CN-122013597-A - Flexible ceramic nanofiber paper based on linear inorganic molecular chain and preparation method and application thereof

CN122013597ACN 122013597 ACN122013597 ACN 122013597ACN-122013597-A

Abstract

The invention belongs to the technical field of nanofiber materials, and in particular relates to flexible ceramic nanofiber paper based on linear inorganic molecular chains, and a preparation method and application thereof; adding catalyst into long ligand modified monomer solution, mixing with short ligand modified monomer solution, adding deionized water, adding chain extender and end capping agent to obtain linear inorganic long chain with long-short side group, preparing spinning solution, spinning in auxiliary force field to obtain precursor, infrared radiation treatment, non-adhesive rolling, instantaneous cooling and shaping, deep ultraviolet irradiation and calcining. Compared with the prior art, the invention solves the problems of insufficient flexibility, poor uniformity and easy brittle fracture of ceramic fiber paper caused by the defect of inner holes of fibers in the prior art. The preparation method of the scheme can realize the preparation of the ceramic nanofiber paper with uniform thickness and gram weight and excellent flexibility.

Inventors

DING BIN
WU FAN
Fang Songchun
TIAN SHIJIN
HUANG JIA
XU RUIXIANG
MIAO RUNWU
YU JIANYONG

Assignees

东华大学

Dates

Publication Date: 20260512
Application Date: 20260325

Claims (10)

