CN115975188B - Nano conductive polymer and preparation method thereof - Google Patents
Nano conductive polymer and preparation method thereof Download PDFInfo
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- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 79
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 36
- 239000003999 initiator Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 239000000178 monomer Substances 0.000 claims description 32
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 18
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000007710 freezing Methods 0.000 claims description 14
- 230000008014 freezing Effects 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 239000006230 acetylene black Substances 0.000 claims description 11
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002041 carbon nanotube Substances 0.000 claims description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 10
- 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 10
- 239000003929 acidic solution Substances 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- 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 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000012621 metal-organic framework Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 3
- 229910003472 fullerene Inorganic materials 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 239000002082 metal nanoparticle Substances 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- 229910021392 nanocarbon Inorganic materials 0.000 claims 2
- 239000002131 composite material Substances 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
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- 239000007864 aqueous solution Substances 0.000 description 23
- 239000000843 powder Substances 0.000 description 17
- 229920000767 polyaniline Polymers 0.000 description 15
- 239000002077 nanosphere Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007774 positive electrode material Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
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- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
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- 239000008367 deionised water Substances 0.000 description 3
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- 230000000977 initiatory effect Effects 0.000 description 2
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- 238000001000 micrograph Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
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Abstract
The invention relates to the field of conductive polymer synthesis, in particular to a nano conductive polymer and a preparation method thereof. The invention provides a synthesis method of ice bath environment and initiator release rate required by conductive polymer polymerization reaction and template material introduction polymerization system rate through melting of the ice body, thereby realizing uniform efficient constant-temperature synthesis of conductive polymer composite material. The nano conductive polymer prepared by the preparation method can be used as an excellent high specific capacity discharge electrode material, and the method has the advantages of simple process, easy control, rapidness and high efficiency.
Description
Technical Field
The invention relates to the technical field of conductive polymer synthesis, in particular to a nano conductive polymer and a preparation method thereof.
Background
Since the invention, conductive polymers have been widely used in the fields of energy storage, photoelectric conversion, catalysis, electromagnetic shielding, conductive coatings, and the like. It has the advantages of simple synthesis, low price of source material, good conductivity, etc. The traditional conductive polymer material can not ensure uniformity of the addition rate of the initiator in the synthesis process, and is easy to agglomerate without a template material as a support, so that a large number of active sites are lost, and the conductive polymer material is particularly applied to the field of energy storage materials. This means that the conductive polymer, which can be an excellent high specific capacity discharge electrode material, is far from its theoretical capacity.
In order to overcome the above disadvantages, the industry generally adopts a template material with high conductivity and high specific surface area as a basis for polymer polymerization reaction, so as to synthesize the conductive polymer composite material with a highly dispersed structure and high specific surface area. In order to ensure a high degree of dispersion of the polymeric material, it is necessary to subject the polymeric material to a hydrophilic and dispersing treatment prior to synthesis, but the non-uniform introduction of the template material during the addition process may result in non-uniform polymerization of the composite material, thereby affecting the properties of the final product.
Disclosure of Invention
The invention aims to provide a nano conductive polymer and a preparation method thereof, wherein the nano conductive polymer is prepared by controlling the reaction temperature and controlling the polymerization reaction to uniformly occur at a two-phase interface through an ice release template method, so that the rapid and efficient synthesis of the conductive polymer can be realized.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides a preparation method of a nano conductive polymer, which comprises the following steps:
(1) Freezing the initiator solution into ice;
(2) Dispersing a template material in water after hydrophilic treatment, and freezing a solution containing the template material into an ice body;
(3) Dispersing conductive polymer monomers in an acidic solution, adding the ice bodies prepared in the step (1) and the step (2), and carrying out polymerization reaction to obtain a nano conductive polymer;
and (3) the step (1) and the step (2) have no requirement on sequence.
