CN117170153A - Preparation method of vine winding electro-spectral regulation fiber device - Google Patents
Preparation method of vine winding electro-spectral regulation fiber device Download PDFInfo
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims description 12
- 159000000002 lithium salts Chemical class 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 11
- 239000004014 plasticizer Substances 0.000 claims description 9
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000009832 plasma treatment Methods 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 7
- 229920000098 polyolefin Polymers 0.000 claims description 7
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 6
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- 239000012528 membrane Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- -1 polypropylene Polymers 0.000 claims description 6
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- 238000011010 flushing procedure Methods 0.000 claims description 5
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- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
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- 239000010931 gold Substances 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
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- 238000003756 stirring Methods 0.000 claims description 3
- SENMPMXZMGNQAG-UHFFFAOYSA-N 3,4-dihydro-2,5-benzodioxocine-1,6-dione Chemical compound O=C1OCCOC(=O)C2=CC=CC=C12 SENMPMXZMGNQAG-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052802 copper Inorganic materials 0.000 claims description 2
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- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
A preparation method of a fiber device for 'vine winding' electro-spectral regulation and control relates to a preparation method of a fiber device. The invention aims to solve the problems of single spectrum regulation wave band, poor mechanical property, low cycle service life and electrochromic property attenuation of a fiber device prepared by the existing method. The method comprises the following steps: 1. preparing an electrode layer; 2. preparing a functional layer; 3. pretreatment of a fiber substrate; 4. preparing a carbon fiber with a gel electrolyte loaded on the surface; 5. constructing a fiber device with a 'vine winding' structure; 6. and constructing a fiber device packaging layer. The fiber device for regulating and controlling the electric spectrum of the vines winding has good infrared heat radiation regulating and controlling capability and visible light management capability; after 5000 times of bending at a bending angle of 60 degrees and 5000 times of redox cycles, the infrared emissivity regulating and controlling capability of the device is still stable. The invention can obtain a vine winding electro-spectral regulation fiber device.
Description
Technical Field
The invention relates to a preparation method of a fiber device.
Background
The wearable electrochromic device with the spectrum regulation function has wide application prospect in the aspects of display, decoration, personal heat management and self-adaptive heat camouflage application. However, the existing fiber device with the spectrum regulation function has the problems of single spectrum regulation wave band, poor mechanical property and the like, and is difficult to meet the abundant practical application demands.
Zhao Jiupeng et al have invented a method for preparing a spectrum-controlled fiber material, which comprises constructing an electrolyte membrane on the surface of a fiber substrate, directly evaporating a metal layer on the surface of the electrolyte membrane, directly electrodepositing an active functional layer on the metal layer, and absorbing an electrolyte solution or ionic liquid into the fiber by means of vacuum pressure, thereby constructing an infrared thermal radiation-controlled fiber device of a core-shell structure. The design method has the following problems: 1. when the electrolyte is absorbed, the active functional layer can fall off to a certain extent due to the swelling phenomenon; 2. the fiber device is not provided with an encapsulation layer, and the electrolyte or the ionic liquid is easy to volatilize and cannot be used for a long time; 3. the infrared emissivity adjusting capability of the fiber device is not high; 4. when a fiber device directly electrodeposited and coated with the electrode is stretched, the electrode is easy to crack due to bearing complete action stress; 5. the recycling service life of the fiber device is not high; 6. the length of the fiber device has a limitation, and when the fiber length is too long, electrochromic properties of the fiber device are affected due to an unstable electrode structure, resulting in attenuation from one end to the other.
Disclosure of Invention
The invention aims to solve the problems of single spectrum regulation wave band, poor mechanical property, low cycle service life and electrochromic property attenuation of a fiber device prepared by the existing method, and provides a preparation method of a vine winding electrochromic spectrum regulation fiber device.
Aiming at the problems, the electrode structure of the fiber device is creatively designed and optimized, and the fiber device (a 'vine winding' electro-spectral regulation fiber device) with excellent mechanical properties and excellent visible-infrared dual-band regulation capability is successfully prepared, and has ultrahigh bending stability and redox cycling stability.
