CN116239769A - Method for preparing crosslinked conductive polymer by adopting ice melting slow release mode and crosslinked conductive polymer obtained by method - Google Patents
Method for preparing crosslinked conductive polymer by adopting ice melting slow release mode and crosslinked conductive polymer obtained by method Download PDFInfo
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- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000002844 melting Methods 0.000 title claims abstract description 9
- 230000008018 melting Effects 0.000 title claims abstract description 9
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 46
- 239000002253 acid Substances 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 230000008014 freezing Effects 0.000 claims abstract description 10
- 238000007710 freezing Methods 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 19
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 12
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000002604 ultrasonography Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- BMQHYGLEATWRFO-UHFFFAOYSA-N 1-n,3-n,5-n-triphenylbenzene-1,3,5-triamine Chemical compound C=1C(NC=2C=CC=CC=2)=CC(NC=2C=CC=CC=2)=CC=1NC1=CC=CC=C1 BMQHYGLEATWRFO-UHFFFAOYSA-N 0.000 claims description 5
- 239000003929 acidic solution Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 5
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 3
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 claims description 3
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 claims description 3
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 3
- 239000001230 potassium iodate Substances 0.000 claims description 3
- 229940093930 potassium iodate Drugs 0.000 claims description 3
- 235000006666 potassium iodate Nutrition 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 2
- 230000000977 initiatory effect Effects 0.000 abstract description 2
- 229920000767 polyaniline Polymers 0.000 description 23
- 238000004132 cross linking Methods 0.000 description 10
- 229920000128 polypyrrole Polymers 0.000 description 9
- 239000002861 polymer material Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229920000123 polythiophene Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C08K5/00—Use of organic ingredients
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- C08K5/17—Amines; Quaternary ammonium compounds
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
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- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
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Abstract
The invention discloses a method for preparing a crosslinked conductive polymer by adopting an ice melting slow release mode and the crosslinked conductive polymer obtained by the method, and relates to the field of conductive polymer synthesis. The method comprises the following specific steps: 1) Dispersing the cross-linking agent into water, and then freezing to form a cross-linking agent ice body; 2) Dispersing conductive polymer monomers in an acid solution to obtain an acid system; 3) And (2) adding the crosslinking agent ice body obtained in the step (1) into the acidic system obtained in the step (2), and simultaneously adding an initiator solution to perform polymerization reaction to generate the crosslinked conductive polymer. The invention controls the rate of melting the ice body so as to control the rate of introducing the cross-linking agent into the reaction system, thereby ensuring the uniformity of the initiation process. The system is easy to amplify and does not influence the reaction process. Thereby realizing a large amount of, rapid and efficient synthesis of uniform and stable crosslinked conductive polymer composite materials.
Description
Technical Field
The invention relates to the field of conductive polymer synthesis, in particular to a method for preparing a crosslinked conductive polymer by adopting an ice melting slow release mode and the crosslinked conductive polymer obtained by the method.
Background
The polymer material is initially applied to the functional insulating material, and as people go deep into the research of the polymer material, in the 70 th century of 20 th, the conductive polymer material is developed, and the conductivity of the conductive polymer material can reach 10 3 Scm -1 Is directly against the conductivity of the metal. By virtue of the characteristics, the conductive polymer material is widely applied in the fields of energy storage, chemical industry, electronic technology, electrocatalysis, electromagnetic shielding and the like.
Although conductive polymers have conductivity comparable to metals, their ease of decomposition hampers their further development. How to synthesize the conductive polymer material with stable structure and reliable performance is an important research subject. The chain conductive polymer material can be woven into a net by adding the cross-linking agent, so that the structural stability and the relative specific surface area of the conductive polymer material are greatly improved. The traditional method for adding the cross-linking agent solution can lead to the problems that the cross-linking agent is not uniformly mixed into a reaction system, the local temperature is too high along with the progress of the reaction, the conductive polymer is agglomerated, and the like.