Preferably, the initiator in step (1) comprises one or more of ammonium persulfate, sodium persulfate, potassium periodate, hydrogen peroxide, and potassium dichromate; the concentration of the initiator solution is 0.1-5 mol/L;
The ice body in the step (1) comprises spheres or cubes, and the volume of the ice body is 1-125 cubic centimeters.
Preferably, the template material in the step (2) is one or more of graphene, carbon nanotubes, hollow carbon nanospheres, solid carbon nanospheres, carbon quantum dots, acetylene black, conductive carbon black, ketjen black, activated carbon, fullerene, metal-organic framework material, covalent organic framework material, titanium carbide, metal oxide and metal nanoparticles.
Preferably, the hydrophilic treatment in the step (2) is a liquid phase treatment method, which comprises the following steps:
S1: adding a template material into a hydrophilic solution according to the addition amount of 1-20 g/L;
s2: stirring the mixture obtained in the step S1 for 30-60 min, and suction-filtering the material to obtain a filter cake, thereby obtaining a template material subjected to hydrophilic treatment;
The concentration of the hydrophilic solution in the step S1 is 2-6 mol/L; the hydrophilic solution comprises hydrochloric acid solution, sulfuric acid solution, nitric acid solution, hydrogen peroxide solution or potassium permanganate solution.
Preferably, the ice body in the step (2) comprises spheres or cubes, and the volume of the ice body is 1-100 cubic centimeters;
The concentration of the template material after hydrophilic treatment in water is 1-30 g/L.
Preferably, the conductive polymer monomer in the step (3) comprises an aniline monomer, a pyrrole monomer or a thiophene monomer;
the concentration of the acid solution is 0.1-6 mol/L; the acidic solution comprises a hydrochloric acid solution, a sulfuric acid solution, a perchloric acid solution, or an acetic acid solution.
Preferably, the dosage ratio of the conductive polymer monomer to the acid solution in the step (3) is 80-990 g:1-15L;
The dosage ratio of the initiator to the template material to the conductive polymer monomer is 0.5-30 mol: 1-20 g: 80-990 g.
Preferably, the reaction temperature of the polymerization reaction in the step (3) is-5 ℃; and after the ice body is completely melted in the polymerization reaction, the reaction is completed.
The invention also provides the nano conductive polymer prepared by the preparation method of the nano conductive polymer.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the invention respectively freezes a water-soluble initiator in an ice body, disperses and dissolves a template material subjected to hydrophilic treatment in water to freeze the ice body, adds the ice body containing the initiator and the ice body containing the template material into a polymerization system containing a polymerization monomer, provides an ice bath environment required by a polymerization reaction of a conductive polymer through the ice body, and controls release rates of the initiator and the template material through melting of the ice body, thereby preparing a nano conductive polymer; the method can effectively control the reaction temperature of a polymerization system, so that the whole polymerization reaction can be always kept at a freezing point, and the release rate of the initiator is successfully controlled by controlling the quantity of ice bodies containing the initiator and the system, so that the slow initiation in the free radical polymerization process is realized. The method has the characteristics of simple process, easy control, high speed and high efficiency by controlling the melting speed of the ice body containing the template material and controlling the speed of introducing the template material into a reaction system.
Drawings
FIG. 1 is a scanning electron microscope image of a 20% titanium carbide doped polyaniline/titanium carbide composite material obtained in example 5;
Fig. 2 is a constant current charge and discharge cycle chart of an aqueous zinc ion battery using the 20% titanium carbide doped polyaniline/titanium carbide composite material obtained in example 5 as a positive electrode material.
Detailed Description
The invention provides a preparation method of a nano conductive polymer, which comprises the following steps:
(1) Freezing the initiator solution into ice;
(2) Dispersing a template material in water after hydrophilic treatment, and freezing a solution containing the template material into an ice body;
(3) Dispersing conductive polymer monomers in an acidic solution, adding the ice bodies prepared in the step (1) and the step (2), and carrying out polymerization reaction to obtain a nano conductive polymer;
and (3) the step (1) and the step (2) have no requirement on sequence.