The preparation method of the 'vine winding' electro-spectral regulation fiber device is completed according to the following steps:
1. preparing an electrode layer:
evaporating a metal layer on the porous planar film by adopting a vacuum thermal evaporation method to obtain an electrode layer;
2. preparing a functional layer:
firstly, flushing an electrode layer, then placing the electrode layer into an oven for heat treatment, and finally preparing a polyaniline film on the electrode layer by an electrodeposition method or an in-situ chemical synthesis method to obtain a functional layer;
3. pretreatment of a fiber substrate:
firstly, cleaning carbon fibers, then carrying out argon plasma treatment, and then depositing an acid-doped aniline electrolyte on the plasma-treated carbon fibers by adopting a constant current method or a constant potential method under a three-electrode system to obtain carbon fibers loaded with polyaniline films;
4. immersing the carbon fiber loaded with the polyaniline film in a gel electrolyte solution, and then taking out to obtain the carbon fiber with the gel electrolyte loaded on the surface;
5. building a fiber device with a 'vine winding' structure:
cutting the functional layer obtained in the second step into a strip-shaped broadband with a certain length and a certain width, and uniformly winding the strip-shaped broadband on the carbon fiber with the gel electrolyte loaded on the surface obtained in the fourth step at a certain angle to obtain a fiber device with a 'vine winding' structure;
6. building a fiber device packaging layer:
uniformly winding the fiber device with the 'vine winding' structure obtained in the step five onto a coil collector, placing the fiber device into a polyolefin thermoplastic pipe with the same length through a roller for thermoplastic packaging, leaving a certain length for carbon fiber at one end, and leaving a certain length for electrode layer pole at the other end, so as to realize connection of electrodes, and obtaining the fiber device with the 'vine winding' electro-spectral regulation.
The principle of the invention is as follows:
the invention obtains inspiration through the phenomenon that the plant with 'vines wound' in nature enhances the structural stability of the plant, and designs the structure of the fiber device; firstly, evaporating a metal layer with high reflectivity on a porous planar film, and then, electrodepositing an active functional material on the metal layer to construct a planar multilayer film (vine) with a sandwich structure; then, carrying out electrodeposition of an active functional material on the surface of the fiber core layer to construct an ion storage layer, and then coating gel electrolyte on the ion storage layer; coating the planar multilayer film on the fiber loaded with the gel electrolyte in a spiral winding mode of 'vine winding', and finally packaging a protective layer to construct an integrated electrochromic fiber device; by applying different voltages, the adjustment of the spectral characteristics of the active functional material (electrochromic layer) in the visible-infrared band can be achieved.
The invention has the advantages that:
1. the fiber device for regulating and controlling the electric spectrum of the vines winding has good infrared heat radiation regulating and controlling capability and visible light management capability; the infrared emissivity delta epsilon is 0.528 in the wave band of 8-14 mu m, the color conversion from yellow to green can be realized in the visible light wave band, and the reaction time is quick; the infrared emissivity regulation and control capability of the device is still stable after the device is provided with an independent packaging layer and is bent for 5000 times at a bending angle of 60 degrees and subjected to oxidation-reduction cycle for 5000 times;
2. the vine winding composite electrode structure prepared by the invention can realize the preparation of fiber devices with any length, and greatly solves the defect that coaxial dynamic infrared radiation regulation fiber devices are affected by the length and cannot be prepared into high-length infrared radiation regulation fiber devices; the preparation method is simple to operate and low in cost, and can be used for mass preparation;
3. the fiber device for the electro-spectral regulation and control of the vines winding can effectively solve the problem that the coaxial fiber working electrode is easy to break when being subjected to tensile force, so that the device is invalid;
4. the fiber device for the ' vine winding ' electro-spectral regulation and control ' prepared by the invention can be perfectly fused with textiles through different braiding technologies so as to realize intelligent wearing.
