CN102176359A - Cyclic annular positive temperature coefficient thermosensitive resistor and applications thereof - Google Patents
Cyclic annular positive temperature coefficient thermosensitive resistor and applications thereof Download PDFInfo
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- CN102176359A CN102176359A CN2011100277307A CN201110027730A CN102176359A CN 102176359 A CN102176359 A CN 102176359A CN 2011100277307 A CN2011100277307 A CN 2011100277307A CN 201110027730 A CN201110027730 A CN 201110027730A CN 102176359 A CN102176359 A CN 102176359A
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Abstract
The invention relates to a cyclic annular positive temperature coefficient thermosensitive resistor and applications thereof. A core layer is manufactured by mixing a high polymer, a conductive filler, an inorganic filler and a manufacturing auxiliary agent, and is composed of the following components in percentage by weight: 38-52% of high polymer, 35-55% of conductive filler; 5-25% of inorganic filler and a manufacturing auxiliary agent accounting for 0.05-3% of the total high polymer, wherein the high polymer is composed of two blends which has the same chemical structure, great difference in physical property and polyethylene is taken as the main resin. The coefficient thermosensitive resistor and applications thereof provided by the invention have the advantages that the resistor is used for over-current protection of a secondary cylinder lithium ion battery, a high polymer system with a self-reinforcing effect is introduced in as a substrate, the self-reinforcing polymer and the filler are subjected to compatibilizaiton treatment by conducting particles and the filler of special structures, the interface compatibility of the composite material is increased, and the resistor has the characteristics of low room temperature resistivity, high loading capability, high withstand voltage capability and excellent current impulsion resistant performances, and has less product lift-drag after current resisting.
Description
Technical field
The present invention relates to a kind of positive temperature coefficient thermistor, being specifically related to the high molecular polymer composite material is the circular positive temperature coefficient thermistor of primary raw material.
Background technology
Positive temperature coefficient (positive temperature coefficient) material refers to that its resistivity increases with the rising of temperature.Some macromolecules and conductive filler blend can make has lower room temperature resistivity, increase with temperature rising resistivity, and in the rapid phenomenon that raises of certain temperature spot resistivity.This class material with ptc characteristics has been made thermistor, is applied to the overcurrent protection setting of circuit.Usually under the state; electric current in the circuit is less relatively; the thermistor actuator temperature is lower; and when the big electric current that is caused by fault passes through this resettable fuse; its temperature can be elevated to the fusing point of polymer crystal suddenly, and swellable polymer cuts off conductive path, causes its resistance value to become very big; so just make circuit be in a kind of approximate " open circuit " state, thereby protected other element in the circuit.And after fault was got rid of, the temperature of thermistor descended, the crystallization again of its macromolecule, and volume contraction, resistance value can return to the low resistance state again, therefore are also referred to as and can recover fuse.Therefore, be necessary for the macromolecule action certain activity space is provided, the unit is under certain pressure state but the technical characterstic of cylindrical lithium ion battery has determined used circular positive temperature coefficient thermistor, promptly requires product being subjected to still bringing into play PTC effect (generally requiring pressurized 3kgf) under the situation of certain pressure.
Therefore be necessary to provide a kind of withstand voltage circular positive temperature coefficient thermistor.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of circular positive temperature coefficient thermistor, has that room temperature resistivity is low, load-carrying ability is high.
Another technical problem to be solved by this invention is to provide the purposes of above-mentioned circular positive temperature coefficient thermistor
The present invention solves the problems of the technologies described above the technical scheme of being taked: a kind of circular positive temperature coefficient thermistor, form by polymer composite sandwich layer and the conducting metal paillon foil that is compound in the sandwich layer two sides, the polymer composite sandwich layer forms by comprising that high molecular polymer, conductive filler, inorganic filler and processing aid are mixed with, wherein, described each components based on weight percentage of polymer composite sandwich layer comprises following composition:
High molecular polymer 38～52%
Conductive filler 20～48%
Inorganic filler 15～38%;
Other comprises the processing aid that accounts for high molecular polymer total amount 0.05～3%;
Wherein, it is identical that described high molecular polymer comprises at least two kinds of chemical constitutions, the poly blend that physical property differs greatly.
Concrete, the consumption of high molecular polymer can be 38,40,42,45,48,50 or 52%;
The consumption of conductive filler can be 20,22,25,30,32,35,38,40,42,45 or 48;
The consumption of inorganic filler can be 15,18,20,22,25,28,30,32,35 or 38%;
Processing aid accounts for 0.05,0.08,0.1,0.15,0.2,0.3,0.5,0.8,1,1.5,2,2.5 or 3% of high molecular polymer total amount.
