CN115895090A - Preparation method of conductive polymer composite material with low percolation threshold - Google Patents

Preparation method of conductive polymer composite material with low percolation threshold Download PDF

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CN115895090A
CN115895090A CN202211646681.XA CN202211646681A CN115895090A CN 115895090 A CN115895090 A CN 115895090A CN 202211646681 A CN202211646681 A CN 202211646681A CN 115895090 A CN115895090 A CN 115895090A
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conductive polymer
composite material
polymer composite
percolation threshold
conductive filler
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张久洋
彭豪
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Southeast University
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Abstract

The invention discloses a preparation method of a low-percolation threshold conductive polymer composite material, which comprises the following steps: mixing liquid metal and other metals, and heating to melt the liquid metal and other metals to form a melt; cooling the melt for recrystallization to obtain a crystalline conductive filler; and mixing the crystalline conductive filler with a polymer matrix, and processing and molding to obtain the conductive polymer composite material. The liquid metal component in the crystalline conductive filler is oxidized ultra-quickly, so that the interface compatibility of the crystalline conductive filler and a macromolecule is improvedThereby remarkably reducing the percolation threshold of the conductive polymer. According to the content of the filler, the resistivity of the conductive polymer is 1 multiplied by 10 5 Omega cm to 1X 10 ‑7 Change in Ω · cm.

Description

Preparation method of conductive polymer composite material with low percolation threshold
Technical Field
The invention relates to a preparation method of a conductive polymer composite material, in particular to a preparation method of a conductive polymer composite material with a low percolation threshold.
Background
The conductive polymer composite material is obtained by blending and compounding conductive filler and polymerConductivity of 10 -4 A polymer material having S/m or more. According to the percolation threshold theory, in the composite conductive polymer, the conductive fillers need a certain filling amount to be contacted with each other in the polymer substrate to form a conductive network, so that the conversion from an insulator to a conductor is realized.
The conductive fillers mainly used at present include carbon-based fillers and metal fillers. The carbon-based filler has low conductivity, so that the conductivity of the carbon-based conductive polymer is poor (< 10) 2 S/m) cannot meet the high-end applications in the modern technology field. The metal has natural high conductivity (10) 6 ～10 8 S/m). However, the metal spherical powder has a small specific surface area, and it is difficult to form a conductive network by contacting each other in a polymer matrix. Therefore, researchers have prepared metal fillers (such as silver nanowires, flaky silver, etc.) with microstructures such as needles and flakes to increase the aspect ratio of the fillers and increase the probability of the fillers contacting each other in the polymer matrix. However, the conventional metal fillers having a microstructure of needle shape, flake shape, etc. have major disadvantages: (1) difficult preparation of fillers: for example, the preparation of silver nanowires requires photolithography, a polyol method, a hydrothermal method, and the like. (2) difficult large-scale preparation, resulting in high filler cost. (3) The metal filler is difficult to disperse in the polymer and easy to agglomerate: the interface difference between metal as an inorganic material and an organic polymer material is large, and the compatibility between the metal and the polymer is poor. (4) The difficulty of dispersion leads to a high percolation threshold (> 40% by volume) for metal-filled conducting polymers, which greatly impairs the mechanical and processing properties of the conducting polymer.
Therefore, a simple method is found for preparing the metal conductive filler with good dispersibility so as to prepare the conductive polymer composite material with low percolation threshold, which is very important for reducing the cost of the conductive polymer composite material and improving the mechanical and processing properties.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a preparation method of a conductive polymer composite material with a low percolation threshold.
The technical scheme is as follows: the preparation method of the conductive polymer composite material with the low percolation threshold comprises the following steps:
(1) Mixing liquid metal and other metals, mixing the liquid metal and other metals, and heating to melt the liquid metal and other metals to form a melt;
(2) Cooling the melt for recrystallization to obtain a crystalline conductive filler;
(3) And mixing the crystalline conductive filler with a polymer matrix, and processing and molding to obtain the conductive polymer composite material.
In the step (1), the heating temperature is only required to enable the liquid metal and other metals to be in a molten state at the same time, and the liquid metal and other metals can form a melt after mixing; the heating temperature is preferably 30 to 1000 ℃.
Wherein the seepage threshold of the conductive polymer composite material is 5-30% of the volume fraction.