1. The preparation method of the flexible ceramic nanofiber paper based on the linear inorganic molecular chain is characterized by comprising the following steps of: S1, respectively preparing an alcohol solution of a long inert ligand and an alcohol solution of a short inert ligand, respectively dripping the alcohol solution of the long inert ligand and the alcohol solution of the short inert ligand into a metal alkoxide monomer solution for coordination modification to obtain a long ligand-modified monomer solution and a short ligand-modified monomer solution, adding a catalyst into the long ligand-modified monomer solution and mixing the catalyst with the short ligand-modified monomer solution, then adding deionized water for hydrolysis-polycondensation reaction to obtain a linear inorganic molecular chain with low polymerization degree of long-short ligand, adding a chain extender for chain extension reaction, and then adding a blocking agent for terminating the chain extension reaction to obtain a linear inorganic long chain with long-short side groups; s2, preparing a linear inorganic long chain with long-short side groups obtained in the step S1 into spinning solution, and spinning and forming in an auxiliary force field to obtain precursor nanofiber paper; And S3, sequentially carrying out infrared radiation treatment, non-adhesion rolling and instantaneous cooling shaping on the precursor nanofiber paper obtained in the step S2, then carrying out deep ultraviolet irradiation to crack an organic ligand, and then calcining to obtain the ceramic nanofiber paper.
2. The preparation method of the flexible ceramic nanofiber paper based on the linear inorganic molecular chain, which is characterized in that the long inert ligand and the alcohol solvent are mixed according to the molar ratio of 1:5-1:10 in the alcohol solution of the long inert ligand, and the short inert ligand and the alcohol solvent are mixed according to the molar ratio of 1:5-1:10 in the alcohol solution of the short inert ligand; the long inert ligand is selected from one or more of citric acid, aminotriacetic acid, ethylenediamine tetraacetic acid, ammonium citrate, stearic acid, oleic acid, n-caproic acid, n-heptanoic acid, n-caprylic acid, n-capric acid and lauric acid; the short inert ligand is selected from one or more of acetic acid, oxalic acid, ethylenediamine, acetylacetone and trifluoroacetylacetone; the alcohol solvent is one or more selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-amyl alcohol, ethylene glycol, butanediol, hexanediol and glycerol; The metal alkoxide is selected from one or more of a titanium source, a zirconium source, an aluminum source, a tin source, a hafnium source, a gallium source, a tantalum source and a niobium source; the titanium source is selected from one or more of titanium tetramethoxide, titanium tetraethoxide, titanium n-propoxide, titanium isopropoxide, titanium n-butoxide, titanium isobutanoxide, titanium tert-butoxide, titanium tetra-butoxide and titanium iso-butoxide, the zirconium source is selected from one or more of zirconium tetra-methoxide, zirconium tetra-ethoxide, zirconium n-propoxide, zirconium iso-butoxide, zirconium tert-butoxide and zirconium tetra-butoxide, the aluminum source is selected from one or more of trimethoxy aluminum, triethanolammonium, tri-n-propoxyaluminum, aluminum isopropoxide, aluminum n-butoxide, aluminum sec-butoxide and aluminum tert-butoxide, the tin source is selected from one or more of tin tetra-methoxide, tin tetra-ethoxide, tin n-propoxide, tin iso-butoxide, tin tert-butoxide and tin tetra-butoxide, the hafnium source is selected from one or more of hafnium tetra-methoxide, hafnium tetra-ethoxide, hafnium n-propoxide, hafnium iso-propoxide, hafnium n-butoxide, hafnium iso-butoxide and hafnium tetra-butoxide, the gallium source is selected from one or more of iso-propoxide and tantalum n-butoxide, the one or two of n-butoxide and niobium n-butoxide; The catalyst is selected from one or more of boron trifluoride, aluminum trichloride, boron tribromide, boron triiodide, stannic chloride, silicon tetrachloride, titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, tetracyanoethylene and trinitrobenzene; The chain extender is selected from one or more of titanium diisopropoxy diacetylacetonate, diisopropyl bis (ethyl acetoacetate) titanate, zirconium bis (diethyl citrate) dipropionate, (ethyl acetoacetate) diisopropoxy aluminate, titanocene dichloride, zirconocene dichloride, hafnocene dichloride, molybdenum dichloride, vanadium dichloride and niobium dichloride; The blocking agent is one or more selected from common chemical blocking agents, visible light response blocking agents and ultraviolet light response blocking agents, the common chemical blocking agents are one or two selected from methyl isocyanate and phenyl isocyanate, the visible light blocking agents are one or more selected from 2-diazonium-1-naphthol-5-sulfonyl chloride, ethyl diazoacetate and 4-azido-2, 3,5, 6-tetrafluorobenzoic acid, and the ultraviolet light response blocking agents are one or more selected from 4-azidobenzoic acid, 3-azidopropyltrimethoxysilane and 1, 3-dioxypentacyclopropyl trimethoxysilane.
3. The method for preparing a flexible ceramic nanofiber paper based on linear inorganic molecular chains according to claim 1, wherein the linear inorganic long chains with long-short side groups are prepared into spinning solution by negative pressure suction; the negative pressure suction condition is that the constant temperature heating is carried out for 30-150 ℃ and the pressure is 0-0.1 MPa; The external force of the auxiliary force field is selected from one or more of electrostatic force, airflow force and centrifugal force.
4. The method for preparing the flexible ceramic nanofiber paper based on the linear inorganic molecular chain according to claim 1, wherein the infrared radiation wave band of the infrared radiation treatment is 0.75-1000 μm; The rolling pressure of the non-adhesion rolling is 0.1-5 MPa; The temperature range of the instantaneous cooling shaping is-5-15 ℃.
5. The method for preparing the flexible ceramic nanofiber paper based on the linear inorganic molecular chain according to claim 1, wherein the wavelength of the deep ultraviolet irradiation is 180-300 nm; The calcination is alternating atmosphere calcination or oxygen-deficient calcination, the alternating atmosphere calcination is a periodic switching atmosphere of mixing oxygen-containing gas and inert gas, wherein the oxygen-containing gas is selected from one or two of air and oxygen, the inert gas is selected from one or more of nitrogen, argon, helium, neon, krypton, xenon and radon, the switching period is 10-600 s/time, the oxygen volume fraction in the oxygen-deficient calcination is controlled to be less than or equal to 18%, and the peak temperature of the calcination is 400-1500 ℃.
6. The method for producing a flexible ceramic nanofiber paper based on linear inorganic molecular chains according to claim 1, characterized in that the spinning forming is performed in a uniform liquid supply spinning system (1); the uniform liquid supply spinning system (1) comprises a spinneret plate (1-1), a main runner (1-2) positioned in the spinneret plate (1-1), a circulating liquid temperature control layer (1-3), a shearing screw (1-4) and a necking fractal liquid supply runner (1-5); the main runner (1-2) is parallel to the spinneret plate (1-1), and the necking fractal liquid supply runner (1-5) is connected to the side edge of the main runner (1-2) and communicated with a bottom nozzle of the spinneret plate (1-1); The circulating liquid temperature control layer (1-3) is arranged around the outer sides of the main runner (1-2) and the necking fractal liquid supply runner (1-5); The shearing screw (1-4) is arranged in the main runner (1-2), and the shearing screw (1-4) is parallel to the spinneret plate (1-1).
7. The method for preparing the flexible ceramic nanofiber paper based on the linear inorganic molecular chain according to claim 6, wherein the uniform liquid supply spinning system (1) further comprises a diversion cone (1-6) and a circulating liquid storage tank (1-9); the diversion cone (1-6) is arranged at a liquid separation port of the necking fractal liquid supply channel (1-5); The liquid inlet end (1-7) and the liquid outlet end (1-8) of the circulating liquid temperature control layer (1-3) are respectively connected with the circulating liquid storage tank (1-9) in a sealing mode through flange interfaces.
8. The method for preparing a flexible ceramic nanofiber paper based on linear inorganic molecular chains according to claim 1, wherein the infrared radiation treatment, the non-blocking rolling and the instantaneous shaping are all performed in an infrared softening welding-instantaneous shaping device (2); The infrared softening welding-instantaneous cooling shaping device (2) comprises an infrared radiation source (2-1), a low surface energy roller (2-2), a low surface energy transition roller (2-3) and a cooling shaping roller (2-4); The infrared radiation source (2-1) is positioned upstream of the low surface energy roller (2-2) and is used for carrying out infrared radiation treatment; the low surface energy roller (2-2), the low surface energy transition roller (2-3) and the cold shaping roller (2-4) are mutually parallel and sequentially arranged, and the axial height of the low surface energy transition roller (2-3) is lower than that of the low surface energy roller (2-2) and the cold shaping roller (2-4); A spiral conveying runner (2-5) is arranged in the roller body of the cold shaping roller (2-4).
9. A flexible ceramic nanofiber paper based on linear inorganic molecular chains, characterized in that the paper is obtained by the preparation method according to any one of claims 1-8; The fiber diameter of the ceramic nanofiber paper is 50-500 nm, the thickness is 20 mu m-5 mm, the gram weight is 20-200 g/m 2 , the fracture toughness is more than or equal to 0.24MJ/m 3 , and the gram weight and the thickness CV value are both less than or equal to 5%.
10. The application of the flexible ceramic nanofiber paper based on the linear inorganic molecular chains in a battery heat insulation pad, a heat control heat insulation layer, a flexible electrode or diaphragm support layer, a fireproof noise reduction heat insulation layer, an energy storage and heat management component, a high-temperature resistant filter medium, a catalytic carrier, a flexible electrolyte support skeleton and interface buffer layer, an ion conduction support network, a high-insulation high-heat conduction encapsulation and structure support layer, a sensitive unit carrier and a high-temperature resistant stable substrate.