Drawings
FIG. 1 is a flow chart of the preparation of a "vine-entangled" electro-spectral regulatory fiber device of the present invention;
FIG. 2 is a schematic illustration of the manner in which the electrode connection of the "vine-wound" electro-spectral regulatory fiber device of the present invention is made during operation;
FIG. 3 is a scanning image of the SEM of the polyaniline functional layer obtained in step two of example 1;
FIG. 4 is an infrared emissivity control power map of a "vine-wound" electro-spectral control fiber device prepared in example 1 over the 2.5-25 μm band;
FIG. 5 is a graph showing the maximum tensile force that can be carried by a fiber device when an electrode breaks, wherein (a) is a "vine-wound" electro-spectral regulatory fiber device prepared in example 1, and (b) is a spectral regulatory fiber device of a single fiber electrode structure;
FIG. 6 is a digital photograph of a "vine-entangled" electro-spectral regulatory fibrous device prepared in example 1 in oxidized (a) and reduced (b) states;
FIG. 7 is an infrared thermogram of a "vine-entangled" electro-spectral regulatory fiber device prepared in example 1 in oxidized (a) and reduced (b) states;
FIG. 8 is a simulated force plot of a "vine-wound" electro-spectral regulatory fiber device prepared in example 1 versus a spectral regulatory fiber device of core-shell structure;
FIG. 9 is CIE 1931 (x, y) coordinates of a "vine-entangled" electro-spectral regulatory fiber device prepared in example 1 in (j) a reduced state and (k) an oxidized state; (l) A reflection spectrum of the fiber device in a wave band range of 400-800 nm;
FIG. 10 is a graph of response time and current density decay for a "vine-wound" electro-spectral regulatory fiber device prepared in example 1, where (a) is the response time of the fiber device and (b) is the maximum current density decay for the fiber device after 5000 cycles of use.
Detailed Description
The first embodiment is as follows: the preparation method of the 'vine winding' electro-spectral regulation fiber device in the embodiment is completed according to the following steps:
1. preparing an electrode layer:
evaporating a metal layer on the porous planar film by adopting a vacuum thermal evaporation method to obtain an electrode layer;
2. preparing a functional layer:
firstly, flushing an electrode layer, then placing the electrode layer into an oven for heat treatment, and finally preparing a polyaniline film on the electrode layer by an electrodeposition method or an in-situ chemical synthesis method to obtain a functional layer;
3. pretreatment of a fiber substrate:
firstly, cleaning carbon fibers, then carrying out argon plasma treatment, and then depositing an acid-doped aniline electrolyte on the plasma-treated carbon fibers by adopting a constant current method or a constant potential method under a three-electrode system to obtain carbon fibers loaded with polyaniline films;
4. immersing the carbon fiber loaded with the polyaniline film in a gel electrolyte solution, and then taking out to obtain the carbon fiber with the gel electrolyte loaded on the surface;
5. building a fiber device with a 'vine winding' structure:
cutting the functional layer obtained in the second step into a strip-shaped broadband with a certain length and a certain width, and uniformly winding the strip-shaped broadband on the carbon fiber with the gel electrolyte loaded on the surface obtained in the fourth step at a certain angle to obtain a fiber device with a 'vine winding' structure;
6. building a fiber device packaging layer:
uniformly winding the fiber device with the 'vine winding' structure obtained in the step five onto a coil collector, placing the fiber device into a polyolefin thermoplastic pipe with the same length through a roller for thermoplastic packaging, leaving a certain length for carbon fiber at one end, and leaving a certain length for electrode layer pole at the other end, so as to realize connection of electrodes, and obtaining the fiber device with the 'vine winding' electro-spectral regulation.
The second embodiment is as follows: the present embodiment differs from the specific embodiment in that: the porous planar membrane in the first step is made of polypropylene, nylon 66 or ethylene glycol phthalate; the metal in the metal layer in the first step is one or more than two of platinum, gold, copper and stainless steel; the thickness of the metal layer in the first step is 100 nm-300 nm. The other steps are the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: the electrodeposition method in the second step comprises the following steps: firstly preparing an acid-doped aniline electrodeposition solution, adopting a constant current method or a constant potential method through an electrochemical workstation, depositing a polyaniline film on a metal layer of a planar film under a three-electrode system, flushing by using absolute ethyl alcohol, and finally placing on filter paper; the acid in the acid doped aniline electrodeposition solution is one or more than two of sulfuric acid, camphorsulfonic acid, dodecylbenzene sulfonic acid, hydrofluoric acid and hydrochloric acid, wherein the mass ratio of the acid to the aniline is (2-60): 1. The other steps are the same as those of the first or second embodiment.
