiourea aqueous solution with sulfur ion concentration of 80 mmol/L);
(2) mixing a flexible textile material (gram weight of 200 g/m)2Specifically, the cotton fabric is subjected to alkali treatment, wherein the alkali treatment adopts 20wt% caustic soda solution, the temperature of the alkali treatment is 92 ℃, and the time is 2.5h), and the precursor ion A solution and the precursor ion B solution are subjected to alternate cyclic padding for 40 times;
when padding the precursor ion A solution, the padding pressure is 2.0kg, the temperature of the precursor ion A solution is 30 ℃, the pH value of the precursor ion A solution is kept at 8, the transmission speed of the flexible textile material is 430m/h, and the padding allowance rate of padding is 85%;
when padding the precursor ion B solution, the padding pressure is 2.0kg, the temperature of the precursor ion B solution is 30 ℃, the pH value of the precursor ion B solution is kept at 6, the transmission speed of the flexible textile material is 430m/h, and the padding allowance rate of padding is 85%;
(3) and (4) drying (in a drying mode, the drying temperature is 92 ℃ and the drying time is 0.9h) to obtain the flexible inorganic semiconductor textile composite material.
The finally prepared flexible inorganic semiconductor textile composite material consists of a flexible textile material and silver sulfide nano-particles uniformly loaded on the flexible textile material, wherein the size of the silver sulfide nano-particles is 150nm (average diameter), the loading amount is 80mg/g, and the coverage rate of target precipitates on the surface of a fabric is more than 90%.

Claims (10)

1. A method for preparing a flexible inorganic semiconductor textile composite material by padding is characterized by comprising the following steps:
(1) preparing a precursor ion A solution and a precursor ion B solution required by preparing an inorganic semiconductor;
(2) sequentially and alternately padding a precursor ion A solution and a precursor ion B solution on the flexible textile material for n times in a circulating and alternating manner, wherein n is a positive integer; the pH value of the precursor ion A solution is kept to be 2-10, and the pH value of the precursor ion B solution is kept to be 6-12;
(3) and (3) drying the product obtained in the step (2) to obtain the flexible inorganic semiconductor textile composite material.
2. A method of padding for producing a flexible inorganic semiconductor textile composite material according to claim 1, wherein the flexible inorganic semiconductor textile composite material is composed of a flexible textile material and an inorganic semiconductor supported thereon; the inorganic semiconductor is nanoparticles or nanosheets, the average diameter of the nanoparticles is 100-1000 nm, and the equivalent diameter of the nanosheets is 0.5-2 mu m; the inorganic semiconductor has a loading amount of 10 to 100 mg/g.
3. The method for padding preparation of a flexible inorganic semiconductor textile composite material according to claim 1, wherein in step (1), the precursor ions A and B correspond to bismuth ions and halogen ions, respectively, or copper ions and sulfur ions, respectively, or zinc ammine complex ions and hydroxide ions, respectively, or cadmium ions and sulfur ions, respectively, or silver ions and sulfur ions, respectively.
4. The method for preparing the flexible inorganic semiconductor textile composite material by padding according to claim 1 or 3, wherein in the step (1), the concentration of the precursor ion A in the precursor ion A solution is 2-100 mmol/L; the concentration of the precursor ions B in the precursor ion B solution is 2-80 mmol/L.
5. A method for padding preparation of a flexible inorganic semiconductor textile composite material according to claim 4, characterized in that the solvent in both the precursor ion A solution and the precursor ion B solution is water.
6. The padding method for preparing the flexible inorganic semiconductor textile composite material according to the claim 1, wherein in the step (2), the flexible textile material is aramid 1313, aramid 1414, cotton or polyester fabric; the gram weight of the flexible textile material is 100-250 g/m2；
When the precursor ion A solution is padded, the padding pressure is 0.5-5 kg, the temperature of the precursor ion A solution is 20-50 ℃, the transmission speed of the flexible textile material is 60-500 m/h, and the padding residual rate is 50-100%;
when the precursor ion B solution is padded, the padding pressure is 0.5-5 kg, the temperature of the precursor ion B solution is 20-50 ℃, the transmission speed of the flexible textile material is 60-500 m/h, and the padding residual rate is 50-100%.
7. A method of padding for producing a flexible inorganic semiconductor textile composite material according to claim 6, wherein the flexible textile material is an alkali treated flexible textile material.
8. The method for padding preparation of the flexible inorganic semiconductor textile composite material according to claim 7, wherein the alkali treatment adopts 5-20 wt% caustic soda solution, the temperature of the alkali treatment is 80-100 ℃, and the time is 1-3 h.
9. The method for preparing the flexible inorganic semiconductor textile composite material by padding according to claim 1, wherein in the step (2), the value of n is in the range of 5-50.
10. The method for preparing the flexible inorganic semiconductor textile composite material by padding according to claim 1, wherein in the step (3), the drying is carried out in a drying manner, the drying temperature is 80-100 ℃, and the drying time is 0.5-1 h.
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