CN109504016B - PTC film, preparation method thereof and thermistor - Google Patents
PTC film, preparation method thereof and thermistor Download PDFInfo
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Abstract
The invention relates to the field of a thermistor and a manufacturing method thereof, in particular to a PTC film and a preparation method thereof and a thermistor. A PTC film is prepared from a high molecular polymer which comprises the following raw materials in parts by weight: 30-40 parts of polystyrene HIPS, and 10-20 parts of one or more of polyethylene HDPE, polypropylene PP, polystyrene PS or polyvinylidene fluoride PVDF. The invention adopts two or three organic matters with different melting points as the matrix, when the temperature of the lithium battery rises, the PTC material generates double percolation action, the process can improve the repeatability of the resistance of the PTC material and weaken the NTC effect. When the lithium battery is in thermal runaway such as short circuit or overcharge, the resistance value of the PTC material is increased along with the rise of the temperature until the internal current is completely blocked, so that safety accidents such as fire and explosion are avoided.
Description
Technical Field
The invention relates to the field of a thermistor and a manufacturing method thereof, in particular to a PTC film and a preparation method thereof and a thermistor.
Background
Along with the rapid development of new energy automobiles, the requirement of the whole industry on the improvement of the energy density of the lithium battery is higher and higher, however, along with the improvement of the energy density, the safety problem of the lithium battery is also paid more and more attention by people. Once a lithium battery is operated under abuse conditions, such as short circuit, overcharge, etc., a series of side reactions occur inside the battery, and a large amount of heat is generated, thereby causing a safety problem.
In order to prevent a battery from generating a large amount of heat in a short time under the conditions of overcharge and short circuit, many battery factories need to install a thermosensitive device (PTC) inside or outside the battery, and at present, common PTC materials mainly use organic substances as a matrix, and conductive materials such as conductive carbon black, graphite, CNT, graphene and the like are doped into the matrix. However, most PTC films in the market have NTC (negative temperature coefficient) effect, and the surfaces of the conductive carbon have polar groups with different degrees, so that cohesive energy is stronger, and in addition, the carbon black has larger specific surface area and is difficult to disperse and easy to agglomerate in an organic matrix, so that the NTC effect of the PTC films is stronger, and the use is influenced.
Since many side reactions continuously occur inside the lithium battery when the temperature exceeds 100 ℃ during the use of the lithium battery, the PTC transition temperature for the lithium battery must be lower than 100 ℃. At present, the PTC material for the lithium battery mainly takes a single polyethylene high molecular polymer as a matrix, carbon black is added into the matrix as a conductive agent, the manufacturing process is simple, the PTC transition temperature is high (most of the PTC transition temperature exceeds 120 ℃), particularly, the NTC effect is obvious (namely, after a certain temperature is exceeded, the resistance value is reduced along with the temperature rise), and the PTC material cannot play a good protection role on the lithium battery.
Disclosure of Invention
Based on the defects, the invention provides a brand-new PTC film, and the preparation raw material of the film comprises high molecular polymer, wherein the high molecular polymer comprises the following components in parts by weight:
30-40 parts of polystyrene HIPS (high impact polystyrene),
10-20 parts of one or more of polyethylene HDPE, polypropylene PP, polystyrene PS or polyvinylidene fluoride PVDF.
Preferably, the high molecular polymer further includes:
10-15 parts of polymethyl methacrylate (PMMA).
More preferably, the high molecular polymer is composed of one or more of polystyrene HIPS, polyethylene HDPE, polypropylene PP, polystyrene PS or polyvinylidene fluoride PVDF, and polymethyl methacrylate PMMA.
The invention adopts two or three organic matters with different melting points as the matrix, when the temperature of the lithium battery rises, the PTC material generates double percolation action (namely the percolation process of the conductive agent in one continuous phase and the percolation process of the continuous phase in another polymer), and the process can improve the repeatability of the resistance of the PTC material and weaken the NTC effect. When the lithium battery is in thermal runaway such as short circuit or overcharge, the resistance value of the PTC material is increased along with the rise of the temperature until the internal current is completely blocked, so that safety accidents such as fire and explosion are avoided.
The PTC film provided by the invention comprises the following raw materials:
preferably, the coupling agent is preferably a titanate;
preferably, the grafting reactant is preferably maleic anhydride.
Preferably, the ceramic substrate is alumina.
In the PTC film, the conductive filler is preferably selected from one or more of carbon black and nickel powder;
more preferably, the conductive filler is made of carbon black and nickel powder according to (2-3): 1 in a certain proportion.