The specific embodiment IV is as follows: one difference between this embodiment and the first to third embodiments is that: firstly, washing an electrode layer for 2-3 times by using absolute ethyl alcohol, then placing the electrode layer into an oven with the temperature of 80-120 ℃ for heat treatment for 3-8 hours, and finally preparing a polyaniline film on the electrode layer by an electrodeposition method or an in-situ chemical synthesis method to obtain a functional layer; the loading of the polyaniline film on the electrode layer in the second step is 200mg/m 2 ～500mg/m 2 . The other steps are the same as those of the first to third embodiments.
Fifth embodiment: one to four differences between the present embodiment and the specific embodiment are: the fiber number of the carbon fiber in the third step is 3k, 5k, 7k or 11k; the plasma treatment time in the third step is 5 min-15 min, and the temperature is 80-200 ℃. Other steps are the same as those of the first to fourth embodiments.
Specific embodiment six: the present embodiment differs from the first to fifth embodiments in that: the acid doped aniline electrolyte in the step three is one or more than two of sulfuric acid, camphorsulfonic acid, dodecylbenzene sulfonic acid, hydrofluoric acid and hydrochloric acid, wherein the mass ratio of the acid to the aniline is (2-60): 1; the loading amount of the polyaniline film in the step three on the carbon fiber is 200mg/m 2 ～500mg/m 2 . Other steps are the same as those of the first to fifth embodiments.
Seventh embodiment: one difference between the present embodiment and the first to sixth embodiments is that: the gel electrolyte solution in the step four is a plasticizer-propylene carbonate-lithium salt-acetone system, and the specific preparation method comprises the following steps: adding lithium salt into propylene carbonate, then adding acetone, stirring for 2-3 h, and then adding plasticizer to obtain a plasticizer-propylene carbonate-lithium salt-acetone system. Other steps are the same as those of embodiments one to six.
Eighth embodiment: one difference between the present embodiment and the first to seventh embodiments is that: in the fourth step, the mass ratio of the lithium salt, propylene carbonate and acetone in the plasticizer-propylene carbonate-lithium salt-acetone system is 1 (3-6) (6-8); the mass of the plasticizer is 15-30% of the mass of the plasticizer-propylene carbonate-lithium salt-acetone system; the lithium salt in the fourth step is one or more than two of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium bisoxalato borate, lithium bis (trifluoromethylsulfonyl) imide and lithium bisfluorosulfonyl imide; the plasticizer in the fourth step is propylene carbonate; the concentration of the lithium salt in the fourth step is 1mol/L to 3mol/L. The other steps are the same as those of embodiments one to seven.
Detailed description nine: one of the differences between this embodiment and the first to eighth embodiments is: the width of the strip broadband in the fifth step is 0.2 cm-1 cm; and step five, the winding angle of the strip-shaped broadband is 30-85 degrees, and the distance between two adjacent strip-shaped broadband after winding is 0.1cm-1cm. Other steps are the same as those of embodiments one to eight.
Detailed description ten: the present embodiment differs from the first to ninth embodiments in that: the diameter of the polyolefin thermoplastic pipe in the step six is 0.25 cm-2 cm; the temperature of the thermoplastic packaging in the step six is 150-200 ℃; the length of the carbon fiber at one end in the sixth step is 0.3 cm-1 cm; the length of the electrode layer electrode at the other end in the step six is 0.2 cm-1cm. The other steps are the same as those of embodiments one to nine.
