CN102231431B - Compound nanofiber diaphragm for lithium ion power battery and manufacturing method - Google Patents
Compound nanofiber diaphragm for lithium ion power battery and manufacturing method Download PDFInfo
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Abstract
The invention discloses a compound nanofiber diaphragm for a lithium ion power battery. The compound nanofiber diaphragm comprises an upper layer, an upper middle layer, a middle layer, a lower middle layer and a lower layer, wherein the upper, middle and lower layers are polyethylene terephthalate (PET) nanofiber layers; the upper and lower middle layers are polyethylene nanofiber layers; the lower middle layer is covered on the lower layer; the middle layer is covered on the lower middle layer; the upper middle layer is covered on the middle layer; and the upper layer is covered on the upper middle layer. Or the compound nanofiber diaphragm adopts a three-layer structure form. The invention also provides the compound nanofiber diaphragm for the lithium ion power battery and a manufacturing method thereof. By the compound nanofiber diaphragm for the lithium ion power battery and the manufacturing method thereof, heat resistance is improved, a difference value between diaphragm rupturing temperature and obturating temperature is increased, and security is enhanced.
Description
Technical field
The present invention relates to a kind of lithium-ion-power cell barrier film and manufacture method thereof.
Background technology
Lithium ion battery (abbreviation lithium battery), have that energy density is high, power is large, service life cycle is high, voltage is high, the outstanding advantage such as memory-less effect and environmental protection, become the new forms of energy of world today's Devoting Major Efforts To Developing, be widely used in the various fields such as automobile, communication, Aero-Space, household electrical appliance.
Lithium battery mainly is comprised of parts such as positive pole, negative pole, electrolyte, barrier film and shells, wherein, barrier film is the vitals of lithium battery, and its effect is isolation positive pole and negative pole, electronics in battery can not freely be passed through, and electrolyte ion---lithium ion flows freely between both positive and negative polarity and allow.The size of lithium ion conduction ability is directly connected to the overall performance of lithium battery; In the situation that battery occurs and overcharges or short circuit, perhaps incorrect link in lithium battery isolation both positive and negative polarity, produce undesired electric current, and, when capacity high use large at power, all can cause the interior temperature of battery sharply to raise, battery diaphragm should have enough heatproof functions; Because battery temperature raises, cause membrane pore size to dwindle, lithium ion can not normally pass through, and causes battery temperature to raise, and reaches fusing point or the electrolytical point of ignition of lithium, will cause the burning of battery and the generation of explosion accident.
the lithium battery safety problem is urgent problems very, lithium-ion-power cell particularly, treat as the first major issue especially, battery Yin Wendu raises, cause diaphragm deflection, the temperature that micropore disappears is called " closed pore temperature ", after internal temperature of battery surpasses described closed pore temperature, the reduced viscosity of film, when reaching a certain temperature, film rupture occurs, because of film rupture, corresponding temperature is referred to as " broken film temperature ", if membrane ruptures, the electron ion of both positive and negative polarity is because of directly contact, and cause battery explosion, this is very dangerous accident to lithium-ion-power cell.
At present, the dynamic lithium battery of minority has entered the numerous areas such as automobile, robot, electric tool, Aero-Space, and dynamic lithium battery is larger due to the magnitude of current, so the security performance of barrier film should be mentioned higher level.
The barrier film of lithium battery should have sufficiently high heat resistance, the broken film temperature of barrier film is the decisive factor that determines battery security with the difference of closing film temperature, the barrier film of for example producing with stretch processes, as the low-pressure polyethylene film, 100 ℃ of closed pore temperatures, because of the polyethylene heat resistance poor, broken film temperature is 110 ℃, broken film temperature is very little, same with the difference of closing film temperature, three layers of stretching PP/PE/PP barrier film, the closed pore temperature of PE is 125 ℃, the broken film temperature of PP is 165 ℃, and the difference of broken film temperature and closed pore temperature is slightly large, neither be very good.The barrier film of producing with electrostatic spinning for another example, the material of use such as Kynoar etc., the difference of broken film temperature and closed pore temperature is also 55 ℃ of up and down, other the difference as the broken film temperatures such as polyacrylonitrile and closed pore temperature is also little; So, existing lithium ion battery separator, what the process production that don't work all exists broken film temperature and the closed pore temperature difference is little, causes the problem of lithium battery potential safety hazard; And dynamic lithium battery is large due to the use energy, and safety requirements is higher.For guaranteeing the safe operation of dynamic lithium battery, a kind of broken film temperature and the large power lithium battery diaphragm of closed pore temperature difference must be provided, reach dynamic lithium battery fail safe and stable on heating needs.
Summary of the invention
, broken film temperature relatively poor for the thermal endurance that overcomes existing power lithium battery diaphragm and the deficiency that the closed pore temperature difference is less, fail safe is relatively poor the invention provides and a kind ofly promote thermal endurance, improve broken film temperature and closed pore temperature difference, strengthen compound nanofiber diaphragm for lithium ion power battery and the manufacture method thereof of fail safe.