In the present invention, the initiator in the step (1) comprises one or more of ammonium persulfate, sodium persulfate, potassium periodate, hydrogen peroxide and potassium dichromate, preferably one or more of ammonium persulfate, sodium persulfate, potassium periodate, hydrogen peroxide and potassium dichromate;
The initiator solution is an aqueous solution of an initiator, and the concentration of the initiator solution is 0.1-5 mol/L, preferably 0.5-3 mol/L;
The ice bodies in step (1) comprise spheres or cubes, preferably spheres; the volume of the ice body is 1 to 125 cubic centimeters, preferably 8 to 100 cubic centimeters, and more preferably 36 to 64 cubic centimeters.
In the present invention, the template material in the step (2) is one or more of graphene, carbon nanotubes, hollow carbon nanospheres, solid carbon nanospheres, carbon quantum dots, acetylene black, conductive carbon black, ketjen black, activated carbon, fullerene, metal-organic framework material, covalent organic framework material, titanium carbide, metal oxide and metal nanoparticles, preferably one or more of carbon nanotubes, hollow carbon nanospheres, acetylene black, metal-organic framework material and titanium carbide.
In the present invention, the hydrophilic treatment in the step (2) is a liquid phase treatment method, comprising the steps of:
S1: adding a template material into a hydrophilic solution according to the addition amount of 1-20 g/L;
s2: stirring the mixture obtained in the step S1 for 30-60 min, and suction-filtering the material to obtain a filter cake, thereby obtaining a template material subjected to hydrophilic treatment;
the addition amount of the template material in the step S1 is 1-20 g/L, preferably 5-15 g/L;
The concentration of the hydrophilic solution in the step S1 is 2-6 mol/L, preferably 3-5 mol/L; the hydrophilic solution comprises hydrochloric acid solution, sulfuric acid solution, nitric acid solution, hydrogen peroxide solution or potassium permanganate solution, and is preferably hydrochloric acid solution, sulfuric acid solution or nitric acid solution;
in step S2, the mixture obtained in step S1 is stirred for 30 to 60 minutes, preferably 40 to 50 minutes.
In the present invention, the ice body in the step (2) comprises spheres or cubes, preferably spheres; the volume of the ice body is 1-100 cubic centimeters, preferably 2-64 cubic centimeters, and more preferably 8-36 cubic centimeters;
The concentration of the template material after hydrophilic treatment in water is 1-30 g/L, preferably 10-20 g/L.
In the present invention, the conductive polymer monomer in the step (3) comprises an aniline monomer, a pyrrole monomer or a thiophene monomer, preferably an aniline monomer or a pyrrole monomer;
the concentration of the acidic solution is 0.1-6 mol/L, preferably 0.5-2 mol/L; the acidic solution comprises a hydrochloric acid solution, a sulfuric acid solution, a perchloric acid solution, or an acetic acid solution, preferably a hydrochloric acid solution.
In the present invention, the ratio of the conductive polymer monomer to the acidic solution in the step (3) is 80 to 990g, 1 to 15L, preferably 135 to 450g: 5-10L;
The dosage ratio of the initiator to the template material to the conductive polymer monomer is 0.5-30 mol: 1-20 g:80 to 990g, preferably 5 to 15mol: 5-15 g:135 g to 450g.
In the present invention, the polymerization reaction in the step (3) is performed under stirring or ultrasonic conditions; the stirring speed is 100-1000 rpm, preferably 300-800 rpm; the ultrasonic power is 500-1000W, preferably 600-800W.
In the invention, the reaction temperature of the polymerization reaction in the step (3) is-5 to 5 ℃, preferably-3 to 2 ℃; and after the ice body is completely melted in the polymerization reaction, the reaction is completed.
In the invention, in the step (3), the mixture after the polymerization reaction is centrifuged or filtered to obtain the conductive polymer, and the conductive polymer is washed and dried to obtain the nano conductive polymer powder.