Description

Flexible ceramic nanofiber paper based on linear inorganic molecular chain and preparation method and application thereof Technical Field The invention belongs to the technical field of nanofiber materials, and particularly relates to flexible ceramic nanofiber paper based on linear inorganic molecular chains, and a preparation method and application thereof. Background The ceramic fiber paper has wide application in the fields of aerospace heat insulation protection, traffic equipment flame retardance and noise reduction, new energy battery thermal runaway protection and the like by virtue of the high temperature resistance, corrosion resistance and flame retardance of the ceramic fiber paper. The traditional preparation method of the ceramic fiber paper mainly comprises wet papermaking and dry forming, wherein the wet papermaking process mainly takes micron-sized ceramic short fibers as raw materials, and the ceramic fiber paper is prepared through the procedures of dispersing, forming, dehydrating and the like. However, the fiber paper has low strength and is easy to fall off due to the fact that the fibers are mainly overlapped by means of simple physics. In addition, the fiber is easy to agglomerate in a wet system, stable dispersion is difficult to realize, the gram weight and thickness uniformity of the finished product are insufficient, and the nanofiber is easier to agglomerate compared with the microfiber due to the high specific surface area, so that the technology is not suitable for forming and preparing high-performance nanofiber paper. The dry forming technology mainly constructs the ceramic fiber into a sheet-shaped structure through the processes of air laying, hot pressing, bonding, solidifying and the like, and the method often needs to add more organic adhesive, thereby affecting the temperature resistance and structural stability of the ceramic fiber paper. Meanwhile, the controllable spreading and uniform regulation and control of the nanofiber are difficult to realize by dry forming, and the obtained nanofiber paper has the problems of poor uniformity and multiple internal defects and cannot meet the application requirements of complex scenes. In recent years, electrospinning has become an important route for preparing ceramic nanofiber paper because of the ability to directly prepare nanoscale continuous fibers. For example, in CN202411668911.1, a PVA solution is mixed with an oxide substrate sol, and a precursor composite nanofiber paper is obtained by using an electrospinning technique, and then a ceramic nanofiber paper is obtained by high-temperature calcination. However, the fibers prepared by the method only depend on simple physical lap joint, and lack of firm binding force, so that the mechanical properties of the fibers are insufficient. The patent ZL202210597804.9 utilizes an electrostatic spinning technology to obtain precursor nanofiber paper, at least two paper edges are overlapped and laid, a strip-shaped connecting layer is covered at the overlapped part, the connecting layer is subjected to spot coating bonding in a mode of dipping diluted precursor sol, and finally, the ceramic nanofiber membrane is obtained through calcination. However, the reinforcement effect of the technology is mainly concentrated on a splicing interface, the integral reinforcement of the fiber paper is difficult to realize, the uniformity of the fiber paper is poor due to the thickness fluctuation of the splicing part, the spot coating adhesion depends on manual operation, the consistency and the repeatability of the spot coating amount and the infiltration degree are poor, and the large-scale production is difficult. In addition, the polymer template is required to be removed in the ceramization process, and the defect of inner holes of fibers is inevitably caused by the thermal decomposition of the polymer, so that the ceramic fiber paper is insufficient in flexibility and easy to crack, and the application requirement of the high-precision field is difficult to meet. Therefore, development of a new method for large-scale continuous manufacturing of flexible ceramic nanofiber paper is needed to meet the application requirements of the flexible ceramic nanofiber paper in the fields of aerospace, new energy sources, flexible electronics and the like. Disclosure of Invention The invention aims to solve at least one of the problems, and provides flexible ceramic nanofiber paper based on a linear inorganic molecular chain, and a preparation method and application thereof, so as to solve the problems of insufficient flexibility, poor uniformity and easy brittle fracture of ceramic fiber paper caused by the defect of inner holes of fibers in the process of removing a polymer template in the prior art. The preparation method of the scheme can realize the preparation of the ceramic nanofiber paper with uniform thickness and gram weight and excellent flexibility. The aim of the invention is achieved by