The technical solution used in the present invention is:
A kind of compound nanofiber diaphragm for lithium ion power battery, described compound nanofiber diaphragm for lithium ion power battery comprise the upper strata, at the middle and upper levels, middle level, middle lower floor and lower floor; Described the upper, middle and lower are the PET nanofiber layer, described is the PE nanofiber layer with middle lower floor at the middle and upper levels, and described middle lower floor covers in described lower floor, and described middle level covers in described middle lower floor, described covering at the middle and upper levels on described middle level, described upper strata cover describedly goes up at the middle and upper levels;
In described compound nanofiber diaphragm for lithium ion power battery, described upper strata, middle level, lower floor's mass content are independently 17～21% separately, and described is 19.5～23.5% with middle lower floor at the middle and upper levels;
Described the upper and lower include PET, SEBS, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of four components is: PET15 part, SEBS1～1.5 part, PS-g-ECMA2～2.5 part, nano-TiO
21～1.5 part;
Described middle level comprises PET, SEBS, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of four components is: PET15 part, SEBS1～1.5 part, PS-g-ECMA1.5～2.5 part, nano-TiO
21～1.5 part;
Describedly include PE, PS-g-ECMA and nano-TiO with middle lower floor at the middle and upper levels
2, the ratio of quality and the number of copies of three components is: PE18 part, PS-g-ECMA1.5～3 part, nano-TiO
20.5～1.5 parts.
A kind of compound nanofiber diaphragm for lithium ion power battery, described compound nanofiber diaphragm for lithium ion power battery comprise upper strata, lower floor and the middle level between upper strata and lower floor; Described the upper and lower are the PET nanofiber layer, and described middle level is the PE nanofiber layer, and described middle level covers in described lower floor, and described upper strata covers on described middle level;
In described compound nanofiber diaphragm for lithium ion power battery, described upper strata, lower floor's mass content are independently 31～37% separately, and described middle level is 28～36%;
Described the upper and lower include PET, SEBS, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of four components is: PET27～29 part, SEBS1～2 part, PS-g-ECMA2～4 part, nano-TiO
21～2 part;
Described middle level comprises PE, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of three components is: PE25～30 part, PS-g-ECMA2～4 part, nano-TiO
21～2 part.
Further, described upper strata, lower floor's mass content are independently 32～35.5% separately, and described middle level is 29.5～33%.
A kind of manufacture method of compound nanofiber diaphragm for lithium ion power battery, described manufacture method comprises the following steps:
(1), raw material preparation: in described compound nanofiber diaphragm for lithium ion power battery, described upper strata, middle level, lower floor's mass content are independently 17～21% separately, and described is 19.5～23.5% with middle lower floor at the middle and upper levels;
Described the upper and lower include PET, SEBS, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of four components is: PET15 part, SEBS1～1.5 part, PS-g-ECMA2～2.5 part, nano-TiO
21～1.5 part;
Described middle level comprises PET, SEBS, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of four components is: PET15 part, SEBS1～1.5 part, PS-g-ECMA1.5～2.5 part, nano-TiO
21～1.5 part;
Describedly include PE, PS-g-ECMA and nano-TiO with middle lower floor at the middle and upper levels
2, the ratio of quality and the number of copies of three components is: PE18 part, PS-g-ECMA1.5～3 part, nano-TiO
20.5～1.5 parts.
(2), extrude operation: the compound that each layer prepares, send into five extruders through each layered material bucket, five layers of extruder are extruded through molten condition, filter through multi-bed filter and enter die head, melt is evenly extruded through the die lip mouth;
The melt of the molten condition that the die lip mouth is flowed out is introduced high pressure syringe pump, melt enters the electrostatic spinning spinning head, provide high-voltage dc voltage at the spinning head mouth, under the promotion of electric field action and syringe pump pressure, form and spray thread, directive by leaps and bounds receives on guipure, forms woven cloths shape nanofiber compound barrier film;
(3), stripping process:
On described reception guipure, nanofiber compound barrier film forms continuously, adopts stripping off device to peel off continuously, and barrier film bead cutter excision burr make compound nanofiber diaphragm for lithium ion power battery.
A kind of manufacture method of compound nanofiber diaphragm for lithium ion power battery, described manufacture method comprises the following steps:
(1), raw material preparation: in described compound nanofiber diaphragm for lithium ion power battery, described upper strata, lower floor's mass content are independently 31～37% separately, and described middle level is 28～36%;
Described the upper and lower include PET, SEBS, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of four components is: PET28 part, SEBS1～2 part, PS-g-ECMA2～4 part, nano-TiO
21～2 part;
Described middle level comprises PE, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of three components is: PE28 part, PS-g-ECMA2～4 part, nano-TiO
21～2 part;
(2), extrude operation: the compound that each layer prepares, send into three extruders through each layered material bucket, three layers of extruder are extruded through molten condition, filter through multi-bed filter and enter die head, melt is evenly extruded through the die lip mouth;
The melt of the molten condition that the die lip mouth is flowed out is introduced high pressure syringe pump, melt enters the electrostatic spinning spinning head, provide high-voltage dc voltage at the spinning head mouth, under the promotion of electric field action and syringe pump pressure, form and spray thread, directive by leaps and bounds receives on guipure, forms woven cloths shape nanofiber compound barrier film;
(3), stripping process:
On described reception guipure, nanofiber compound barrier film forms continuously, adopts stripping off device to peel off continuously, and barrier film bead cutter excision burr make compound nanofiber diaphragm for lithium ion power battery.