The invention also provides the nano conductive polymer prepared by the preparation method of the nano conductive polymer.
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) Ammonium persulfate is used as an initiator, dissolved in 1 liter of water to prepare 0.5mol/L aqueous solution, and frozen into ice balls with the diameter of 5cm at the temperature of minus 20 ℃;
(2) 15g of carbon nano tube is selected as a template material, dispersed in 1 liter of 2mol/L hydrochloric acid solution, stirred for 30min, and filtered to obtain a filter cake, thus obtaining a template material with hydrophilic treatment; ultrasonically dispersing the template material subjected to hydrophilic treatment in an aqueous solution to prepare 15g/L aqueous solution, rapidly cooling the aqueous solution by liquid nitrogen, and freezing the aqueous solution containing carbon nano tubes into ice balls with the diameter of 2 cm;
(3) 135g of aniline monomer are dissolved in 1 liter of 1mol/L hydrochloric acid solution; adding the ice ball in the steps (1) and (2), and stirring and polymerizing under the conditions that the ultrasonic power is 1000W and the temperature is 0-5 ℃ to obtain a mixture in which polymerization is carried out; after the ice body is completely melted, the polymerization reaction is completed, the mixture after the reaction is centrifuged to obtain a conductive polymer, the polymer is washed by 2L of deionized water and dried at 60 ℃ to obtain 10% carbon nanotube doped polyaniline/carbon nanotube composite material powder. The particle size of the powder material is less than 100nm, and the carbon nano tube is embedded therein, so that the structure is uniform.
(4) The polyaniline/carbon nano tube composite material prepared in the step (3) is used as a positive electrode material of a zinc ion battery, conductive carbon paper is used as a current collector, glass fiber is used as a diaphragm, a mixed solution of 1mol/L ZnCl 2 and 0.5mol/L NH 4 Cl is used as electrolyte, an analytically pure zinc metal plate with the thickness of 0.5mm is used as a negative electrode, and the positive electrode, the diaphragm and the negative electrode are stacked in sequence, sealed in an aluminum plastic bag, and a tab is reserved, and the test is carried out after standing for 24 hours.
(5) The battery manufactured in the step (4) is tested under the current density of 0.1A/g, the specific charge and discharge capacity of the battery is 115mAh/g, and the battery can stably circulate for more than 300 circles.
Example 2
(1) Potassium periodate is selected as an initiator, 1 liter of 0.5mol/L initiator solution is prepared by dissolving the potassium periodate in water, and the initiator solution is frozen into cubes with side length of 2 cm at the temperature of minus 18 ℃;
(2) Selecting 5gUIO-66 (MOF) as a template material, dispersing in 1 liter of 3mol/L hydrogen peroxide solution, stirring for 60min, and filtering the material to obtain a filter cake to obtain a hydrophilic template material; ultrasonically dispersing the template material subjected to hydrophilic treatment in an aqueous solution to prepare 5g/L aqueous solution, rapidly cooling by liquid nitrogen, and freezing the aqueous solution of the obtained MOF material into an ice ball with the diameter of 5 cm;
(3) 450g of pyrrole monomer are dissolved in 1.5L of 2mol/L hydrochloric acid solution; adding the ice ball in the steps (1) and (2), and carrying out polymerization under the conditions that the ultrasonic power is 500W and the temperature is-3 ℃ to obtain a mixture in which the polymerization is carried out; after the ice body is completely melted, the polymerization reaction is completed, the mixture after the reaction is centrifuged to obtain a conductive polymer, and the polymer is washed by 2.5L of ultrapure water and dried at 60 ℃ to obtain polypyrrole/MOF composite material powder with the MOF content of 1 percent. The powder material is in the form of a UIO-66 (MOF) block, the surface of the powder material has a uniform polypyrrole structure, the particle size of polypyrrole monomers is less than 100nm, and the texture is uniform.