In the step (1), the volume part ratio of the liquid metal to other metals is 5-95: 0 to 70 percent; with end point values excluded.
In the step (1), at least one simple substance of the liquid metals gallium, zinc, bismuth, indium, tin and aluminum, or an alloy of two or more elements.
Wherein, in step (1), the other metal is gold, silver, copper, zinc, mercury, platinum, cadmium, aluminum, iron, cobalt, nickel, gallium, indium, tin, bismuth, lead, chromium, tellurium, cesium, titanium, vanadium, lanthanoid, actinide, scandium, iridium, tungsten, yttrium, lithium, manganese, magnesium, antimony, thallium, calcium, sodium, potassium, rubidium, cesium, francium, beryllium, strontium, barium, radium, germanium, polonium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, holmium, dysprosium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, rhenium, osmium, thorium, protactinium, uranium, thulium, neptunium, plutonium, americium, curium, californium, pinum, crinite, ferum, mendeleum, seum, simple substance, or an alloy of two or more elements.
Wherein in the step (3), the volume part of the polymer matrix is 5-95 parts.
Wherein, in the step (3), the coating also comprises a functional additive, and the volume part of the functional additive is 0-5 parts.
Wherein in the step (2), the crystalline conductive filler has a microscopic morphology of a sphere, a needle, a rod, a sheet, a pentagram, or a snowflake.
In the step (3), the polymer matrix is thermoplastic resin, thermosetting resin or rubber.
Wherein the thermoplastic resin is at least one of polyethylene, polypropylene, polystyrene, polyvinyl chloride, polymethyl methacrylate, polyetheretherketone, polyoxymethylene, polycarbonate, polybutylene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, polybutylene terephthalate, thermoplastic polyurethane, polytetrafluoroethylene, nylon, polyvinylidene fluoride, polyimide, polychlorotrifluoroethylene, ethylene-propylene copolymer, ethylene-tetrafluoroethylene copolymer, polyvinyl alcohol, chlorinated polypropylene, polyacrylonitrile, polyphenylene ether ketone, polyphenylene sulfide, polyvinylidene chloride, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymer, styrene-isoprene copolymer, or hydrogenated styrene-isoprene copolymer.
The thermosetting resin is at least one of phenolic resin, urea resin, melamine resin, epoxy resin, silicon resin, unsaturated polyester resin, alkyd resin, polybutadiene resin, vinyl resin, furan resin, organic silicon resin, thermosetting polyimide, thermosetting polyurethane resin, cellulose resin, aldehyde ketone resin or fluorocarbon resin.
Wherein the rubber is at least one of styrene-butadiene rubber, chloroprene rubber, butadiene rubber, butyl rubber, isoprene rubber, ethylene-propylene-diene monomer rubber, natural rubber, nitrile rubber, silicone rubber, fluororubber, polyurethane rubber, polysulfide rubber, polyacrylate rubber, epichlorohydrin rubber, chlorosulfonated polyethylene, chlorinated polyethylene or butadiene-pyridine rubber.
Wherein the functional additive is at least one of a plasticizer, an antioxidant, a heat stabilizer, a light stabilizer, a lubricant, a vulcanizing agent, a coloring agent, a flame retardant, an antistatic agent or a thickening agent.
Wherein the plasticizer is at least one of dioctyl phthalate, dibutyl phthalate, dioctyl sebacate, dioctyl adipate, tricresyl phosphate, chlorinated paraffin, epoxidized soybean oil, propylene glycol sebacate polyester, propylene glycol adipate polyester, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, phenyl alkylsulfonate, process oil, heavy oil, paraffin, vaseline, asphalt, petroleum resin, coal tar, coumarone resin, coal tar, rosin, pine tar, terpene resin, factice, phthalate, phosphate ester, aliphatic dibasic ester, nitrile rubber, liquid polybutadiene or liquid polyisobutylene.
Wherein the antioxidant is at least one of alkyl monophenol, alkyl polyphenol, thiobisphenol, semi-solid phenol derivatives, aminophenol derivatives, p-phenylenediamine, diaromatic secondary amine, ketoamine, thioester or phosphite.