Further, described upper strata, lower floor's mass content are independently 32～35.5% separately, and described middle level is 29.5～33%.
In the present invention, according to the size of the magnitude of current of electrokinetic cell, select the barrier film of five-layer structure or three-decker, for example usually can select the barrier film of seven and above electric automobile is five-layer structure, and the barrier film of the electric automobile below seven is three-decker.
Beneficial effect of the present invention is mainly reflected in: promote thermal endurance, improve broken film temperature and closed pore temperature difference, strengthen fail safe.
Figure of description
Fig. 1 is a kind of structural representation of compound nanofiber diaphragm for lithium ion power battery.
Fig. 2 is the structural representation of another kind of compound nanofiber diaphragm for lithium ion power battery.
Fig. 3 is the manufacturing approach craft flow chart of compound nanofiber diaphragm for lithium ion power battery.
Embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1
With reference to Fig. 1, a kind of compound nanofiber diaphragm for lithium ion power battery, described compound nanofiber diaphragm for lithium ion power battery comprise upper strata 1, at the middle and upper levels 4, middle level 2, middle lower floor 5 and lower floor 3; Described upper strata 1, middle level 2 and lower floor 3 are the PET nanofiber layer, described at the middle and upper levels 4 and middle lower floor 5 be the PE nanofiber layer, described middle lower floor covers in described lower floor, described middle level covers in described middle lower floor, described covering at the middle and upper levels on described middle level, described upper strata cover describedly goes up at the middle and upper levels;
In described compound nanofiber diaphragm for lithium ion power battery, described upper strata, middle level, lower floor's mass content are independently 17～21% separately, and described is 19.5～23.5% with middle lower floor at the middle and upper levels;
Described the upper and lower include PET, SEBS, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of four components is: PET15 part, SEBS1～1.5 part, PS-g-ECMA2～2.5 part, nano-TiO
21～1.5 part;
Described middle level comprises PET, SEBS, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of four components is: PET15 part, SEBS1～1.5 part, PS-g-ECMA1.5～2.5 part, nano-TiO
21～1.5 part;
Describedly include PE, PS-g-ECMA and nano-TiO with middle lower floor at the middle and upper levels
2, the ratio of quality and the number of copies of three components is: PE18 part, PS-g-ECMA1.5～3 part, nano-TiO
20.5～1.5 parts.
In the present embodiment, described upper strata mass content is 17%, and mass content is 23% at the middle and upper levels, and the middle level mass content is 20%, and middle lower floor mass content is 23%, and lower floor's mass content is 17%.
In described the upper and lower, the ratio of quality and the number of copies of four components is: PET15 part, SEBS1 part, PS-g-ECMA2 part, nano-TiO
21 part;
In described middle lower floor, the ratio of quality and the number of copies of four components is: PET15 part, SEBS1 part, PS-g-ECMA1.5 part, nano-TiO
21 part;
Wherein, the trade mark of PET is CB-608, and manufacturing enterprise is the Far East, Taiwan textile company; The trade mark of SEBS is 3333C, and manufacturing enterprise is Japanese Kunal Co., Ltd.; PS-g-ECMA (PE: CMA: PS=59.5: 10.5: 30), manufacturing enterprise is NOF Corp; Nano-TiO
2The trade mark of (battery special-purpose) is T-258, and manufacturing enterprise is female space nano material Co., Ltd;
Described middle lower floor and comprise at the middle and upper levels PE, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of three components is: PE18 part, PS-g-ECMA1.5 part, nano-TiO
20.5 part.Wherein, the trade mark of PE is 168Y, and manufacturing enterprise is Malaysian PETRONAS company; PS-g-ECMA (PE: CMA: PS=59.5: 10.5: 30), manufacturing enterprise is NOF Corp; Nano-TiO
2The trade mark of (battery special-purpose) is T-258, and manufacturing enterprise is female space nano material Co., Ltd.
The lithium ion compound fibre diaphragm of the present embodiment, to adopt high molecular polymer to carry out by the molten condition extrusion way barrier film that electrostatic spinning forms, the electrostatic spinning of general high molecular polymer all adopts the organic solvent dissolution high molecular polymer, becomes Polymer Solution, then carries out spinning; With respect to the solution method of electrostatic spinning, high molecular polymer molten condition electrostatic spinning has more advantage, the solution electrostatic spinning is because high molecular polymer is dissolved in solvent, solution concentration is very restricted, so production efficiency is relatively low, and cost is higher, but also need configuration solution-treated recovery system, solvent exists the volatilization problem in spinning process, not only exists air pollution, and involves operator's health problem.
and the electrostatic spinning under molten condition does not need the solvent processing procedure, but carry out spinning by extruding under the high molecular polymer molten condition, has high efficiency, low-cost, easily large-scale production and the obviously advantage of environmental protection, in addition, the electrostatic spinning of the extrusion way of molten condition obtains the nanometer barrier film and belongs to Nano grade, diameter is the composite fibre net of 40～500nm yardstick, when processing heat material high polymer, this technology demonstrates relative economy, the ability that also has simultaneously scale spinning nanofiber, therefore, electrostatic spinning under molten condition is a kind of innovation in electrostatic spinning.