On the basis of such scheme, the LLDPE that described high molecular polymer also comprises the surface grafting maleic anhydride that is used for increase-volume between polyethylene and the filler is an assisted resin, and this assisted resin accounts for 10～20% of high molecular polymer total amount.
Concrete, assisted resin accounts for the high molecular polymer total amount can be 10,12,154,16,18 or 20%.
On the basis of such scheme, the differential scanning calorimetry fusing point peak temperature difference of described any two kinds of high molecular polymers is not more than 10 ℃.
On the basis of such scheme, in the polyethylene of described physical property difference maximum, first kind of polyethylene is that weight average molecular weight is 100,000～300,000 polyethylene, and second kind of polyethylene is that weight average molecular weight is 1,000,000～4,000,000 ultra-high molecular weight polyethylene.
On the such scheme basis, described two kinds of poly heat distortion temperatures are all greater than 80 ℃, and the yield strength of first kind of polymer is 15～25Mpa, and the yield strength of second kind of polymer is not less than 35Mpa.
On the such scheme basis, described conductive filler at least conductive black, strengthen a kind of in the carbon black, and the dibutyl phthalate absorption of two kinds of conductive fillers of conductivity difference maximum differs and is not less than 50cc/100g.
On the such scheme basis, the particle diameter of described conductive black is 25～65 nanometers, and dibutyl phthalate (DBP) absorption value is 120～150cc/100g, BET nitrogen adsorption method specific area＜60m
2/ g;
The particle diameter of described enhancing carbon black is 80～120 nanometers, and dibutyl phthalate (DBP) absorption value is 70～100cc/100g, BET nitrogen adsorption method specific area＜30m
2/ g;
On the such scheme basis, described conductive black or enhancing carbon black are handled 3～5h through 200～300 ℃ of inert gases earlier, handle with silanes or titante coupling agent then.
On the such scheme basis, described conductive filler also comprises one or both in graphite, the carbon fiber.
On the such scheme basis, described inorganic filler comprises one or more of laminar nano imvite, nanometer or micron order calcium carbonate, nanometer or micron order magnesium hydroxide at least.
On the basis of such scheme, described processing aid comprises antioxidant, crosslinking accelerator and coupling agent, and wherein, antioxidant is phenols or aminated compounds, as phenolic antioxidant ANOX20; Crosslinking accelerator is the polyfunctional group unsaturated compound, as triallyl isocyanurate (TAIC); Coupling agent is one or more the mixture in silane coupler, aluminic acid ester or the titanate ester organic compound.
At the purposes of above-mentioned circular positive temperature coefficient thermistor, be used for secondary cylindrical lithium ion battery overcurrent protection.
The circular positive temperature coefficient thermistor of this secondary cylindrical lithium ion battery overcurrent protection, the resistance of finished product have the speciality that raises and increase with temperature, and voltage withstand class reaches 32V in the time of using under the pressure environment of 3kgf.
The invention has the beneficial effects as follows:
The circular positive temperature coefficient thermistor of the present invention is used for secondary cylindrical lithium ion battery overcurrent protection, compare with existing document, by two kinds of chemical constitutions are identical, the polyethylene blend that physical property differs greatly carries out self-reinforcing, introduced high molecular polymerization objects system at the polymer composite layer and done base material with self-strengthening, the conducting particles of special construction and filler, the LLDPE that adopts the surface grafting maleic anhydride simultaneously carries out increase-volume to the polymer of self-reinforcing and filler to be handled, increase the interface compatibility of composite material, improved the bearing capacity of polymer composite sandwich layer, have room temperature resistivity low (＜0.3ohm/cm), the load-carrying ability height (＞3kgf), under 3kgf pressure, still has positive preferably temperature characterisitic, proof voltage ability height (=32V), the characteristic of the excellent performance of anti-the rush of current, and the resistance of product liter is less behind anti-electric current.Therefore be a kind of ring-type PPTC of overcurrent protection reliability excellence.
Embodiment
A kind of circular positive temperature coefficient thermistor, form by polymer composite sandwich layer and the conducting metal paillon foil that is compound in the sandwich layer two sides, the polymer composite sandwich layer forms by comprising that high molecular polymer, conductive filler, inorganic filler and processing aid are mixed with, wherein, described high molecular polymer is identical for comprising at least two kinds of chemical constitutions, the polyethylene that physical property differs greatly is that the blend of main resin is formed, and described each components based on weight percentage of polymer composite sandwich layer comprises following composition:
High molecular polymer 38～52%
Conductive filler 20～48%
Inorganic filler 15～38%;
Other comprises the processing aid that accounts for high molecular polymer total amount 0.05～3%;
Wherein, it is identical that described high molecular polymer comprises at least two kinds of chemical constitutions, the poly blend that physical property differs greatly.