The following examples are used to verify the benefits of the present invention:
example 1: the preparation method of the 'vine winding' electro-spectral regulation fiber device is completed according to the following steps:
1. preparing an electrode layer:
evaporating a metal layer on the porous planar film by adopting a vacuum thermal evaporation method to obtain an electrode layer;
the porous planar membrane in the first step is a porous PP membrane, and the pore diameter is 200nm;
the metal in the metal layer in the first step is gold;
the thickness of the metal layer in the first step is 100nm;
2. preparing a functional layer:
firstly, washing an electrode layer for 3 times by using absolute ethyl alcohol, then placing the electrode layer into an oven with the temperature of 100 ℃ for heat treatment for 3 hours, and finally preparing a polyaniline film on the electrode layer by an electrodeposition method to obtain a functional layer;
the electrodeposition method in the second step comprises the following steps: firstly, preparing an acid-doped aniline electrodeposition solution, and using a constant current method (current density of 0.1 mA/cm) through an electrochemical workstation 2 ) Under a three-electrode system (Pt is used as a cathode, an electrode layer obtained in the first step is used as an anode, ag/AgCl is used as a reference electrode), depositing a polyaniline film on a metal layer of a planar film, washing with absolute ethyl alcohol, and finally placing on filter paper; the acid in the acid doped aniline electrodeposition solution is dodecylbenzene sulfonic acid, wherein the mass ratio of the acid to the aniline is 30:1;
the loading of the polyaniline film on the electrode layer in the second step is 350mg/m 2 ；
3. Pretreatment of a fiber substrate:
firstly, cleaning carbon fibers, then carrying out argon plasma treatment, and then depositing an acid-doped aniline electrolyte on the carbon fibers subjected to the argon plasma treatment by adopting a constant potential method (0.8V) under a three-electrode system (Pt is a cathode, the carbon fibers are an anode and Ag/AgCl is a reference electrode) through an electrochemical workstation to obtain the carbon fibers loaded with polyaniline films;
the fiber number of the carbon fiber in the third step is 7k;
the argon plasma treatment time in the third step is 10min, and the temperature is 150 ℃;
the acid doped aniline electrolyte in the step three is dodecylbenzene sulfonic acid, wherein the mass ratio of acid to aniline is 30:1;
loading polyaniline film in the third step on carbon fiberThe amount is 350mg/m 2 ；
4. Immersing the carbon fiber loaded with the polyaniline film in a gel electrolyte solution, and then taking out to obtain the carbon fiber with the gel electrolyte loaded on the surface;
the gel electrolyte solution in the step four is a plasticizer-propylene carbonate-lithium salt-acetone system, and the specific preparation method comprises the following steps: adding lithium salt into propylene carbonate, then adding acetone, stirring for 2 hours, and then adding a plasticizer to obtain a plasticizer-propylene carbonate-lithium salt-acetone system;
in the fourth step, the mass ratio of lithium salt, propylene carbonate and acetone in the plasticizer-propylene carbonate-lithium salt-acetone system is 1:3:8; the mass of the plasticizer is 20% of the mass of a plasticizer-propylene carbonate-lithium salt-acetone system;
the lithium salt in the fourth step is lithium perchlorate;
the plasticizer in the fourth step is propylene carbonate;
the concentration of the lithium salt in the fourth step is 1mol/L;
5. building a fiber device with a 'vine winding' structure:
cutting the functional layer obtained in the second step into a strip-shaped broadband with a certain length and a certain width, and uniformly winding the strip-shaped broadband on the carbon fiber with the gel electrolyte loaded on the surface obtained in the fourth step at a certain angle to obtain a fiber device with a 'vine winding' structure;
the width of the strip broadband in the fifth step is 0.3cm;
the winding angle of the strip-shaped wideband is 75 degrees, and the distance between two adjacent strip-shaped wideband after winding is 0.1cm;
6. building a fiber device packaging layer:
uniformly winding the fiber device with the 'vine winding' structure obtained in the step five onto a coil collector, placing the fiber device into a polyolefin thermoplastic pipe with the same length through a roller for thermoplastic packaging, leaving a certain length for carbon fiber at one end, and leaving a certain length for electrode layer pole at the other end so as to realize connection of electrodes, thus obtaining the fiber device with the 'vine winding' electro-spectral regulation and control;
the diameter of the polyolefin thermoplastic pipe in the step six is 0.5cm;
the temperature of the thermoplastic packaging in the step six is 175 ℃;
the length of the carbon fiber at one end in the sixth step is 0.5cm;
the electrode layer at the other end in the step six is set to have a length of 0.5cm.