(4) The polypyrrole/MOF composite material powder with the MOF content of 1% prepared in the step (3) is used as a positive electrode material of a zinc ion battery, conductive carbon paper is used as a current collector, glass fiber is used as a diaphragm, a mixed solution of ZnCl 2 with the concentration of 1mol/L and NH 4 Cl with the concentration of 0.5mol/L is used as an electrolyte, an analytically pure zinc metal plate with the thickness of 0.5mm is used as a negative electrode, lugs are reserved in aluminum plastic bags in a stacked mode according to the sequence of the positive electrode, the diaphragm and the negative electrode, and the test is carried out after standing for 24 hours.
(5) The battery manufactured in the step (4) is tested under the high current density of 1A/g, the specific charge and discharge capacity of the battery is 105mAh/g, and the battery can stably circulate for more than 100 circles.
Example 3
(1) Sodium persulfate is selected as an initiator, dissolved in water to prepare an initiator solution with the concentration of 5 liters and 1mol/L, and frozen into ice balls with the diameter of 5 cm at the temperature of-18 ℃;
(2) 1g of acetylene black is selected as a template material, dispersed in 1 liter of 2mol/L hydrochloric acid solution, stirred for 30min, and filtered to obtain a filter cake, thus obtaining a template material subjected to hydrophilic treatment; ultrasonically dispersing the template material subjected to hydrophilic treatment in an aqueous solution to prepare 1g/L aqueous solution, rapidly cooling the aqueous solution by liquid nitrogen, and freezing the aqueous solution of the acetylene black material into a square ice body with the side length of 2 cm;
(3) 99g of aniline monomer is dissolved in 5L of 1mol/L hydrochloric acid solution; adding the ice balls in the steps (1) and (2), and carrying out polymerization reaction under the conditions that the stirring speed is 100rpm and the temperature is 3 ℃ to obtain a mixture in which the polymerization reaction is carried out; after the ice body is completely melted, the polymerization reaction is completed, the mixture after the reaction is centrifuged to obtain a conductive polymer, the polymer is washed by 2L of ultrapure water and dried at 60 ℃ to obtain polyaniline/acetylene black powder with the doping amount of 1 percent of acetylene black. The powder material is a core-shell structure with acetylene black powder as a core and uniformly covered on the surface, the particle size of the polyaniline monomer is less than 100nm, and the texture is uniform.
(4) Polyaniline/acetylene black powder with the doping amount of 1% of acetylene black prepared in the step (3) is used as a positive electrode material of a zinc ion battery, conductive carbon paper is used as a current collector, glass fiber is used as a diaphragm, a mixed solution of 1mol/L ZnCl 2 and 0.5mol/L NH 4 Cl is used as electrolyte, an analytically pure zinc metal plate with the thickness of 0.5mm is used as a negative electrode, tabs are reserved in aluminum plastic bags in sequence of the positive electrode, the diaphragm and the negative electrode, and the test is carried out after standing for 24 hours.
(5) The battery manufactured in the step (4) is tested under the current density of 0.5A/g, the specific charge and discharge capacity of the battery is 130mAh/g, and the battery can stably circulate for more than 180 circles.
Example 4
(1) Hydrogen peroxide is selected as an initiator, dissolved in water to prepare 10L of 3mol/L initiator solution, and frozen at the temperature of minus 20 ℃ to form a cube with the side length of 5 cm;
(2) 10g of hollow carbon nanospheres are selected as template materials, dispersed in 1 liter of 5mol/L hydrochloric acid solution, stirred for 30min, and filtered to obtain a filter cake, thus obtaining a template material with hydrophilic treatment; ultrasonically dispersing the template material subjected to hydrophilic treatment in an aqueous solution to prepare 10g/L aqueous solution, rapidly cooling the aqueous solution by liquid nitrogen, and freezing the aqueous solution of the carbon nanosphere material into a square ice body with the side length of 4 cm;
(3) 990g of aniline monomer are dissolved in 15L of 0.5mol/L hydrochloric acid solution; adding the ice balls in the steps (1) and (2), and carrying out polymerization reaction under the conditions that the stirring speed is 1000rpm and the temperature is 0 ℃ to obtain a mixture in which the polymerization reaction is carried out; after the ice body is completely melted, the polymerization reaction is completed, the mixture after the reaction is centrifuged to obtain a conductive polymer, the polymer is washed by 25L of ultrapure water and dried at 60 ℃ to obtain the polyaniline/carbon nanosphere powder doped with 1% hollow carbon nanospheres. The powder material is a core-shell structure with carbon nanospheres as cores and uniformly covered with polyaniline monomers, and has overall particle size smaller than 1 micron and uniform texture.