Wherein the heat stabilizer is at least one of tribasic lead sulfate, dibasic lead phosphite, dibasic lead stearate, dibasic lead phthalate, tribasic lead maleate, stearic acid, lauric acid, palmitic acid, oleic acid, metal salts, thiolate, fatty acid salts, maleate, stibium mercaptide, epoxide, phosphite ester, semi-solid alcohol, beta-diketone, solid Ga/Zn composite stabilizer or lanthanide rare earth metal elements.
Wherein the light stabilizer is at least one of titanium dioxide, zinc oxide, lithopone, iron oxide red, hindered amine, benzophenone or benzotriazole.
Wherein the lubricant is at least one of stearic acid, stearic acid soap, n-butyl stearate, stearic acid monoglyceride, tristearin, higher fatty alcohol, semisolid alcohol, polyethylene glycol, polypropylene glycol, oleamide, stearic acid amide, ethylene bis-oleamide, ethylene bis-stearamide or paraffin.
Wherein the vulcanizing agent is at least one of thiazoles, thiurams, sulfenamides, guanidines, dithiocarbamates, aldamines, xanthates, thioureas, zinc oxide, magnesium oxide, calcium oxide, stearic acid, lauric acid, diethanolamine or triethanolamine.
Wherein the colorant is at least one of carbon black, gold powder, silver powder, titanium dioxide, lithopone, chrome yellow, cadmium red, azo compounds, phthalocyanine compounds, dioxazine compounds or fluorescent compounds.
Wherein the flame retardant is at least one of tetrabromobisphenol A, decabromodiphenyl ether, hexabromocyclododecane, octabromodiphenyl ether, bis (tribromophenoxy) ethane, hexabromobenzene, brominated polystyrene, ethylene bis (tetrabromophthalimide), polydibromophenyl ether, phosphate ester, halogen-containing phosphate ester, polyphosphate ester, red phosphorus, triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, aluminum hydroxide, magnesium hydroxide or zinc borate.
Wherein the antistatic agent is at least one of stearyl trimethyl quaternary ammonium hydrochloride, stearamidopropyl hydroxyethyl quaternary ammonium nitrate, sodium p-nonylphenoxypropyl sulfonate, alkyl bis (alpha-hydroxyethyl amine phosphate), polyacrylate, salt of maleic anhydride and other unsaturated monomer copolymers, polystyrene benzene sulfonic acid, tetrabromobisphenol A, stearic acid monoglyceride, alkyl dicarboxymethyl ammonium ethyl lactone or dodecyl dimethyl quaternary ethyl inner salt.
Wherein the thickener is at least one of carboxyethyl cellulose, nitrocellulose, polyisobutylene, starch, gelatin, ethyl cellulose, hydroxypropyl methyl cellulose, diatomite, white carbon black, sodium carboxymethylcellulose, organic bentonite, sodium bentonite silica gel or carbon nano tube.
Wherein, in the step (3), the processing and forming method is at least one of curing, open milling, banburying, extruding, blow molding, pressing, injecting, calendering, blow molding, tentering film, static casting, insert casting, centrifugal casting, casting, slush molding, rotational molding, cold-pressing sintering, coating, spinning and foaming methods.
The invention principle is as follows: the crystalline conductive filler with different morphologies can be prepared by a simple melting recrystallization process, and the morphologies are favorable for reducing the percolation threshold. Wherein, the liquid metal is used as a solvent phase, other metals are used as solute phases, the solute phases form a uniform molten alloy phase in the liquid metal solvent phase through heating and melting, and the molten alloy is cooled and recrystallized at room temperature. During the recrystallization process, the liquid metal can guide the crystal growth process after the nucleation of the solute metal through the preference of symmetry or orientation, so that crystalline conductive fillers with different micro-morphologies, particularly high-length-diameter ratio micro-morphologies such as a rod shape, a sheet shape or a needle shape, are obtained after cooling. The high aspect ratio micro-morphology increases the probability that the crystalline conductive fillers contact each other in the polymer matrix to form a conductive network. More importantly, the liquid metal component in the crystalline conductive filler is quickly oxidized to form a liquid metal oxide layer, so that the surface energy of the crystalline conductive filler is effectively reduced, the compatibility between the crystalline conductive filler and a polymer matrix is improved, and the crystalline conductive filler is uniformly dispersed in the polymer matrix. Therefore, under the combined action of the high-length-diameter ratio micro-morphology and the improved dispersibility, the seepage threshold value of the conductive polymer composite material is obviously reduced, the mechanical property and the processing property of the material are improved, and the production cost is reduced.