FIG. 1 is a flow chart of the preparation of a "vine-entangled" electro-spectral regulatory fiber device of the present invention;
FIG. 2 is a schematic illustration of the manner in which the electrode connection of the "vine-wound" electro-spectral regulatory fiber device of the present invention is made during operation;
as shown in fig. 2, when the 'vine winding' electro-spectral regulation fiber device works, carbon fiber is used as a counter electrode, connected with a negative electrode, and a metal layer on a planar film is used as a working electrode and connected with a positive electrode; the applied working voltage ranges from-0.8V to 0.8V, and the response time is 2 to 3s; the length of the fiber device for the 'vine winding' electro-spectral regulation and control can be controlled according to requirements, and the electrochromic performance of the fiber device is not affected by the change of the length.
FIG. 3 is a scanning image of the SEM of the polyaniline functional layer obtained in step two of example 1;
as can be seen from fig. 3: polyaniline presents a typical cluster-like structure and is uniform in texture.
FIG. 4 is an infrared emissivity control power map of a "vine-wound" electro-spectral control fiber device prepared in example 1 over the 2.5-25 μm band;
as can be seen from fig. 4: the "vine winding" electro-spectral regulation fiber device prepared in example 1 has excellent infrared emissivity regulation capability, and the regulation capability at the 8-14 micron wave band is 0.528, which is far superior to that of the traditional spectral regulation fiber with a core-shell structure (application number is 202210071310.7, and the invention is named as a preparation method of a dynamic infrared thermal radiation regulation fiber functional device).
The invention performs a comparison test of mechanical stretching capability on a vine winding electro-spectral regulation fiber device and a coaxial fiber structure spectral regulation fiber device prepared in the embodiment 1, and the resistance value of a working electrode under the applied tensile force is recorded through a universal meter, which is shown in fig. 5;
FIG. 5 is a graph showing the maximum tensile force that can be carried by a fiber device when an electrode breaks, wherein (a) is a "vine-wound" electro-spectral regulatory fiber device prepared in example 1, and (b) is a spectral regulatory fiber device of a single fiber electrode structure;
the spectrum regulation fiber device with the single fiber electrode structure in fig. 5 is prepared according to the application number 202210071310.7 and the invention name of the spectrum regulation fiber device is a dynamic infrared heat radiation regulation fiber function device preparation method;
as can be seen from fig. 5: when the working electrode breaks, the value displayed by the universal meter is 1; the results show that for the "vine-wound" electro-spectral regulatory fiber device prepared in example 1, the working electrode breaks when a tensile force of 40N is applied to both ends of the working electrode, whereas for the spectral regulatory fiber device of single fiber structure, the electrode breaks when only a tensile force of 23.5N is carried by the electrode; and for the spectrum regulation fiber device with the 'vine natural' electrode structure, the working electrode has higher elongation rate when the working electrode breaks due to spiral winding and pulling force application.
FIG. 6 is a digital photograph of a "vine-entangled" electro-spectral regulatory fibrous device prepared in example 1 in oxidized (a) and reduced (b) states;
as can be seen from fig. 6: the "vine-wound" electro-spectral control fiber device prepared in example 1 can be freely bent into any shape, and the invention herein makes a heart-shaped patterning design, and the fiber can be freely switched between dark green (oxidized state) and golden yellow (reduced state).
FIG. 7 is an infrared thermogram of a "vine-entangled" electro-spectral regulatory fiber device prepared in example 1 in oxidized (a) and reduced (b) states;
as can be seen from fig. 7: when the reduced state of the fiber device is controlled by the 'vine winding' electro-spectral control prepared in the embodiment 1, the reflectivity is high, the corresponding emissivity is low, and the apparent temperature is reduced; when the fiber device is in an oxidized state, the reflectivity becomes low, the corresponding emissivity becomes high, and the apparent temperature increases.
FIG. 8 is a simulated force plot of a "vine-wound" electro-spectral regulatory fiber device prepared in example 1 versus a spectral regulatory fiber device of core-shell structure;
according to the invention, mechanical simulation analysis is carried out on the spectral fibers of the 'vine winding' structure and the spectral fibers of the core-shell structure, and the analysis shows that when tensile force is applied to the two ends of the fiber in parallel and perpendicular to the two ends of the fiber, the vine structures of the 'vine winding' structure can offset more stress mutually, so that the working electrode is protected.