The raw material that electrostatic spinning of the present invention drops into is PET and PE, and PET is the polymer of highly crystalline, and is high temperature resistant, and good mechanical property is arranged, and has the performance of excellent high-low temperature resistant degree; And endurance, rub resistance, good stability of the dimension, melting temperature is the product that belongs to higher in high molecular polymer.Become lithium battery diaphragm for adapting to PET, must why be improved with the situation that some function can not adapt to lithium-ion power battery dissepiment the situation of the high crystallization of PET, for PET and PE due to chemical constitution difference, do not have compatibility, pass through polymer blending modification, must improve by the increase-volume means both compatibilities, we are through screening, confirm that SEBS and PS-g-ECMA can increase the compatibility of two kinds of polymer, crystal property, microstructure and the mechanical property that can be simultaneously intermingling material all change, and reach the blending and modifying melting of PET and PE; And corresponding raising melt temperature, method improvement processability and the electric property of employing enhancing, filling and blend; Pass through again test of many times, PET is when certain specific high some melt temperature, its PET chemical constitution will change, the compatibility of its PET and PE more improves, adhesion, elongation at break are improved simultaneously, degree of crystallinity reduces, and this is also for SEBS and adding of PS-g-ECMA more increasing compatible basis.
For improving PET electricity electric conductivity, increase the porosity of tunica fibrosa, improve electrolytical adsorption rate, we add the special-purpose TiO of nanometer
2, effectively improve the divergent function of polymer, reduce the degree of crystallinity of polymer composite fibrous matrix, increase the porosity of polymer fiber, improve conductivity.Work as TiO
2Nano raw material mix in the compound fiber with suitable ratio, conductivity can reach heavy rain 10
-3S/cm meets the requirement of lithium rechargeable battery, at suitable TiO
2In formula range, the electrochemistry of composite fibre barrier film and lithium ion compatibility all are improved, in the situation that identical current density, increase specific capacity, magnitude of the stored charge, charge discharge amount all are improved, reduce the self-discharge of battery rate, improve the cycle life of battery.
PS-g-ECMA (PE: CMA: PS=59.5: 10.5: 30), namely use ethylene-methyl methacrylate ethylene oxidic ester grafted polystyrene (PS-g-ECMA) to do bulking agent, the epoxy-functional of CMA and PET terminal carboxyl group reaction on the one hand, on the other hand, PS block and SEBS have good physical compatibility, realize increase-volume to SEBS and PET with this.the crystal property of the mixed material of its centering, microstructure and mechanical property are tested, show that bulking agent can react with the PET terminal carboxyl group, and with SEBS, good compatibility is arranged, PET degree of crystallinity after modification reduces, crystallite dimension is dwindled, impact strength improves, bulking agent makes SEBS be scattered in PET and bond good with PET with less particle, having under potent bulking agent modification, PET/PE forms continuous phase, the PET of part orientation is distributed to PE mutually, in the netted matrix that PET and bulking agent form, the elongation at break of PET/PE is mentioned 5 times and 2 times than pure PET and PE respectively, thereby adopting the composite fibre barrier film, intensity is better than the membrane for polymer that the biaxial tension method is produced greatly.
The lithium-ion-power cell of the present embodiment compound fibre diaphragm, the polyethylene layer of its low melting point, make barrier film have lower closed pore temperature, and dystectic pet layer, make barrier film have higher broken film temperature, broken film temperature and closed pore temperature difference are very large, so supporting lithium-ion membrane has good fail safe with it, promote the security performance of lithium-ion-power cell to increase substantially.
Embodiment 2
With reference to Fig. 1, in the present embodiment, described upper strata mass content is 18.5%, and mass content is 23.5% at the middle and upper levels, and the middle level mass content is 17%, and middle lower floor mass content is 20.5%, and lower floor's mass content is 21%.
In described the upper and lower, the ratio of quality and the number of copies of four components is: PET15 part, SEBS1.1 part, PS-g-ECMA2.1 part, nano-TiO
21.1 part;
In described middle lower floor, the ratio of quality and the number of copies of four components is: PET15 part, SEBS1.1 part, PS-g-ECMA1.6 part, nano-TiO
21.1 part;
Described middle lower floor and comprise at the middle and upper levels PE, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of three components is: PE18 part, PS-g-ECMA1.6 part, nano-TiO
20.6 part.
Other schemes of the present embodiment are all identical with embodiment 1.
Embodiment 3
With reference to Fig. 1, in the present embodiment, described upper strata mass content is 21%, and mass content is 19.5% at the middle and upper levels, and the middle level mass content is 21%, and middle lower floor mass content is 19.5%, and lower floor's mass content is 20%.