The invention adopts maleic anhydride as a grafting reactant to graft lipophilic groups on the surface of carbon black, thereby improving the compatibility of a conductive agent and a polymer. The surface of the carbon black is treated by adopting titanate as a coupling agent, so that carboxyl and hydroxyl groups on the surface of the carbon black are improved, and a proper amount of nickel powder is added, so that the conductivity is improved, the stability of the PTC material is improved, and the NTC effect is weakened.
The invention uses two or three polymers to replace the traditional single polymer as the raw material for preparing the PTC film, one organic phase in the PTC film mainly uses high impact polystyrene HIPS as the main material, the material has the largest resistivity at 100 ℃, does not react with electrolyte and electrodes at normal temperature, has certain PTC strength, the other organic phase is high melting point polyethylene HDPE, polypropylene PP and polyvinylidene fluoride PVDF with slightly higher melting point, the melting point of the material is between 130 ℃ and 180 ℃, the material does not react with the electrolyte and the electrodes at the same normal temperature, the third organic phase is polymethyl methacrylate PMMA (melting point 210 ℃) with higher melting point, and the material does not react with the electrolyte and the electrodes at the normal temperature. The conductive filler is carbon black and nickel powder.
As a preferred technical scheme of the invention, the preparation formula of the PTC film is as follows:
the high-molecular polymer is prepared by compounding polystyrene HIPS, one of polyethylene HDPE or polypropylene PP, polystyrene PS and polyvinylidene fluoride PVDF, and polymethyl methacrylate PMMA.
Preferably, the high molecular polymer is prepared by mixing, by mass, 15: (5-6): (4-6) polystyrene HIPS, polyethylene HDPE or polypropylene PP, polystyrene PS, one of polyvinylidene fluoride PVDF and polymethyl methacrylate PMMA.
The invention aims to invent a PTC film suitable for a lithium ion battery.
The invention takes high impact polystyrene HIPS as a matrix, and two or three kinds of high molecular organic polymers with different melting points are mixed as the matrix; maleic anhydride is used as a grafting reactant, and titanate is used as a coupling agent. The invention adopts the mixture of carbon black and nickel powder as the conductive agent, and the conductive effect is excellent when the conductive agent is used under the normal temperature condition. The high impact polystyrene is adopted as a main film matrix, and the resistance value of the film can be rapidly improved at about 100 ℃ (the battery has more side reactions and the initial stage of thermal runaway) to play the PTC effect. The NTC effect is obviously weakened by adopting two or more specific matrix main materials with different melting points, and the resistance value of the matrix main materials is always in an ascending trend when the temperature is continuously increased.
In summary, the invention adopts two or three organic matters with different melting points as the matrix, when the temperature of the lithium battery rises, the PTC material generates double percolation action, the process can improve the repeatability of the resistance of the PTC material and weaken the NTC effect. When the lithium battery is in thermal runaway such as short circuit or overcharge, the resistance value of the PTC material is increased along with the rise of the temperature until the internal current is completely blocked, so that safety accidents such as fire and explosion are avoided.
The invention further provides a preparation method of the PTC film in any technical scheme, which comprises the following steps:
and mixing the high molecular polymer, the conductive filler, the ceramic substrate, the coupling agent and the grafting reaction agent in a molten state, and stirring at a high speed. The invention also provides the application of the PTC film in any technical scheme in the thermistor.
The thermistor comprises the PTC film uniformly coated in the middle of a double-layer aluminum foil.
The preparation method of the thermistor comprises the following steps: and uniformly coating the PTC film between the double-layer aluminum foils, and pressing into sheets.
The thermistor has good thermal effect and stability, effectively reduces NTC effect, and has an applicable working temperature of-40 ℃ to 250 ℃; simple and convenient manufacturing process, easily obtained materials and strong overload capacity.
Drawings
Fig. 1 is a graph showing the relationship between the resistance and the temperature of the PTC film provided in examples 1 to 3.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
This example provides a PTC film, which is prepared according to the following formulation:
35% of molten high impact polystyrene HIPS, 15% of molten polyethylene HDPE or (polypropylene PP, polyvinylidene fluoride PVDF), 15% of carbon black, 10% of nickel powder, 20% of alumina, 2.5% of coupling agent titanate and 2.5% of grafting reactant maleic anhydride.