FIG. 9 is CIE 1931 (x, y) coordinates of a "vine-entangled" electro-spectral regulatory fiber device prepared in example 1 in (j) a reduced state and (k) an oxidized state; (l) A reflection spectrum of the fiber device in a wave band range of 400-800 nm;
as can be seen from fig. 9: the "vine winding" electro-spectral regulation fiber device prepared in the embodiment 1 can realize the switching between golden yellow (reduced state) and dark green (oxidized state) in a visible light wave band, and the change range of the emissivity is 23% in the wave band range of 400-800 nm.
FIG. 10 is a graph of response time and current density decay for a "vine-wound" electro-spectral regulatory fiber device prepared in example 1, where (a) is the response time of the fiber device and (b) is the maximum current density decay for the fiber device after 5000 cycles of use.
As can be seen from fig. 10: the fiber device with the "vine-wound" electro-spectral regulation prepared in example 1 has a relatively fast response time of 2.44 seconds, and the maximum current density of the fiber device is not significantly attenuated after 5000 redox cycling reactions, which proves that the fiber device has excellent cycling stability.
Claims (10)
1. The preparation method of the 'vine winding' electro-spectral regulation fiber device is characterized by comprising the following steps of:
1. preparing an electrode layer:
evaporating a metal layer on the porous planar film by adopting a vacuum thermal evaporation method to obtain an electrode layer;
2. preparing a functional layer:
firstly, flushing an electrode layer, then placing the electrode layer into an oven for heat treatment, and finally preparing a polyaniline film on the electrode layer by an electrodeposition method or an in-situ chemical synthesis method to obtain a functional layer;
3. pretreatment of a fiber substrate:
firstly, cleaning carbon fibers, then carrying out argon plasma treatment, and then depositing an acid-doped aniline electrolyte on the plasma-treated carbon fibers by adopting a constant current method or a constant potential method under a three-electrode system to obtain carbon fibers loaded with polyaniline films;
4. immersing the carbon fiber loaded with the polyaniline film in a gel electrolyte solution, and then taking out to obtain the carbon fiber with the gel electrolyte loaded on the surface;
5. building a fiber device with a 'vine winding' structure:
cutting the functional layer obtained in the second step into a strip-shaped broadband with a certain length and a certain width, and uniformly winding the strip-shaped broadband on the carbon fiber with the gel electrolyte loaded on the surface obtained in the fourth step at a certain angle to obtain a fiber device with a 'vine winding' structure;
6. building a fiber device packaging layer:
uniformly winding the fiber device with the 'vine winding' structure obtained in the step five onto a coil collector, placing the fiber device into a polyolefin thermoplastic pipe with the same length through a roller for thermoplastic packaging, leaving a certain length for carbon fiber at one end, and leaving a certain length for electrode layer pole at the other end, so as to realize connection of electrodes, and obtaining the fiber device with the 'vine winding' electro-spectral regulation.
2. The method for manufacturing a "vine winding" electro-spectral control fiber device according to claim 1, wherein the porous planar membrane in the first step is made of polypropylene, nylon 66 or ethylene phthalate; the metal in the metal layer in the first step is one or more than two of platinum, gold, copper and stainless steel; the thickness of the metal layer in the first step is 100 nm-300 nm.
3. The method for preparing the "vine winding" electro-spectral regulation fiber device according to claim 1, wherein the electro-deposition method in the second step is specifically: firstly preparing an acid-doped aniline electrodeposition solution, adopting a constant current method or a constant potential method through an electrochemical workstation, depositing a polyaniline film on a metal layer of a planar film under a three-electrode system, flushing by using absolute ethyl alcohol, and finally placing on filter paper; the acid in the acid doped aniline electrodeposition solution is one or more than two of sulfuric acid, camphorsulfonic acid, dodecylbenzene sulfonic acid, hydrofluoric acid and hydrochloric acid, wherein the mass ratio of the acid to the aniline is (2-60): 1.
4. The preparation method of the 'vine winding' electro-spectral regulation fiber device is characterized in that absolute ethyl alcohol is used for washing an electrode layer for 2-3 times, then the electrode layer is put into an oven with the temperature of 80-120 ℃ for heat treatment for 3-8 hours, and finally a polyaniline film is prepared on the electrode layer by an electrodeposition method or an in-situ chemical synthesis method to obtain a functional layer; the loading of the polyaniline film on the electrode layer in the second step is 200mg/m 2 ～500mg/m 2 。
5. The method for preparing a fiber device for "vine winding" electro-spectral control according to claim 1, wherein the number of fibers of the carbon fiber in the third step is 3k, 5k, 7k or 11k; the plasma treatment time in the third step is 5 min-15 min, and the temperature is 80-200 ℃.