In described the upper and lower, the ratio of quality and the number of copies of four components is: PET15 part, SEBS1.2 part, PS-g-ECMA2.3 part, nano-TiO
21.4 part;
In described middle lower floor, the ratio of quality and the number of copies of four components is: PET15 part, SEBS1.4 part, PS-g-ECMA2.1 part, nano-TiO
21.35 part;
Described middle lower floor and comprise at the middle and upper levels PE, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of three components is: PE18 part, PS-g-ECMA2.2 part, nano-TiO
201.2 part.
Other schemes of the present embodiment are all identical with embodiment 1.
Embodiment 4
With reference to Fig. 1, in the present embodiment, described upper strata mass content is 20%, and mass content is 21% at the middle and upper levels, and the middle level mass content is 18%, and middle lower floor mass content is 23.5%, and lower floor's mass content is 17.5%.
In described the upper and lower, the ratio of quality and the number of copies of four components is: PET15 part, SEBS1.5 part, PS-g-ECMA2.5 part, nano-TiO
21.5 part;
In described middle lower floor, the ratio of quality and the number of copies of four components is: PET15 part, SEBS1.5 part, PS-g-ECMA2.5 part, nano-TiO
21.5 part;
Described middle lower floor and comprise at the middle and upper levels PE, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of three components is: PE18 part, PS-g-ECMA3 part, nano-TiO
21.5 part.
Other schemes of the present embodiment all and embodiment, 1 is identical.
Embodiment 5
With reference to Fig. 2, a kind of compound nanofiber diaphragm for lithium ion power battery, described compound nanofiber diaphragm for lithium ion power battery comprise upper strata 1, lower floor 2 and the middle level between upper strata and lower floor 3; Described upper strata 1 and lower floor 2 are the PET nanofiber layer, and described middle level 3 is the PE nanofiber layer, and described middle level covers in described lower floor, and described upper strata covers on described middle level;
In described compound nanofiber diaphragm for lithium ion power battery, described upper strata, lower floor's mass content are independently 31～37% separately, and described middle level is 28～36%;
Described the upper and lower include PET, SEBS, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of four components is: PET28 part, SEBS1～2 part, PS-g-ECMA2～4 part, nano-TiO
21～2 part;
Described middle level comprises PE, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of three components is: PE28 part, PS-g-ECMA2～4 part, nano-TiO
21～2 part.
In the present embodiment, described upper strata mass content is 31%, and lower floor's mass content is 33%, and described middle level is 36%.
In described the upper and lower, the ratio of quality and the number of copies of four components is: PET28 part, SEBS1 part, PS-g-ECMA2 part, nano-TiO
21 part;
Wherein, the trade mark of PET is CB-608, and manufacturing enterprise is the Far East, Taiwan textile company; The trade mark of SEBS is 3333C, and manufacturing enterprise is Japanese Kunal Co., Ltd.; PS-g-ECMA (PE: CMA: PS=59.5: 10.5: 30), manufacturing enterprise is NOF Corp; Nano-TiO
2The trade mark of (battery special-purpose) is T-258, and manufacturing enterprise is female space nano material Co., Ltd;
Described middle level comprises PE, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of three components is: PE28 part, PS-g-ECMA2 part, nano-TiO
21 part.Wherein, the trade mark of PE is 168Y, and manufacturing enterprise is Malaysian PETRONAS company; PS-g-ECMA (PE: CMA: PS=59.5: 10.5: 30), manufacturing enterprise is NOF Corp; Nano-TiO
2The trade mark of (battery special-purpose) is T-258, and manufacturing enterprise is female space nano material Co., Ltd;
Embodiment 6
With reference to Fig. 2, in the present embodiment, described upper strata mass content is 35.5%, and lower floor's mass content is 35.5%, and described middle level is 29%.
In described the upper and lower, the ratio of quality and the number of copies of four components is: PET28 part, SEBS1.1 part, PS-g-ECMA2.2 part, nano-TiO
21.05 part;
Wherein, the trade mark of PET is CB-608, and manufacturing enterprise is the Far East, Taiwan textile company; The trade mark of SEBS is 3333C, and manufacturing enterprise is Japanese Kunal Co., Ltd.; PS-g-ECMA (PE: CMA: PS=59.5: 10.5: 30), manufacturing enterprise is NOF Corp; Nano-TiO
2The trade mark of (battery special-purpose) is T-258, and manufacturing enterprise is female space nano material Co., Ltd;
Described middle level comprises PE, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of three components is: PE28 part, PS-g-ECMA2.1 part, nano-TiO
21.2 part.Wherein, the trade mark of PE is 168Y, and manufacturing enterprise is Malaysian PETRONAS company; PS-g-ECMA (PE: CMA: PS=59.5: 10.5: 30), manufacturing enterprise is NOF Corp; Nano-TiO
2The trade mark of (battery special-purpose) is T-258, and manufacturing enterprise is female space nano material Co., Ltd.
Other schemes of the present embodiment are all identical with embodiment 5.
Embodiment 7
With reference to Fig. 2, in the present embodiment, described upper strata mass content is 33%, and lower floor's mass content is 37%, and described middle level is 30%.