The percolation threshold theory of fig. 1 is a classical conduction theory in composite conductive polymers, which means that when the conductive filler reaches a certain critical value, the conductivity of the material rises sharply, and a sudden change occurs from the insulator to the conductor. The amplitude of the conductivity change in the mutation process can reach 10 orders of magnitude. At this time, the corresponding critical value of the conductive filler is called the percolation threshold, i.e., point a in fig. 1.
Has the advantages that: compared with the prior art, the invention has the following remarkable effects: (1) The material seepage threshold is low, and the seepage threshold of the conductive macromolecule can be as low as 5% by volume. (2) The conductive polymer has good conductivity, and the conductivity resistivity can be as low as 1 × 10 -7 Omega cm. (3) The mechanical property is good, and the tensile Young modulus of the conductive polymer can be more than 700MPa. (4) The conductive polymer has good processability, and can be processed in batches.
Drawings
FIG. 1 shows the percolation threshold theory of a composite conductive polymer;
fig. 2 is a scanning electron microscope image of the crystalline conductive filler of example 9.
Detailed Description
The present invention is described in further detail below.
Example 1
The invention discloses a preparation method of a conductive polymer composite material with a low percolation threshold, which comprises the following steps:
(1) Weighing gallium simple substance, lead simple substance powder, polyethylene and antioxidant 264 according to the mixture ratio in Table 1;
(2) Roughly mixing elementary gallium powder and elementary lead powder, heating the mixture to 600 ℃, uniformly mixing, and cooling at room temperature to obtain a conductive filler;
(3) Coarsely mixing the conductive filler, polyethylene and the antioxidant 264;
(4) And (3) forming the mixture at 180 ℃ by applying 6MPa pressure through a hot-press forming method.
Example 2
The basic procedure was the same as in example 1, with the specific parameters shown in Table 1.
Example 3
The basic procedure was the same as in example 1, and the specific parameters are shown in Table 1.
Example 4
The basic procedure was the same as in example 1, and the specific parameters are shown in Table 1.
TABLE 1
Figure BDA0004009906920000051
For examples 1-4, after the processing and forming of steps 1-4, the liquid metal content of the material is respectively 8%, 7%, 10%, 90% by volume; the proportion of other metals is 0.6%, 2.8%, 7.3% and 2% respectively; the conductive filler of the material accounts for 8.6 percent, 9.8 percent, 17.3 percent and 92 percent of volume fraction respectively; the seepage threshold of the material is respectively 6%, 8%, 15% and 28% by volume fraction; the resistivity of the material is 1.2X 10 respectively -6 Ω·cm、2.7×10 -6 Ω·cm、3.5×10 -6 Ω·cm、9.0×10 -6 Ω·cm。
Example 5
(1) Weighing gallium simple substance, aluminum simple substance powder, polyvinyl chloride and tribasic lead sulfate according to the mixture ratio in the table 2;
(2) Roughly mixing a gallium elementary substance and aluminum elementary substance powder, heating the mixture to 800 ℃, uniformly mixing, and cooling at room temperature to obtain a conductive filler;
(3) Roughly mixing conductive filler, polyvinyl chloride and tribasic lead sulfate;
(4) The mixture is molded by hot press molding under 6MPa pressure at 200 ℃.
Example 6
The basic procedure was the same as in example 5, and is specifically shown in Table 2.
Example 7
The basic procedure was the same as in example 5, and is specifically shown in Table 2.
Example 8
The basic procedure was the same as in example 5, and is specifically shown in Table 2.