Disclosure of Invention
The invention aims to provide a method for preparing a crosslinked conductive polymer by adopting an ice melting slow-release mode and the crosslinked conductive polymer, so as to solve the problems that the traditional method for adding a crosslinking agent solution can lead to uneven mixing of the crosslinking agent into a reaction system, and local overhigh temperature can be caused along with the progress of reaction, so that the conductive polymer is agglomerated and the like.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for preparing a crosslinked conductive polymer by adopting a deicing slow-release mode, which comprises the following steps:
1) Dispersing the cross-linking agent into water, and then freezing to form a cross-linking agent ice body;
2) Dispersing conductive polymer monomers in an acid solution to obtain an acid system;
3) Adding the crosslinking agent ice body obtained in the step 1) into the acidic system obtained in the step 2), and simultaneously adding an initiator solution to perform polymerization reaction to generate a crosslinked conductive polymer;
wherein, the step 1) and the step 2) are not in sequence;
the volume of the cross-linking agent ice body is 1-100 cm 3 ；
The polymerization reaction is carried out under the condition of ultrasound, the time of the ultrasound is 0.5-2 h, and the power of the ultrasound is 100-1000W.
Preferably, the concentration of the cross-linking agent in the step 1) is 0.1-2 mol/L; the crosslinker ice bodies comprise spheres or cubes.
Preferably, the concentration of the acid solution in the step 2) is 1-6 mol/L; the concentration of the conductive polymer monomer in the acid system is 0.1-2 mol/L.
Preferably, the initiator solution is an aqueous solution of an initiator, and the concentration is 0.1-2 mol/L; the initiator solution is added in the step 3) in a dropwise manner, and the dropwise adding rate is 1-6 g/min.
Preferably, the molar ratio of the crosslinking agent, the conductive polymer monomer and the initiator is 0.1 to 1.0mol:0.2 to 2mol:0.1 to 1.0mol.
Preferably, the crosslinking agent comprises one or more of 1,3, 5-tris (anilino) benzene, disodium salt of bis-benzenesulfonic acid, acid blue, p-phenylenediamine and triphenylamine;
the initiator comprises one or more of ammonium persulfate, potassium dichromate, potassium iodate, ferric chloride, hydrogen peroxide, and ceric sulfate.
Preferably, the conductive polymer monomer comprises an aniline monomer, a pyrrole monomer, or a thiophene monomer;
the acidic solution comprises an aqueous solution of hydrochloric acid, sulfuric acid or perchloric acid.
Preferably, the reaction temperature of the polymerization reaction in step 3) is-5 to 5 ℃.
Preferably, the post-treatment is carried out after the polymerization reaction in the step 3), and the post-treatment process sequentially comprises centrifugation, water washing and drying; the centrifugal speed is 1000-10000 rpm, and the time is 10-60 mins; washing with water until the pH of the material is more than 5; the temperature of the drying is 40-60 ℃ and the time is 2-6 h.
It is another object of the present invention to provide a crosslinked conductive polymer prepared by the method.
The technical principle of the invention is as follows: ice is added to the reaction system to provide the ice bath environment necessary for the synthesis of the conductive polymer, initiator is introduced into the system and ultrasound is performed, and the reaction occurs at the two-phase interface around the ice. The constant-temperature uniform synthesis of the crosslinked conductive polymer with the determined crosslinking degree is comprehensively realized by controlling the release rate of the crosslinking agent and the addition ratio of the crosslinking agent to the conductive polymer monomer by controlling the size of the ice body and the ultrasonic power.
Compared with the prior art, the invention has the following beneficial effects:
the invention controls the synthesis rate of the crosslinked conductive polymer by controlling the volume of the ice body and the ultrasonic power. On the other hand, the technical scheme of the invention can prepare the crosslinked conductive polymer with the crosslinking degree controllable within 1-30%, and specifically comprises the following steps: the degree of crosslinking is controlled by controlling the adding proportion of the crosslinking agent and the conductive polymer monomer, the proportion is about large, and the higher the crosslinking degree of the crosslinked polyaniline is, the more compact the synthesized material is. The technical scheme of the invention ensures the stability of the synthesis temperature at the freezing point and the uniformity of the initiation process. The system is easy to amplify and does not influence the reaction process. Thereby realizing a large amount of, rapid and efficient synthesis of uniform and stable crosslinked conductive polymer composite materials.