Example 2
This example provides a PTC film, which is prepared according to the following formulation:
30 percent of molten high impact polystyrene HIPS, 10 percent of molten polyethylene HDPE or (polypropylene PP, polyvinylidene fluoride PVDF), 10 percent of polymethyl methacrylate PMMA, 15 percent of carbon black, 10 percent of nickel powder, 20 percent of alumina, 2.5 percent of coupling agent titanate and 2.5 percent of grafting reactant maleic anhydride.
Example 3
The embodiment provides a PTC film and a preparation method thereof, and the preparation method comprises the following specific steps:
mixing 35% of molten high impact polystyrene HIPS, 15% of molten polystyrene PS, 10% of polymethyl methacrylate PMMA, 20% of carbon black, 5% of nickel powder, 10% of alumina, 2.5% of coupling agent titanate and 2.5% of grafting reactant maleic anhydride, and then stirring at a high speed to obtain the composite material.
Examples 4 to 6
Examples 4 to 6 each provide a thermistor obtained by uniformly applying the PTC film provided in examples 1 to 3 to the middle of a double-layered aluminum foil and pressing the resultant into a sheet.
Test example 1
This test example provides the relationship between the resistance and temperature of the PTC films provided in examples 1-3.
The measurement was carried out in a manner conventional in the art, and the results are shown in FIG. 1.
It can be seen that the PTC film of the present invention has the following characteristics:
the sensitivity is high, the working temperature range is wide, the applicable temperature of a high-temperature device is higher than 80 ℃, and the applicable temperature of a low-temperature device is at least-40 ℃; the product is easy to be processed into a complex shape and can be produced in large batch; good stability and strong overload capacity.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A PTC film is prepared from high-molecular polymer as raw material, and is characterized in that the raw material comprises:
50 parts of the high-molecular polymer is prepared,
15-35 parts of conductive filler,
20-30 parts of a ceramic substrate,
1-5 parts of a coupling agent,
1-8 parts of a grafting reactant;
the high molecular polymer comprises the following components in parts by weight:
30-40 parts of polystyrene HIPS (high impact polystyrene),
10-20 parts of one or more of polyethylene HDPE, polypropylene PP, polystyrene PS or polyvinylidene fluoride PVDF,
10-15 parts of polymethyl methacrylate (PMMA).
2. The PTC film according to claim 1, wherein the coupling agent is titanate;
and/or the ceramic substrate is alumina.
3. The PTC film according to claim 1, wherein the grafting reactant is maleic anhydride.
4. A PTC film according to any one of claims 1-3, wherein the conductive filler is one or two selected from carbon black and nickel powder.
5. The PTC film according to claim 4, wherein the conductive filler is composed of carbon black and nickel powder according to the ratio of (2-3): 1 in a certain proportion.
6. The PTC film according to claim 1, wherein the coupling agent is titanate; the ceramic substrate is aluminum oxide; the grafting reactant is maleic anhydride; the conductive filler is prepared from carbon black and nickel powder according to the following ratio of (2-3): 1 in proportion;
the PTC film comprises the following raw materials in parts by weight:
50 parts of the high-molecular polymer is prepared,
10-15 parts of carbon black,
8-12 parts of nickel powder,
20-25 parts of aluminum oxide(s),
2-3 parts of titanate, namely,
1-5 parts of maleic anhydride;
the high-molecular polymer is prepared by compounding polystyrene HIPS, one of polyethylene HDPE, polypropylene PP, polystyrene PS and polyvinylidene fluoride PVDF and polymethyl methacrylate PMMA.
7. The PTC film according to claim 6, wherein the high molecular polymer is prepared by mixing a polymer having a mass ratio of 15: (5-6): (4-6) polystyrene HIPS, one of polyethylene HDPE, polypropylene PP, polystyrene PS or polyvinylidene fluoride PVDF, and polymethyl methacrylate PMMA.
8. A method of preparing the PTC film according to any one of claims 1 to 5,
and mixing the high molecular polymer, the conductive filler, the ceramic substrate, the coupling agent and the grafting reaction agent in a molten state, and stirring at a high speed.
9. Use of a PTC film according to any one of claims 1-7 for the preparation of a thermistor.
10. A thermistor, characterized in that it comprises the PTC film applied between double layers of aluminum foil, the PTC film being as defined in any one of claims 1 to 7.
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| CN117757178B (en) * | 2024-02-22 | 2024-04-23 | 山东森博斯特塑胶科技有限公司 | Preparation method of temperature-sensing self-adjusting agricultural film |
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