In described the upper and lower, the ratio of quality and the number of copies of four components is: PET28 part, SEBS1.3 part, PS-g-ECMA2.4 part, nano-TiO
21.2 part;
Wherein, the trade mark of PET is CB-608, and manufacturing enterprise is the Far East, Taiwan textile company; The trade mark of SEBS is 3333C, and manufacturing enterprise is Japanese Kunal Co., Ltd.; PS-g-ECMA (PE: CMA: PS=59.5: 10.5: 30), manufacturing enterprise is NOF Corp; Nano-TiO
2The trade mark of (battery special-purpose) is T-258, and manufacturing enterprise is female space nano material Co., Ltd;
Described middle level comprises PE, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of three components is: PE28 part, PS-g-ECMA2.4 part, nano-TiO
21.3 part.Wherein, the trade mark of PE is 168Y, and manufacturing enterprise is Malaysian PETRONAS company; PS-g-ECMA (PE: CMA: PS=59.5: 10.5: 30), manufacturing enterprise is NOF Corp; Nano-TiO
2The trade mark of (battery special-purpose) is T-258, and manufacturing enterprise is female space nano material Co., Ltd.
Other schemes of the present embodiment are all identical with embodiment 5.
Embodiment 8
With reference to Fig. 2, in the present embodiment, described upper strata mass content is 37%, and lower floor's mass content is 35%, and described middle level is 28%.
In described the upper and lower, the ratio of quality and the number of copies of four components is: PET28 part, SEBS1.6 part, PS-g-ECMA2.8 part, nano-TiO
21.5 part;
Wherein, the trade mark of PET is CB-608, and manufacturing enterprise is the Far East, Taiwan textile company; The trade mark of SEBS is 3333C, and manufacturing enterprise is Japanese Kunal Co., Ltd.; PS-g-ECMA (PE: CMA: PS=59.5: 10.5: 30), manufacturing enterprise is NOF Corp; Nano-TiO
2The trade mark of (battery special-purpose) is T-258, and manufacturing enterprise is female space nano material Co., Ltd;
Described middle level comprises PE, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of three components is: PE28 part, PS-g-ECMA2.71 part, nano-TiO
21.6 part.Wherein, the trade mark of PE is 168Y, and manufacturing enterprise is Malaysian PETRONAS company; PS-g-ECMA (PE: CMA: PS=59.5: 10.5: 30), manufacturing enterprise is NOF Corp; Nano-TiO
2The trade mark of (battery special-purpose) is T-258, and manufacturing enterprise is female space nano material Co., Ltd.
Other schemes of the present embodiment are all identical with embodiment 5.
Embodiment 9
With reference to Fig. 2, in the present embodiment, described upper strata mass content is 36%, and lower floor's mass content is 31%, and described middle level is 33%.
In described the upper and lower, the ratio of quality and the number of copies of four components is: PET28 part, SEBS1.7 part, PS-g-ECMA3.2 part, nano-TiO
21.8 part;
Wherein, the trade mark of PET is CB-608, and manufacturing enterprise is the Far East, Taiwan textile company; The trade mark of SEBS is 3333C, and manufacturing enterprise is Japanese Kunal Co., Ltd.; PS-g-ECMA (PE: CMA: PS=59.5: 10.5: 30), manufacturing enterprise is NOF Corp; Nano-TiO
2The trade mark of (battery special-purpose) is T-258, and manufacturing enterprise is female space nano material Co., Ltd;
Described middle level comprises PE, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of three components is: PE28 part, PS-g-ECMA3 part, nano-TiO
21.75 part.Wherein, the trade mark of PE is 168Y, and manufacturing enterprise is Malaysian PETRONAS company; PS-g-ECMA (PE: CMA: PS=59.5: 10.5: 30), manufacturing enterprise is NOF Corp; Nano-TiO
2The trade mark of (battery special-purpose) is T-258, and manufacturing enterprise is female space nano material Co., Ltd.
Other schemes of the present embodiment are all identical with embodiment 5.
Embodiment 10
With reference to Fig. 2, in the present embodiment, described upper strata mass content is 35.5%, and lower floor's mass content is 35%, and described middle level is 29.5%.
In described the upper and lower, the ratio of quality and the number of copies of four components is: PET28 part, SEBS1.1 part, PS-g-ECMA4 part, nano-TiO
22 parts;
Wherein, the trade mark of PET is CB-608, and manufacturing enterprise is the Far East, Taiwan textile company; The trade mark of SEBS is 3333C, and manufacturing enterprise is Japanese Kunal Co., Ltd.; PS-g-ECMA (PE: CMA: PS=59.5: 10.5: 30), manufacturing enterprise is NOF Corp; Nano-TiO
2The trade mark of (battery special-purpose) is T-258, and manufacturing enterprise is female space nano material Co., Ltd;
Described middle level comprises PE, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of three components is: PE28 part, PS-g-ECMA4 part, nano-TiO
22 parts.Wherein, the trade mark of PE is 168Y, and manufacturing enterprise is Malaysian PETRONAS company; PS-g-ECMA (PE: CMA: PS=59.5: 10.5: 30), manufacturing enterprise is NOF Corp; Nano-TiO
2The trade mark of (battery special-purpose) is T-258, and manufacturing enterprise is female space nano material Co., Ltd.