In the polyethylene of described physical property difference maximum, first kind of polyethylene weight average molecular weight is 100,000～300,000 polyethylene, and second kind of polyethylene weight average molecular weight is 1,000,000～4,000,000 ultra-high molecular weight polyethylene.
Experimental formula is shown in Table 1.
The remarks explanation:
1, main resin PE is that to comprise at least two kinds of chemical constitutions identical, the poly blend that physical property differs greatly;
2, assisted resin PE is the LLDPE of surface grafting maleic anhydride;
3, all comparative examples and embodiment all add 1010 antioxidant that account for high molecular polymer total content 0.5%; 0.8% TAIC crosslinking coagent; Account for the K550 silane coupler of total filler content 1%;
4, nano imvite (MMT) is provided by Zhejiang Feng Hong new material Co., Ltd;
5, strengthening carbon black (N762) is provided by the rich auspicious worker in Tianjin hundred million Co., Ltd;
6, L3000 surpasses at 15% o'clock and is difficult to processing.
With the granular high molecular polymer in the above-mentioned prescription through ball mill grinding powder process and and conductive filler, inorganic filler is pre-mixed, again by the even extruding pelletization of twin-screw melting mixing, with integral machine two surfaces up and down that the conducting metal paillon foil is compound in above-mentioned sandwich layer are obtained the long 200mm of size when extruding by single screw rod again, wide 150mm, thickness is the sheet material of 0.1～0.5mm, then with above-mentioned sheet material gamma-rays (Co60) or electron beam to irradiate crosslinked, dosage is 5～100Mrad, size design according to the cylindrical battery installing space, above-mentioned sheet material is cut into the circular chip of suitable size, can make finished product.
The properties of product test:
1, finished product room temperature resistivity measurement;
2, finished product is tested 15V/40A/6s energising, 60s outage and 32V/40A/6s energising, 60s outage respectively, follow-on test overcurrent 100 times, test resistance rate once more under the condition that applies 3kgf load;
3, finished product is under the condition that applies 3kgf load, tests behind 15V/40A and the 32V/40A overcurrent resistivity behind the withstand voltage 1h respectively;
Test result is as shown in table 2:
Claims (10)
1. circular positive temperature coefficient thermistor, form by polymer composite sandwich layer and the conducting metal paillon foil that is compound in the sandwich layer two sides, the polymer composite sandwich layer forms by comprising that high molecular polymer, conductive filler, inorganic filler and processing aid are mixed with, and it is characterized in that: described each components based on weight percentage of polymer composite sandwich layer comprises following composition:
High molecular polymer 38～52%
Conductive filler 20～48%
Inorganic filler 15～38%;
Other comprises the processing aid that accounts for high molecular polymer total amount 0.05～3%;
Wherein, it is identical that described high molecular polymer comprises at least two kinds of chemical constitutions, the poly blend that physical property differs greatly.
2. circular positive temperature coefficient thermistor according to claim 1, it is characterized in that: the LLDPE that described high molecular polymer also comprises the surface grafting maleic anhydride that is used for increase-volume between polyethylene and the filler is an assisted resin, and this assisted resin accounts for 10～20% of high molecular polymer total amount.
3. circular positive temperature coefficient thermistor according to claim 1 and 2, it is characterized in that: in the polyethylene of described physical property difference maximum, first kind of polyethylene is that weight average molecular weight is 100,000～300,000 polyethylene, and second kind of polyethylene is that weight average molecular weight is 1,000,000～4,000,000 ultra-high molecular weight polyethylene.
4. circular positive temperature coefficient thermistor according to claim 3, it is characterized in that: described two kinds of poly heat distortion temperatures are all greater than 80 ℃, the yield strength of first kind of polymer is 15～25Mpa, and the yield strength of second kind of polymer is not less than 35Mpa.
5. circular positive temperature coefficient thermistor according to claim 1, it is characterized in that: described conductive filler comprises conductive black at least, the particle diameter of described conductive black is 25～65nm, its dibutyl phthalate absorption is 120～150cc/100g, BET nitrogen adsorption method specific area＜60m
2/ g.
6. circular positive temperature coefficient thermistor according to claim 5, it is characterized in that: described conductive filler also comprises one or both in graphite, the carbon fiber, and the dibutyl phthalate absorption of two kinds of conductive fillers of conductivity difference maximum differs and is not less than 50cc/100g.
7. circular positive temperature coefficient thermistor according to claim 1 is characterized in that: described inorganic filler comprises one or more that strengthen carbon black, laminar nano imvite, nanometer or micron order calcium carbonate, nanometer or micron order magnesium hydroxide at least.