Drawings
FIG. 1 is an SEM image of crosslinked nano conductive polyaniline in example 1;
FIG. 2 is an X-ray diffraction image of the crosslinked nano conductive polyaniline in example 1;
fig. 3 is a constant current charge-discharge cycle chart of an aqueous zinc ion battery using the crosslinked nano conductive polyaniline of example 1 as a positive electrode material.
Detailed Description
The invention provides a method for preparing a crosslinked conductive polymer by adopting a deicing slow-release mode, which comprises the following steps:
1) Dispersing the cross-linking agent into water, and then freezing to form a cross-linking agent ice body;
2) Dispersing conductive polymer monomers in an acid solution to obtain an acid system;
3) Adding the crosslinking agent ice body obtained in the step 1) into the acidic system obtained in the step 2), and simultaneously adding an initiator solution to perform polymerization reaction to generate a crosslinked conductive polymer;
wherein, the step 1) and the step 2) are not in sequence;
the volume of the cross-linking agent ice body is 1-100 cm 3 ；
The polymerization reaction is carried out under the condition of ultrasound, the time of the ultrasound is 0.5-2 h, and the power of the ultrasound is 100-1000W.
In the present invention, the crosslinking agent comprises one or more of 1,3, 5-tris (anilino) benzene, disodium salt of bis-benzenesulfonic acid, acid blue, p-phenylenediamine and triphenylamine; the concentration of the crosslinking agent is preferably 0.1 to 2mol/L, more preferably 0.2 to 1.8mol/L, still more preferably 0.5 to 1.5mol/L; ice body of cross-linking agentPreferably a sphere or cube; the volume of the cross-linking agent ice body is 1-100 cm 3 Preferably 10 to 90cm 3 More preferably 20 to 80cm 3 More preferably 40 to 60cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The crosslinking agent ice body may be plural.
In the present invention, the acidic solution in step 2) comprises an aqueous solution of hydrochloric acid, sulfuric acid or perchloric acid; the concentration of the acidic solution is preferably 1 to 6mol/L, more preferably 2 to 5mol/L, and still more preferably 3 to 4mol/L; the conductive polymer monomer comprises crosslinked polyaniline, crosslinked polypyrrole or crosslinked polythiophene; the concentration of the conductive polymer monomer in the acidic system is preferably 0.1 to 2mol/L, more preferably 0.2 to 1.8mol/L, and still more preferably 0.5 to 1.5mol/L.
In the present invention, the initiator comprises one or more of ammonium persulfate, potassium dichromate, potassium iodate, ferric chloride, hydrogen peroxide, and ceric sulfate; the initiator solution is preferably an aqueous solution of an initiator, and the concentration is preferably 0.1 to 2mol/L, more preferably 0.2 to 1.8mol/L, and still more preferably 0.5 to 1.5mol/L; the initiator solution is preferably added dropwise in the step 3), and the dropping rate is preferably 1 to 6g/min, more preferably 2 to 5g/min, and still more preferably 3 to 4g/min.
In the present invention, the molar ratio of the crosslinking agent, the conductive polymer monomer and the initiator is preferably 0.1 to 1.0mol:0.2 to 2mol:0.1 to 1.0mol, more preferably 0.2 to 0.8mol:0.4 to 1.5mol:0.2 to 0.8mol, more preferably 0.4 to 0.6mol:0.5 to 1.0mol:0.2 to 0.8mol.
In the present invention, the reaction temperature of the polymerization reaction in step 3) is preferably from-5 to 5 ℃, more preferably from-3 to C, and still more preferably from-1 to 1 ℃.