6. The method for preparing the 'vine winding' electro-spectral regulation fiber device according to claim 1, which is characterized by comprising the following steps ofThe acid-doped aniline electrolyte in the third step is one or more than two of sulfuric acid, camphorsulfonic acid, dodecylbenzenesulfonic acid, hydrofluoric acid and hydrochloric acid, wherein the mass ratio of the acid to the aniline is (2-60): 1; the loading amount of the polyaniline film in the step three on the carbon fiber is 200mg/m 2 ～500mg/m 2 。
7. The method for preparing the "vine winding" electro-spectral regulation fiber device according to claim 1, wherein the gel electrolyte solution in the fourth step is a plasticizer-propylene carbonate-lithium salt-acetone system, and the specific preparation method comprises the following steps: adding lithium salt into propylene carbonate, then adding acetone, stirring for 2-3 h, and then adding plasticizer to obtain a plasticizer-propylene carbonate-lithium salt-acetone system.
8. The preparation method of the 'vine winding' electro-spectral regulation fiber device is characterized in that the mass ratio of lithium salt, propylene carbonate and acetone in the plasticizer-propylene carbonate-lithium salt-acetone system in the fourth step is 1 (3-6): 6-8; the mass of the plasticizer is 15-30% of the mass of the plasticizer-propylene carbonate-lithium salt-acetone system; the lithium salt in the fourth step is one or more than two of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium bisoxalato borate, lithium bis (trifluoromethylsulfonyl) imide and lithium bisfluorosulfonyl imide; the plasticizer in the fourth step is propylene carbonate; the concentration of the lithium salt in the fourth step is 1mol/L to 3mol/L.
9. The method for manufacturing a fiber device for "vine winding" electro-spectral regulation and control according to claim 1, wherein the width of the strip-shaped broadband in the fifth step is 0.2 cm-1 cm; and step five, the winding angle of the strip-shaped broadband is 30-85 degrees, and the distance between two adjacent strip-shaped broadband after winding is 0.1-1 cm.
10. The method for manufacturing a "vine winding" electro-spectral regulatory fiber device according to claim 1, wherein the diameter of the polyolefin thermoplastic tube in the step six is 0.25 cm-2 cm; the temperature of the thermoplastic packaging in the step six is 150-200 ℃; the length of the carbon fiber at one end in the sixth step is 0.3 cm-1 cm; the length of the electrode layer electrode at the other end in the step six is 0.2 cm-1cm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102881463A (en) * | 2012-08-14 | 2013-01-16 | 北京大学 | Fibrous supercapacitor and manufacturing method thereof |
| CN106932992A (en) * | 2017-03-31 | 2017-07-07 | 中国航发北京航空材料研究院 | The flexible electro-chromic device and preparation method of a kind of regulation and control near infrared light |
| CN110729518A (en) * | 2019-09-08 | 2020-01-24 | 复旦大学 | Manganese dioxide/graphene-based water-based zinc ion battery and preparation method thereof |
| CN114200728A (en) * | 2022-01-21 | 2022-03-18 | 哈尔滨工业大学 | Preparation method of dynamic infrared thermal radiation fiber function regulating device |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102881463A (en) * | 2012-08-14 | 2013-01-16 | 北京大学 | Fibrous supercapacitor and manufacturing method thereof |
| CN106932992A (en) * | 2017-03-31 | 2017-07-07 | 中国航发北京航空材料研究院 | The flexible electro-chromic device and preparation method of a kind of regulation and control near infrared light |
| CN110729518A (en) * | 2019-09-08 | 2020-01-24 | 复旦大学 | Manganese dioxide/graphene-based water-based zinc ion battery and preparation method thereof |
| CN114200728A (en) * | 2022-01-21 | 2022-03-18 | 哈尔滨工业大学 | Preparation method of dynamic infrared thermal radiation fiber function regulating device |
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