(4) The polyaniline/carbon nanosphere powder doped with the hollow carbon nanospheres prepared in the step (3) is used as a positive electrode material of a zinc ion battery, conductive carbon paper is used as a current collector, glass fiber is used as a diaphragm, a mixed solution of 1mol/L ZnCl 2 and 0.5mol/L NH 4 Cl is used as electrolyte, an analytically pure zinc metal plate with the thickness of 0.5mm is used as a negative electrode, lugs are reserved in aluminum plastic bags in sequence of the positive electrode, the diaphragm and the negative electrode, and the test is carried out after standing for 24 hours.
(5) The battery manufactured in the step (4) is tested under the current density of 0.5A/g, the specific charge and discharge capacity of the battery is 115mAh/g, and the battery can stably circulate for more than 190 circles.
Example 5
(1) Dissolving potassium dichromate serving as an initiator into 1 liter of water to prepare 0.5mol/L aqueous solution, and freezing the aqueous solution into ice balls with the diameter of 5cm at the temperature of minus 18 ℃;
(2) Selecting 20g of titanium carbide as a template material, dispersing the template material in 1 liter of 6mol/L sulfuric acid solution, stirring for 30min, and filtering the material to obtain a filter cake to obtain a template material subjected to hydrophilic treatment; ultrasonically dispersing the template material subjected to hydrophilic treatment in an aqueous solution to prepare a 20g/L aqueous solution, rapidly cooling the aqueous solution by liquid nitrogen, and freezing the aqueous solution containing the titanium carbide material into an ice ball with the diameter of 5 cm;
(3) 80g of aniline monomer is dissolved in 1 liter of 1mol/L hydrochloric acid solution; adding the ice balls in the steps (1) and (2), stirring and polymerizing under the conditions that the stirring speed is 1000rpm and the temperature is 5 ℃, and adding deionized water into the system to freeze the ice balls to control the polymerization time to be more than 4 hours; after the ice body is completely melted, the polymerization reaction is completed, the reacted mixture is centrifuged to obtain a conductive polymer, the polymer is washed five times by 2L of deionized water and dried at 60 ℃ to obtain polyaniline/titanium carbide composite material powder with 20% titanium carbide content, and a scanning electron microscope image of the polyaniline/titanium carbide composite material powder is shown in figure 1.
As can be seen from FIG. 1, the synthesized polyaniline/titanium carbide composite material with 20% titanium carbide content has uniform texture, and the template material titanium carbide is inlaid therein. Meanwhile, the polyaniline material has small particle size, which endows the material with high porosity and high specific surface area required to be used as an electrode material.
(4) And (3) using the powder obtained in the step (3) as a positive electrode material, using conductive carbon paper as a current collector, using glass fiber as a diaphragm, using a mixed solution of 1mol/L ZnCl 2 and 0.5mol/L NH 4 Cl as an electrolyte, using an analytically pure zinc metal plate with the thickness of 0.5mm as a negative electrode, stacking according to the sequence of the positive electrode, the diaphragm and the negative electrode, sealing in an aluminum plastic bag to leave a tab, and standing for 24 hours for testing.
(5) The battery produced in (4) was used for testing at a current density of 0.5A/g, and the charge-discharge cycle curve of the obtained battery was shown in FIG. 2.