In the invention, after the polymerization reaction in the step 3) is finished, post-treatment is carried out, and the post-treatment process sequentially comprises centrifugation, water washing and drying; the speed of centrifugation is preferably 1000 to 10000rpm, more preferably 3000 to 8000rpm, and even more preferably 3500 to 5000rpm; the time for centrifugation is preferably 10 to 60 minutes, more preferably 20 to 50 minutes, and still more preferably 30 to 40 minutes; the water wash is preferably a material pH greater than 5, more preferably a pH greater than 5.5, more preferably a pH greater than 6; the temperature of the drying is preferably 40 to 60 ℃, more preferably 45 to 55 ℃, and even more preferably 47 to 53 ℃; the drying time is preferably 2 to 6 hours, more preferably 2.5 to 5 hours, and still more preferably 3 to 4 hours.
It is another object of the present invention to provide a crosslinked conductive polymer prepared by the method.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
1) The molar ratio of p-phenylenediamine to triphenylamine used was 2:1 as a crosslinking agent, dispersed in 1L of water, wherein the addition amount of p-phenylenediamine is 0.2mol and triphenylamine is 0.1mol. Freezing the dispersion system of the cross-linking agent and water into ice balls with the diameter of 3 cm at the temperature of-20 ℃ by using a die;
2) 180g of aniline monomer is dispersed in 3L 1mol/L hydrochloric acid solution to obtain an acid system;
3) Ammonium persulfate is selected as an initiator, dissolved in 1L of water to prepare 0.5mol/L ammonium persulfate aqueous solution, and placed in a constant pressure funnel;
4) Adding the ice ball prepared in the step 1) into the acid system of the step 2), simultaneously dropwise adding an ammonium persulfate aqueous solution by using a constant-pressure funnel at a speed of 2g/min, regulating the reaction temperature to be 1 ℃, and reacting for 1h under the ultrasonic power of 500W to obtain the crosslinked nano conductive polyaniline.
5) Centrifuging the crosslinked nano conductive polyaniline obtained in the step 4) at 4500rpm for 30min, then washing the polyaniline with ultrapure water to enable the pH value of the material to be 5, and finally drying the material at 45 ℃ for 4h to obtain crosslinked nano conductive polyaniline powder with the crosslinking degree of 25.6%.
Testing and characterization:
(1) The scanning electron microscope image of the crosslinked nano conductive polyaniline powder in the step 5) is shown in fig. 1, and the X-ray diffraction image is shown in fig. 2. As can be seen from fig. 1: the cross-linked polyaniline material prepared by the scheme has uniform structure and rich cross-linked network structure. As can be seen from fig. 2, the crosslinked polyaniline material prepared using this scheme has typical characteristic peaks of polyaniline material, and three characteristic peaks appear between 18 and 30 °.
(2) Taking the crosslinked nano conductive polyaniline powder in the step 5) as a zinc ion battery positive electrode material, wherein the mol/L ZnCl is 1mol/L 2 And (3) taking the solution as electrolyte, taking a glass fiber diaphragm as a battery diaphragm, taking a 1mm thick analytically pure zinc plate as a negative electrode, assembling the button cell according to the sequence of the positive electrode diaphragm and the negative electrode, and standing for 24 hours to be tested. The assembled button cell was subjected to charge and discharge test using a blue electric test system with a charge and discharge current of 0.5A/g, and a charge and discharge cycle chart was obtained as shown in FIG. 3. As can be seen from the figure: the polyaniline zinc cell using the cross-linked polyaniline material prepared by the scheme as the positive electrode material has high specific capacity of 170mAh/g, and meanwhile, the cell can be stably circulated for more than 60 times, and the charge and discharge efficiency is close to 100%. The cross-linked polyaniline material can be used as an ideal positive electrode material of a zinc ion battery.