8. circular positive temperature coefficient thermistor according to claim 7 is characterized in that: the particle diameter of described enhancing carbon black is 80～120nm, and its dibutyl phthalate absorption is 70～100cc/100g, BET nitrogen absorption process specific area＜30m
2/ g.
9. according to the described circular positive temperature coefficient thermistor in one of claim 1 or 5 to 8, it is characterized in that: described conductive filler and inorganic filler are handled 3～5h through 200～300 ℃ of inert gases earlier, handle with silanes or titante coupling agent then.
10. at the purposes of the described circular positive temperature coefficient thermistor of one of claim 1 to 9, be used for secondary cylindrical lithium ion battery overcurrent protection.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011100277307A CN102176359A (en) | 2011-01-26 | 2011-01-26 | Cyclic annular positive temperature coefficient thermosensitive resistor and applications thereof |
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| CN2011100277307A CN102176359A (en) | 2011-01-26 | 2011-01-26 | Cyclic annular positive temperature coefficient thermosensitive resistor and applications thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013019A (en) * | 2012-12-03 | 2013-04-03 | 上海科特高分子材料有限公司 | Novel positive-temperature-coefficient thermistor element core layer material and application thereof |
| CN104821400A (en) * | 2015-03-18 | 2015-08-05 | 江苏乐能电池股份有限公司 | Safe conductive liquid for lithium iron phosphate and preparation method thereof |
| CN117551317A (en) * | 2024-01-09 | 2024-02-13 | 四川大学 | Low-Curie point positive temperature coefficient polymer composite material and preparation method and application thereof |
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| CN1202264A (en) * | 1995-09-29 | 1998-12-16 | 保险丝公司 | Improved polymeric PTC compositions |
| CN1416142A (en) * | 2002-11-19 | 2003-05-07 | 上海维安热电材料股份有限公司 | High molecular PTC thermistor without electric arc and method for producing same |
| CN2891303Y (en) * | 2005-12-12 | 2007-04-18 | 比亚迪股份有限公司 | Cylindrical lithium ion battery |
| EP2189989A1 (en) * | 2007-08-14 | 2010-05-26 | Tyco Electronics Japan G.K. | Ptc device and process for manufacturing the same |
| CN101870783A (en) * | 2010-06-25 | 2010-10-27 | 合肥上雅电子科技有限公司 | Polyvinyl PTC thermo-sensitive conductive composite material and manufacturing method thereof |
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2011
- 2011-01-26 CN CN2011100277307A patent/CN102176359A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202264A (en) * | 1995-09-29 | 1998-12-16 | 保险丝公司 | Improved polymeric PTC compositions |
| CN1416142A (en) * | 2002-11-19 | 2003-05-07 | 上海维安热电材料股份有限公司 | High molecular PTC thermistor without electric arc and method for producing same |
| CN2891303Y (en) * | 2005-12-12 | 2007-04-18 | 比亚迪股份有限公司 | Cylindrical lithium ion battery |
| EP2189989A1 (en) * | 2007-08-14 | 2010-05-26 | Tyco Electronics Japan G.K. | Ptc device and process for manufacturing the same |
| CN101870783A (en) * | 2010-06-25 | 2010-10-27 | 合肥上雅电子科技有限公司 | Polyvinyl PTC thermo-sensitive conductive composite material and manufacturing method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013019A (en) * | 2012-12-03 | 2013-04-03 | 上海科特高分子材料有限公司 | Novel positive-temperature-coefficient thermistor element core layer material and application thereof |
| CN104821400A (en) * | 2015-03-18 | 2015-08-05 | 江苏乐能电池股份有限公司 | Safe conductive liquid for lithium iron phosphate and preparation method thereof |
| CN104821400B (en) * | 2015-03-18 | 2017-01-25 | 江苏乐能电池股份有限公司 | Safe conductive liquid for lithium iron phosphate and preparation method thereof |
| CN117551317A (en) * | 2024-01-09 | 2024-02-13 | 四川大学 | Low-Curie point positive temperature coefficient polymer composite material and preparation method and application thereof |
| CN117551317B (en) * | 2024-01-09 | 2024-04-05 | 四川大学 | Low-Curie point positive temperature coefficient polymer composite material and preparation method and application thereof |
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Address after: Seven road 201202 Shanghai Pudong New Area Shiwan No. 1001 Applicant after: Shanghai Changyuan Wayon Circuit Protection Co., Ltd. Address before: Seven road 201202 Shanghai Pudong New Area Shiwan No. 1001 Applicant before: Shanghai Changyuan Wayon Circuit Protection Co., Ltd. |
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Application publication date: 20110907 |