Other schemes of the present embodiment are all identical with embodiment 5.
Embodiment 11
With reference to Fig. 1 and Fig. 3, a kind of manufacture method of compound nanofiber diaphragm for lithium ion power battery, described manufacture method comprises the following steps:
(1), raw material preparation: in described compound nanofiber diaphragm for lithium ion power battery, described upper strata, middle level, lower floor's mass content are independently 17～21% separately, and described is 19.5～23.5% with middle lower floor at the middle and upper levels;
Described the upper and lower include PET, SEBS, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of four components is: PET15 part, SEBS1～1.5 part, PS-g-ECMA2～2.5 part, nano-TiO
21～1.5 part;
Described middle level comprises PET, SEBS, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of four components is: PET15 part, SEBS1～1.5 part, PS-g-ECMA1.5～2.5 part, nano-TiO
21～1.5 part;
Describedly include PE, PS-g-ECMA and nano-TiO with middle lower floor at the middle and upper levels
2, the ratio of quality and the number of copies of three components is: PE18 part, PS-g-ECMA1.5～3 part, nano-TiO
20.5～1.5 parts.
(2), extrude operation: the compound that each layer prepares, send into five extruders through each layered material bucket, five layers of extruder are extruded through molten condition, filter through multi-bed filter and enter die head, melt is evenly extruded through the die lip mouth;
The melt of the molten condition that the die lip mouth is flowed out is introduced high pressure syringe pump, melt enters the electrostatic spinning spinning head, provide high-voltage dc voltage at the spinning head mouth, under the promotion of electric field action and syringe pump pressure, form and spray thread, directive by leaps and bounds receives on guipure, forms woven cloths shape nanofiber compound barrier film;
(3), stripping process:
On described reception guipure, nanofiber compound barrier film forms continuously, adopts stripping off device to peel off continuously, and barrier film bead cutter excision burr make compound nanofiber diaphragm for lithium ion power battery.
In the present embodiment, the finished product operation is: with the barrier film after rolling, proportionally carry out the scene sampling, test and test, the volume film after test passes is according to customer requirement, put into cutting machine and cut, cut metacneme and pack, after packing, the warehouse-in supply is produced.
The main technologic parameters of the manufacture method of the present embodiment is:
Base material speed of production: 0.5～14m/min;
Spinning voltage: 0～140Kv;
Nano fibrous membrane Breadth Maximum: 0.3～1.0 meter;
Operating ambient temperature: 20～30 ℃;
Working temperature: 20 ℃ ± 1 ℃;
Textile fabric diameter: 40～500nm;
PET raw material drying: pre-crystallized baking temperature: 120 ℃～145 ℃; Baking temperature: 160 ℃～195 take the photograph ℃; Drying time: 2.5 hours;
PE raw material drying: 120～160 ℃ of baking temperatures, drying time: 3 hours;
The compound nanofiber diaphragm for lithium ion power battery of the present embodiment is five-layer structure, wherein,
1. the melt temperature of upper strata PET extruder and melt (unit ℃):
| One district | 2nd district | 3rd district | 4th district | 5th district | 6th district | 7th district |
| 245～285 | 265～320 | 285～330 | 285～335 | 285～340 | 260～320 | 260～300 |
2. the temperature of PE extruder and melting die head thereof (unit ℃) at the middle and upper levels:
| One district | 2nd district | 3rd district | 4th district | 5th district | Draping | Runner |
| 120～220 | 120～230 | 120～240 | 120～250 | 120～260 | 120～260 | 120～260 |
3. the melt temperature of middle level PET extruder and melt (unit ℃):
| One district | 2nd district | 3rd district | 4th district | 5th district | 6th district | 7th district |
| 245～285 | 265～320 | 285～330 | 285～335 | 285～340 | 260～320 | 260～300 |
4. the temperature of the middle PE of lower floor extruder and melting die head thereof (unit ℃):
| One district | 2nd district | 3rd district | 4th district | 5th district | Draping | Runner |
| 120～220 | 120～230 | 120～240 | 120～250 | 120～260 | 120～260 | 120～260 |
5. the melt temperature of the PET of lower floor extruder and melt (unit ℃):
| One district | 2nd district | 3rd district | 4th district | 5th district | 6th district | 7th district |
| 245～285 | 265～320 | 285～330 | 285～335 | 285～340 | 260～320 | 260～300 |
Wherein, the mean temperature in the PET melt chamber is 260～330 ℃; The temperature of filter is 260～340 ℃.
In the present embodiment, the PET melt viscosity is large, change the viscosity of PET, can reduce viscosity by the method that improves temperature, improve mobility, increase the amalgamation with PE, spin the trickle composite fibre of diameter in order to reach, can adopt and reduce nozzle diameter, increase nozzle temperature and electrospinning temperature, increase electric field strength and adjust receiving range etc., the electrospun fibers diameter is obviously reduced.So we use heating collar to heat in the molten mass spinning process, increase high pressure syringe pump and nozzle temperature, raising electric field strength etc. is all effective approach.