Example 2
1) Dispersing 1,3, 5-tri (anilino) benzene serving as a cross-linking agent in 0.5L of water, wherein the adding amount of the 1,3, 5-tri (anilino) benzene is 0.1mol/L, and freezing a dispersing system of the cross-linking agent and water into a cube with a side length of 4 cm at the temperature of-20 ℃ by using a die;
2) 120g of pyrrole monomer is dispersed in 2L of 0.5mol/L perchloric acid solution to obtain an acid system;
3) Potassium dichromate is selected as an initiator, dispersed in 1L of water to prepare 0.5mol/L potassium dichromate solution, and placed in a constant pressure funnel;
4) Adding the ice ball prepared in the step 1) into the acid system of the step 2), simultaneously dropwise adding a potassium dichromate solution by using a constant pressure funnel at a speed of 4g/min, regulating the reaction temperature to-1 ℃, and reacting for 2 hours under the ultrasonic power of 1000W to obtain the crosslinked nano conductive polypyrrole.
5) Centrifuging the crosslinked nano conductive polyaniline obtained in the step 4) at 9000rpm for 15min, then washing the polyaniline with ultrapure water to enable the pH value of the material to be 6, and finally drying the material at 40 ℃ for 6h to obtain crosslinked nano conductive polypyrrole powder with the crosslinking degree of 29.3%.
Example 3
1) Dispersing the solution into 0.5L of water by using acid blue as a cross-linking agent, wherein the adding amount of the acid blue is 0.1mol, and freezing the cross-linking agent solution into ice balls with the diameter of 4 cm at the temperature of-20 ℃ by using a die;
2) 165g of thiophene monomer is dissolved in 2.5L4mol/L hydrochloric acid solution to obtain an acid system;
3) Dispersing potassium periodate serving as an initiator in 1L of water to prepare 0.2mol/L potassium periodate solution, and placing the solution in a constant-pressure funnel;
4) Adding the ice ball prepared in the step 1) into the acid system of the step 2), simultaneously dropwise adding a potassium periodate solution by using a constant pressure funnel at a speed of 6g/min, regulating the reaction temperature to-2 ℃, and reacting for 1.5h under the ultrasonic power of 600W to obtain the crosslinked nano conductive polythiophene.
5) Centrifuging the crosslinked nano conductive polypyrrole obtained in the step 4) for 40min at 2500rpm, then washing the polypyrrole with ultrapure water to enable the pH value of the material to be 5.5, and finally drying the material at 50 ℃ for 3h to obtain the crosslinked nano conductive polythiophene powder with the crosslinking degree of 23.8%.
Example 4
1) Using p-phenylenediamine as a cross-linking agent, dispersing the p-phenylenediamine in 0.3L of water, wherein the addition amount of the p-phenylenediamine is 0.1mol, and freezing a dispersion system of the cross-linking agent and water into cubes with 3 cm side length at the temperature of-20 ℃ by using a die;
2) 180g of aniline monomer is dissolved in 2.5L of 3mol/L sulfuric acid solution to obtain an acid system;
3) Ferric chloride is selected as an initiator, dissolved in 1L of water to prepare 0.5mol/L ferric chloride solution, and placed in a constant pressure funnel;
4) Adding the ice ball prepared in the step 1) into the acid system of the step 2), simultaneously dropwise adding an iron chloride solution by using a constant pressure funnel at a speed of 5g/min, regulating the reaction temperature to 0 ℃, and reacting for 1.2h under the ultrasonic power of 800W to obtain the crosslinked nano conductive polyaniline.
5) Centrifuging the crosslinked nano conductive polypyrrole obtained in the step 4) for 40min at 2500rpm, then washing the polypyrrole with ultrapure water to enable the pH value of the material to be 6.5, and finally drying the material at 60 ℃ for 2.5h to obtain crosslinked nano conductive polyaniline powder with the crosslinking degree of 6%.
Example 5
1) Using p-phenylenediamine as a cross-linking agent, dispersing the p-phenylenediamine in 0.3L of water, wherein the addition amount of the p-phenylenediamine is 0.3mol, and freezing a dispersion system of the cross-linking agent and water into cubes with 3 cm side length at the temperature of-20 ℃ by using a die;
2) 180g of aniline monomer is dissolved in 2.5L of 3mol/L sulfuric acid solution to obtain an acid system;
3) Ferric chloride is selected as an initiator, dissolved in 1L of water to prepare 0.5mol/L ferric chloride solution, and placed in a constant pressure funnel;
4) Adding the ice ball prepared in the step 1) into the acid system of the step 2), simultaneously dropwise adding an iron chloride solution by using a constant pressure funnel at a speed of 5g/min, regulating the reaction temperature to 0 ℃, and reacting for 1.2h under the ultrasonic power of 800W to obtain the crosslinked nano conductive polyaniline.