TABLE 2
Figure BDA0004009906920000061
For examples 5 to 8, after the processing and forming in steps 1 to 4, the volume fractions of the liquid metal in the conductive polymer composite material are 20%, 12.8%, 20% and 20%, respectively; the volume fraction of other metals is 0.9%, 10%, 6.9% and 9.6%; the volume fractions of the conductive filler are respectively 20.9%, 22.8%, 26.9% and 29.6%; after detection, the seepage threshold values of the conductive polymer composite material are respectively 7%, 20%, 10% and 25% in volume fraction; resistivity of 4.2 × 10 respectively -6 Ω·cm、2.3×10 -6 Ω·cm、5.4×10 -6 Ω·cm、3.2×10 -6 Ω·cm。
Example 9
(1) Weighing gallium simple substance, silver simple substance powder, polyethylene and antioxidant 264 according to the mixture ratio in the table 3;
(2) Roughly mixing elementary gallium and elementary silver powder, heating the mixture to 600 ℃, uniformly mixing, and cooling at room temperature to obtain the conductive filler (the microscopic morphology is shown in figure 2);
(3) Coarsely mixing the conductive filler, polyethylene and the antioxidant 264;
(4) Molding the mixture at 180 deg.C under 6MPa by hot press molding
TABLE 3
Figure BDA0004009906920000071
For example 9, after the processing steps 1 to 4, the volume fraction of the liquid metal in the conductive polymer composite material was 14.5%; the proportion of other metals is 5 percent by volume; after detection, the volume fraction of the conductive filler is 19.5%; the seepage threshold of the composite material is 15% by volume; resistivity of 3X 10 -6 Ω·cm。
As shown in fig. 2, the conductive filler micro-morphology is characterized by scanning electron microscopy, and it can be seen that the conductive filler exhibits needle-like morphology with high aspect ratio.
Example 10
(1) Weighing gallium-zinc alloy, lead simple substance powder, polyethylene and antioxidant 264 according to the mixture ratio in Table 4;
(2) Roughly mixing gallium-zinc alloy and lead simple substance powder, heating the mixture to 600 ℃, uniformly mixing, and cooling at room temperature to obtain a conductive filler;
(3) Coarsely mixing the conductive filler, polyethylene and the antioxidant 264;
(4) And (3) forming the mixture at 180 ℃ by applying 6MPa pressure through a hot-press forming method.
TABLE 4
Figure BDA0004009906920000072
ForExample 10, after the processing steps 1 to 4, the volume fraction of the liquid metal in the conductive polymer composite material is 13.5%; the proportion of other metals is 0.9 percent by volume; after detection, the volume fraction of the conductive filler is 14.4%; the percolation threshold of the composite material is 10% by volume; resistivity of 2X 10 -6 Ω·cm。
Example 11
(1) Weighing gallium elementary substance, aluminum elementary substance powder, copper elementary substance powder, polyethylene and antioxidant 264 according to the mixture ratio in the table 5;
(2) Roughly mixing a gallium elementary substance, aluminum elementary substance powder and copper elementary substance powder, heating the mixture to 950 ℃, uniformly mixing, and cooling at room temperature to obtain a conductive filler;
(3) Coarsely mixing the conductive filler, polyethylene and the antioxidant 264;
(4) And (3) forming the mixture at 180 ℃ by applying 6MPa pressure through a hot-press forming method.
TABLE 5
Figure BDA0004009906920000081
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For example 11, after processing steps 1-4, the composite had a liquid metal content of 12.5% by volume; the volume fraction of other metals is 1.9%; after detection, the volume fraction of the conductive filler is 14.4%; the percolation threshold of the composite material is 10% by volume; resistivity of 5X 10 -6 Ω·cm。
Example 12
(1) Weighing gallium-indium alloy, aluminum elemental powder, copper elemental powder, polyethylene and antioxidant 264 according to the mixture ratio in the table 6;
(2) Roughly mixing gallium-indium alloy, aluminum elementary substance powder and copper elementary substance powder, heating the mixture to 950 ℃, uniformly mixing, and cooling at room temperature to obtain a conductive filler;
(3) Coarsely mixing the conductive filler, polyethylene and the antioxidant 264;
(4) And (3) forming the mixture at 180 ℃ by applying 6MPa pressure through a hot-press forming method.
TABLE 6
Figure BDA0004009906920000082
For example 12, after processing steps 1-4, the composite material had a liquid metal content of 10.5% by volume; the volume fraction of other metals is 12.9%; after detection, the volume fraction of the conductive filler is 23.4%; the seepage threshold of the composite material is 15% by volume; resistivity of 4X 10 -6 Ω·cm。
Example 13
(1) Weighing gallium indium tin alloy, aluminum simple substance powder, copper simple substance powder, polyethylene and antioxidant 264 according to the mixture ratio in Table 7;
(2) Roughly mixing gallium-indium-tin alloy, aluminum elementary substance powder and copper elementary substance powder, heating the mixture to 950 ℃, uniformly mixing, and cooling at room temperature to obtain a conductive filler;
(3) Coarsely mixing the conductive filler, polyethylene and the antioxidant 264;
(4) And (3) forming the mixture at 180 ℃ by applying 6MPa pressure through a hot-press forming method.
