Conductive polymer composition, conductive polymer sheet, electrical device, and their preparation methods
The present invention provides a conductive polymer composition, a conductive polymer sheet, an electrical device, and their preparation methods. The conductive polymer composition of the present invention includes a polymer and a conductive powder at a volume ratio of 35:65 to 65:35. The polymer includes at least one semicrystalline polymer selected from polyolefin, a copolymer of at least one olefin and at least one non-olefinic monomer copolymerizable therewith, and a thermoformable fluorine-containing polymer. The stated conductive powder includes at least one powder of a transition metal carbide, a transition metal carbon silicide, a transition metal carbon aluminide, and a transition metal carbon stannide. And the stated size distribution of the conductive powder satisfies: 20>D 100 /D 50 >6, where D 50 denotes a corresponding particle size when a cumulative particle-size distribution percent in the conductive powder reaches 50%, and D 100 denotes a maximum particle size. The stated conductive polymer composition has excellent processability, and can be used for preparing a PPTC device with ultralow resistance and stability in air without an oxygen barrier coating.
1. A conductive polymer composition comprising a polymer and a conductive powder at a volume ratio of 65:35 to 35:65, wherein the polymer includes at least one semicrystalline polymer selected from polyolefin, a copolymer of at least one olefin and at least one non-olefinic monomer copolymerizable therewith, and a thermoformable fluorine-containing polymer, wherein the stated conductive powder includes at least one powder of a transition metal carbide, a transition metal carbon silicide, a transition metal carbon aluminide, and a transition metal carbon stannide, and a size distribution of the conductive powder satisfies: 20>D 100 /D 50 >6, wherein D 50 denotes a corresponding particle size when a cumulative particle-size distribution percent in the conductive powder reaches 50%, and D 100 denotes a maximum particle size.
2. The conductive polymer composition according to claim 1 , wherein the stated polyolefin includes polypropylene, polyethylene or a copolymer of ethylene and propylene, the stated copolymer including at least one of ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylate copolymer, and ethylene-butyl acrylate copolymer and the stated thermoformable fluorine-containing polymer including polyvinylidene fluoride or ethylene/tetrafluoroethylene copolymer.
3. The conductive polymer composition according to claim 2 , wherein the stated polyethylene includes high-density polyethylene, middle-density polyethylene, low-density polyethylene or linear low-density polyethylene.
4. The conductive polymer composition according to claim 1 , wherein the conductive powder is dispersed in the polymer.
5. The conductive polymer composition according to claim 1 , wherein the conductive powder includes titanium carbide, tungsten carbide, titanium silicon carbide, titanium aluminum carbide or titanium tin carbide.
6. The conductive polymer composition according to claim 1 , wherein the conductive powder is quasi-spherical.
7. The conductive polymer composition according to claim 1 , wherein the conductive powder has D 50 <5 μm and D 100 <50 μm.
8. The conductive polymer composition according to claim 1 , wherein the size distribution of the conductive powder satisfies: 10>D 100 /D 50 >6.
9. The conductive polymer composition according to claim 1 , wherein the carbon content in the transition metal carbide is less than theoretical total carbon content in a transition metal carbide MC of a stoichiometric ratio by 2% to 5%, wherein M denotes a transition metal element.
10. The conductive polymer composition according to claim 9 , wherein the conductive powder is tungsten carbide WC, and carbon content T.C. in WC is 5.90% to 6.00%, wherein T.C. is 100%×C/WC by mass; or the conductive powder is titanium carbide TiC, and carbon content T.C. in TiC is 19.0% to 19.5%, wherein T.C. is 100%×C/TiC by mass.
11. A conductive polymer sheet obtained by melting and extruding the conductive polymer composition according to claim 1 .
12. An electrical device, including a first electrode, a second electrode, and a conductive polymer layer sandwiched between the first and second electrodes, wherein the conductive polymer layer is formed from the conductive polymer composition according to claim 1 .
13. The electrical device according to claim 12 , wherein the electrical device is an overcurrent protection device with a positive temperature coefficient characteristic.
14. The electrical device according to claim 13 , wherein resistivity of the overcurrent protection device in a non-protected state is less than 200 μΩ·cm.
15. A method for obtaining a positive temperature coefficient polymer material with air stability and ultralow resistance, the method comprising: blending a polymer and a conductive powder at a volume ratio of 65:35 to 35:65, wherein the polymer includes at least one semicrystalline polymer selected from polyolefin, a copolymer of at least one olefin and at least one non-olefinic monomer copolymerizable therewith, and a thermoformable fluorine-containing polymer, the stated conductive powder includes at least one powder of a transition metal carbide, a transition metal carbon silicide, a transition metal carbon aluminide, and a transition metal carbon stannide, and a size distribution of the stated conductive powder satisfies: 20>D 100 /D 50 >6, wherein D 50 denotes a corresponding particle size when a cumulative particle-size distribution percent in the conductive powder reaches 50%, and D 100 denotes a maximum particle size.
16. The method according to claim 15 , wherein the conductive powder includes titanium carbide, tungsten carbide, titanium silicon carbide, titanium aluminum carbide or titanium tin carbide.
17. The method according to claim 15 , wherein the conductive powder is quasi-spherical.
18. The method according to claim 17 , wherein a conductive powder of the stated quasi-spherical is prepared by using centrifugal rotation, rotary atomization, centrifugal rotation and condensation, induction or resistance heating spheroidization, plasma spheroidization or gas atomization.
19. The method according to claim 15 , wherein the size distribution of the conductive powder satisfies: 10>D 100 /D 50 >6.
20. The method according to claim 19 , wherein the conductive powder is obtained by using an airflow screening manner.
21. The method according to claim 20 , wherein the conductive powder is separated by using a cyclonic separator.
22. The method according to claim 19 , wherein the conductive powder is obtained by compounding more than two conductive powders.
23. The method according to claim 15 , wherein the carbon content in the transition metal carbide is controlled to be less than theoretical total carbon content in a transition metal carbide MC of a stoichiometric ratio by 2% to 5%, wherein M denotes a transition metal element.
24. The method according to claim 23 , wherein the conductive powder is tungsten carbide WC, and carbon content T.C. in WC is 5.90% to 6.00%, wherein T.C. is 100%×C/WC by mass; or, the conductive powder is titanium carbide TiC, and carbon content T.C. in TiC is 19.0% to 19.5%, wherein T.C. is 100%×C/TiC by mass.
25. The method according to claim 15 , wherein the blending includes physical mixing in a high-speed mixer or melting, blending, and extrusion in an extruder.
26. A method for preparing an overcurrent protection device with a positive temperature coefficient characteristic and air stability, the method including extruding a positive temperature coefficient polymer material obtained by using the method according to claim 15 , and laminating the first and second electrodes.
27. The method according to claim 26 , further including a step of sheet cutting after lamination and optional post-assembly steps, wherein the post-assembly steps include sheet punching, cutting, and molding.