5) Centrifuging the crosslinked nano conductive polypyrrole obtained in the step 4) for 40min at 2500rpm, then washing the polypyrrole with ultrapure water to enable the pH value of the material to be 6.5, and finally drying the material at 60 ℃ for 2.5h to obtain crosslinked nano conductive polyaniline powder with the crosslinking degree of 18%.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A method for preparing a crosslinked conductive polymer by adopting a deicing slow release mode, which is characterized by comprising the following steps:
1) Dispersing the cross-linking agent into water, and then freezing to form a cross-linking agent ice body;
2) Dispersing conductive polymer monomers in an acid solution to obtain an acid system;
3) Adding the crosslinking agent ice body obtained in the step 1) into the acidic system obtained in the step 2), and simultaneously adding an initiator solution to perform polymerization reaction to generate a crosslinked conductive polymer;
wherein, the step 1) and the step 2) are not in sequence;
the volume of the cross-linking agent ice body is 1-100 cm 3 ；
The polymerization reaction is carried out under the condition of ultrasound, the time of the ultrasound is 0.5-2 h, and the power of the ultrasound is 100-1000W.
2. The method for preparing a crosslinked conductive polymer by adopting a slow release mode of ice melting according to claim 1, wherein the concentration of the crosslinking agent in the step 1) is 0.1-2 mol/L; the cross-linking agent ice body is a sphere or a cube.
3. The method for preparing a crosslinked conductive polymer by means of ice melting slow release according to claim 1 or 2, wherein the concentration of the acidic solution in the step 2) is 1-6 mol/L; the concentration of the conductive polymer monomer in the acid system is 0.1-2 mol/L.
4. The method for preparing a crosslinked conductive polymer by adopting a deicing slow release mode according to claim 3, wherein the initiator solution is an aqueous solution of an initiator, and the concentration is 0.1-2 mol/L; the initiator solution is added in the step 3) in a dropwise manner, and the dropwise adding rate is 1-6 g/min.
5. The method for preparing a crosslinked conductive polymer according to claim 1, 2 or 4, wherein the molar ratio of the crosslinking agent, the conductive polymer monomer and the initiator is 0.1 to 1.0mol:0.2 to 2mol:0.1 to 1.0mol.
6. The method of preparing a crosslinked conductive polymer according to claim 5, wherein the crosslinking agent comprises one or more of 1,3, 5-tris (anilino) benzene, disodium salt of bis-benzenesulfonic acid, acid blue, p-phenylene diamine, and triphenylamine;
the initiator comprises one or more of ammonium persulfate, potassium dichromate, potassium iodate, ferric chloride, hydrogen peroxide, and ceric sulfate.
7. The method for preparing a crosslinked conductive polymer according to claim 1, 2, 4 or 6, wherein the conductive polymer monomer comprises an aniline monomer, a pyrrole monomer or a thiophene monomer;
the acidic solution comprises an aqueous solution of hydrochloric acid, sulfuric acid or perchloric acid.
8. The method for preparing a crosslinked conductive polymer according to claim 7, wherein the reaction temperature of the polymerization reaction in the step 3) is-5 to 5 ℃.
9. The method for preparing the crosslinked conductive polymer by adopting the ice melting slow release mode according to claim 1, 2, 4, 6 or 8, wherein the step 3) is carried out after the polymerization reaction is finished, and the post-treatment process sequentially comprises centrifugation, water washing and drying; the centrifugal speed is 1000-10000 rpm, and the time is 10-60 min; washing with water until the pH of the material is more than 5; the temperature of the drying is 40-60 ℃ and the time is 2-6 h.
10. A crosslinked conductive polymer prepared by the method of any one of claims 1-9.
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