TABLE 7
Figure BDA0004009906920000091
For example 13, after processing steps 1-4, the composite material had a liquid metal content of 9.5% by volume; the volume fraction of other metals is 13.9 percent; the volume fraction of the conductive filler of the composite material is 23.4 percent; after detection, the seepage threshold of the composite material is 15% by volume; resistivity of 3X 10 -6 Ω·cm。
Example 14
(1) Weighing gallium indium tin alloy, copper aluminum alloy, polyethylene and antioxidant 264 according to the proportion in table 8;
(2) Roughly mixing gallium indium tin alloy and copper aluminum alloy, then heating the mixture to 950 ℃, uniformly mixing, and cooling at room temperature to obtain a conductive filler;
(3) Coarsely mixing the conductive filler, polyethylene and the antioxidant 264;
(4) And (3) forming the mixture at 180 ℃ by applying 6MPa pressure through a hot-press forming method.
TABLE 8
Figure BDA0004009906920000092
For example 14, the liquid metal of the composite material accounted for 16.7% by volume after processing steps 1-4; the volume fraction of other metals is 11 percent; the volume fraction of the conductive filler in the composite material is 27.7%; after detection, the seepage threshold of the composite material is 20% of volume fraction; resistivity of 4X 10 -6 Ω·cm。
Comparative example 1
The basic procedure was the same as in example 1, and is specifically shown in Table 9.
TABLE 9
Figure BDA0004009906920000101
For comparative example 1, the volume fraction of the liquid metal in the composite material was 4% after the same processing steps 1 to 4 as in example 1; the volume fraction of other metals is 30.6 percent; the volume fraction of the conductive filler is 34.6 percent; after detection, the seepage threshold of the composite material is 50% of volume fraction; resistivity of 4X 10 9 Ω·cm。
Comparative example 2
The basic procedure was the same as in example 1, as shown in Table 10.
Watch 10
Figure BDA0004009906920000102
Comparative example 2 was subjected to the same processing steps 1 to 4 as in example 1, and then repeatedThe volume fraction of the liquid metal of the composite material is 96%; the volume fraction of other metals is 1%; the volume fraction of the conductive filler is 97%; after detection, the seepage threshold of the composite material is 90%; resistivity of 3X 10 -5 Ω·cm。
Comparative example 3
The basic procedure was the same as in example 1, and is specifically shown in Table 11.
TABLE 11
Figure BDA0004009906920000103
For comparative example 3, the liquid metal of the composite material accounts for 7% by volume after the same processing steps 1-4 as in example 1; the volume fraction of other metals is 72 percent; the volume fraction of the conductive filler is 79 percent; after detection, the seepage threshold of the composite material is 85% of the volume fraction; resistivity of 1X 10 10 Ω·cm。
Comparative example 4
The basic procedure was the same as in example 5, and is specifically shown in Table 12.
TABLE 12
Figure BDA0004009906920000111
For comparative example 4, the liquid metal of the composite material accounts for 3% by volume after the same processing steps 1-4 as example 5; 76% of other metals by volume; the volume fraction of the conductive filler is 75 percent; after detection, the seepage threshold of the composite material is 80% of the volume fraction; resistivity of 2X 10 10 Ω·cm。
Comparative example 5
The basic procedure was the same as in example 10, as shown in Table 13.
Watch 13
Figure BDA0004009906920000112
For comparative example 5, the liquid metal of the composite material accounts for 2% by volume after the same processing steps 1-4 as example 10; the volume fraction of other metals is 77%; the volume fraction of the conductive filler accounts for 76%; after detection, the seepage threshold of the composite material is 80% by volume; resistivity of 1X 10 10 Ω·cm。
Comparative example 6
The basic procedure was the same as in example 11, and is specifically shown in Table 14.