As can be seen from FIG. 2, when the polyaniline/titanium carbide composite material with 20% titanium carbide content prepared by the method is used as a positive electrode material of a zinc ion battery, the discharge capacity of the battery can reach 125mAh/g, and the battery can stably circulate for more than 200 circles. This demonstrates that the material has rich reactive sites to provide high specific capacity of the battery material. Meanwhile, the long cycle performance of the material synthesized by the method proves that the material has a stable structure and is not easy to collapse in the charge and discharge process.
From the above examples, the present invention provides a nano conductive polymer and a preparation method thereof; the method can effectively control the reaction temperature of a polymerization system, so that the whole polymerization reaction can be always kept at a freezing point, and the release rate of the initiator is successfully controlled by controlling the quantity of ice bodies containing the initiator and the system, so that the slow initiation in the free radical polymerization process is realized. The method has the characteristics of simple process, easy control, high speed and high efficiency.
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 (7)
1. A method for preparing a nano conductive polymer, which is characterized by comprising the following steps:
(1) Freezing the water-soluble initiator solution into ice;
(2) Dispersing a template material in water after hydrophilic treatment, and freezing a solution containing the template material into an ice body;
(3) Dispersing conductive polymer monomers in an acidic solution, adding the ice bodies prepared in the step (1) and the step (2), and carrying out polymerization reaction to obtain a nano conductive polymer;
the step (1) and the step (2) have no requirement of sequence;
The template material in the step (2) is one or more of graphene, carbon nano tubes, hollow nano carbon spheres, solid nano carbon spheres, carbon quantum dots, acetylene black, conductive carbon black, ketjen black, active carbon, fullerene, metal-organic framework material, titanium carbide and metal nano particles;
The conductive polymer monomer in the step (3) comprises aniline monomer, pyrrole monomer or thiophene monomer;
the concentration of the acid solution is 0.1-6 mol/L; the acid solution comprises hydrochloric acid solution, sulfuric acid solution and perchloric acid solution;
the dosage ratio of the water-soluble initiator to the template material to the conductive polymer monomer is 0.5-30 mol:1-20 g:80-990 g;
The reaction temperature of the polymerization reaction in the step (3) is-5 ℃.
2. The method of preparing a nano-conductive polymer according to claim 1, wherein the water-soluble initiator in step (1) comprises one or more of ammonium persulfate, sodium persulfate, potassium periodate, hydrogen peroxide, and potassium dichromate; the concentration of the water-soluble initiator solution is 0.1-5 mol/L;
The ice body in the step (1) comprises spheres or cubes, and the volume of the ice body is 1-125 cubic centimeters.
3. The method for preparing a nano conductive polymer according to any one of claims 1 to 2, wherein the hydrophilic treatment in the step (2) is a liquid phase treatment method, comprising the steps of:
S1: adding a template material into a hydrophilic solution according to the addition amount of 1-20 g/L;
s2: stirring the mixture obtained in the step S1 for 30-60 min, and suction-filtering the material to obtain a filter cake, thereby obtaining a template material subjected to hydrophilic treatment;
The concentration of the hydrophilic solution in the step S1 is 2-6 mol/L; the hydrophilic solution comprises hydrochloric acid solution, sulfuric acid solution, nitric acid solution, hydrogen peroxide solution or potassium permanganate solution.
4. A method of preparing a nano-conductive polymer according to claim 3, wherein the ice body in the step (2) comprises spheres or cubes, and the volume of the ice body is 1-100 cubic centimeters;
The concentration of the template material after hydrophilic treatment in water is 1-30 g/L.
5. The method of claim 4, wherein the conductive polymer monomer and the acidic solution in the step (3) are used in an amount of 80-990 g/1-15L.
6. The method for preparing a nano conductive polymer according to any one of claims 1 to 2 or 4 or 5, wherein the polymerization reaction in the step (3) is completed after the ice body is completely melted.
7. The nano conductive polymer prepared by the preparation method of the nano conductive polymer according to any one of claims 1 to 6.
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