TABLE 14
Figure BDA0004009906920000113
For comparative example 6, the liquid metal of the composite material occupied 3% by volume after the same processing steps 1 to 4 as in example 11; 76% of other metals by volume; the volume fraction of the conductive filler is 79 percent; after detection, the seepage threshold of the composite material is 85% of the volume fraction; resistivity of 3X 10 10 Ω·cm。
Comparative example 7
The basic procedure was the same as in example 12, and is specifically shown in Table 15.
Watch 15
Figure BDA0004009906920000121
For comparative example 7, the volume fraction of the liquid metal in the composite material was 3% after the same processing steps 1 to 4 as in example 12; the volume fraction of other metals is 80.5 percent; the volume fraction of the conductive filler is 83.5 percent; after detection, the seepage threshold of the composite material is 90% of the volume fraction; resistivity of 1X 10 10 Ω·cm。
Comparative example 8
The basic procedure was the same as in example 13, and is specifically shown in Table 16.
TABLE 16
Figure BDA0004009906920000122
For comparative example 8, the liquid metal of the composite material accounted for 4% by volume after the same processing steps 1-4 as in example 13; 78% of other metals by volume; the volume fraction of the conductive filler is 82%; after detection, the seepage threshold of the composite material is 85% of the volume fraction; resistivity of 2X 10 10 Ω·cm。
Comparative example 9
The basic procedure was the same as in example 14, and is specifically shown in Table 17.
TABLE 17
Figure BDA0004009906920000123
For comparative example 9, the liquid metal of the composite material was 3% by volume after the same processing steps 1 to 4 as in example 14; the volume fraction of other metals is 18.7 percent; the volume fraction of the conductive filler of the composite material is 21.7 percent; the seepage threshold of the composite material is 50% by volume; resistivity of 2X 10 10 Ω·cm。

Claims (9)

1. A preparation method of a low-percolation threshold conductive polymer composite material is characterized by comprising the following steps:
(1) Mixing liquid metal and other metals, and heating to melt the liquid metal and other metals to form a melt;
(2) Cooling the melt for recrystallization to obtain a crystalline conductive filler;
(3) And mixing the crystalline conductive filler with a polymer matrix, and processing and molding to obtain the conductive polymer composite material.
2. The method for preparing a low percolation threshold conductive polymer composite according to claim 1, wherein the percolation threshold of the conductive polymer composite is 5-30% by volume.
3. The method for preparing the low percolation threshold conductive polymer composite material according to claim 1, wherein in the step (1), the volume part ratio of the liquid metal to the other metal is 5-95: 0 to 70 percent; wherein endpoint values are not included.
4. The method for preparing the low percolation threshold conductive polymer composite material according to claim 1, wherein in step (1), the liquid metal is at least one simple substance of gallium, zinc, bismuth, indium, tin, and aluminum, or an alloy of two or more elements.
5. The method according to claim 1, wherein in step (1), the other metal is at least one of gold, silver, copper, zinc, mercury, platinum, cadmium, aluminum, iron, cobalt, nickel, gallium, indium, tin, bismuth, lead, chromium, tellurium, cesium, titanium, vanadium, lanthanide, actinide, scandium, iridium, tungsten, yttrium, lithium, manganese, magnesium, antimony, thallium, calcium, sodium, potassium, rubidium, cesium, francium, beryllium, strontium, barium, radium, germanium, polonium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, rhenium, osmium, thorium, protactinium, uranium, plutonium, americium, curium, californium, fermium, ferrite, lutetium, hafnium, and alloys of more than two metals.
6. The method for preparing the low percolation threshold conductive polymer composite according to claim 1, wherein in step (3), the volume fraction of the polymer matrix is 5 to 95 parts.
7. The method for preparing the conductive polymer composite material with the low percolation threshold according to claim 1, further comprising a functional additive in the step (3), wherein the functional additive is 0 to 5 parts by volume.
8. The method for preparing a low percolation threshold conductive polymer composite according to claim 1, wherein in step (2), the crystalline conductive filler has a spherical, needle-like, rod-like, flake-like, pentagram-like, or snowflake-like micro-morphology.
9. The method for preparing a low percolation threshold conductive polymer composite according to claim 1, wherein in step (3), the polymer matrix is a thermoplastic resin, a thermosetting resin or a rubber.
CN202211646681.XA 2022-12-21 2022-12-21 Preparation method of conductive polymer composite material with low percolation threshold Pending CN115895090A (en)

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