Battery special-purpose nanometer titanium dioxide has good fast charging and discharging performance and higher capacity, adds the barrier film of nano titanium oxide, has higher electrochemical reversibility; Comprise many electricity in good conductivity of metals and charge and discharge process right, read soon, continuous, reversible faraday's reaction.Nano titanium oxide has more mixing oxyhydroxide, and this nano material is nontoxic, with other raw materials, fabulous compatibility is arranged.Because this material particle size is little, reference area is large, purity is high, chemical property obviously improves, and is used on barrier film, increases the service life cycle of battery, reduces self-discharge rate, under identical current density, increases specific capacity.
Through studies show that, battery special-purpose nanometer titanium dioxide and PET have good compatibility, and the shrinkage of composite fibre is improved after electrostatic spinning, and the porosity of barrier film increases, and promote the advantages such as increase of electrolyte electric charge activity.
Lithium-ion power battery dissepiment must have: 1. good insulating properties guarantees the isolation of both positive and negative polarity; 2. have good fiber aperture and voidage, reach resistance low high with the particle conductivity, make lithium ion that fabulous permeability be arranged; 3. the difference of the broken film temperature of barrier film and closed pore temperature is the key of check diaphragm quality, so lithium battery broken film temperature and closed pore temperature difference must be large, this is protection lithium-ion-power cell thermal stability and the capable measure that automatically shuts down, and avoids the great-capacity power battery key technology that accidents happened; 4. the corrosion of the necessary electrolyte-resistant of barrier film, have stable chemistry and chemical property; 5. the wettability to electrolyte is good, and has enough moisturizing imbibition abilities; 6. have good mechanical property, as hot strength, puncture intensity etc., the thickness of barrier film adapts to the requirement that battery uses the field.
And lithium-ion-power cell compound fibre diaphragm is the barrier film that meets the dynamic lithium battery of above requirement fully.
Lithium-ion-power cell compound fibre diaphragm, maximum advantage can be adjusted the electrospinning technological parameter, the porosity, fibre diameter, aperture, thickness etc. that effectively change film want characteristic to adapt to the actual needs in application, and this characteristic is that the barrier film that stretch processes is produced does not reach.Because process using melt extrudes the mode electrostatic spinning, than using the more real superiority of solution mode electrostatic spinning performance: 1. output is high: when preparing raw material because of the solution-type electrostatic spinning, must first dissolve raw material with solvent, dissolution time is long, and in solution, real material rate is low, and above several factors cause solution-type electrostatic spinning output to yield poorly 70% than melting formula electrostatic spinning; 2. environmental nonpollution: without any pollution, and solution-type electrostatic spinning is because need melt raw material to environment for melting formula electrostatic spinning, adopt multi-solvents, many solvents contain poisonous composition, in spinning process, solvent evaporates, contaminated environment affect again operator's health; 3. melting formula electrostatic spinning barrier film broken film temperature and closed pore temperature difference are large, security performance is good, mechanical property is good, be applicable to large-scale production, be applicable to lithium-ion-power cell supporting, and solution-type electrostatic spinning mode, due to the impact of raw material dissolving, broken film temperature and closed pore temperature difference are little, and coefficient of safety is little; 4. melting formula electrostatic spinning compound fibre diaphragm is lower than existing dissolvant type electrostatic spinning cost; Cost is lower than three layers of dry method of biaxial tension or wet production barrier film, but effect substantially exceeds three layers of barrier film of biaxial tension formula.
In sum, the composite fibre barrier film that the melting formula electrostatic spinning of the present embodiment is produced meets safe, efficient, energy-conservation, the requirement cheaply of lithium-ion-power cell fully, is the barrier film of lithium-ion-power cell.
Table 1 is illustrated with the Performance Ratio of external import barrier film for the compound nanofiber diaphragm of the present embodiment:
Table 1.
Embodiment 12
With reference to Fig. 2 and Fig. 3, a kind of manufacture method of compound nanofiber diaphragm for lithium ion power battery, described manufacture method comprises the following steps:
(1), raw material preparation: in described compound nanofiber diaphragm for lithium ion power battery, described upper strata, lower floor's mass content are independently 31～37% separately, and described middle level is 28～36%;
Described the upper and lower include PET, SEBS, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of four components is: PET28 part, SEBS1～2 part, PS-g-ECMA2～4 part, nano-TiO
21～2 part;
Described middle level comprises PE, PS-g-ECMA and nano-TiO
2, the ratio of quality and the number of copies of three components is: PE28 part, PS-g-ECMA2～4 part, nano-TiO
21～2 part;
(2), extrude operation: the compound that each layer prepares, send into three extruders through each layered material bucket, three layers of extruder are extruded through molten condition, filter through multi-bed filter and enter die head, melt is evenly extruded through the die lip mouth;
The melt of the molten condition that the die lip mouth is flowed out is introduced high pressure syringe pump, for guaranteeing the melt normal flow, the high-pressure injection pump housing should be added with the heating lasso, melt enters the electrostatic spinning spinning head, provide high-voltage dc voltage at the spinning head mouth, under the promotion of electric field action and syringe pump pressure, form and spray thread, directive by leaps and bounds receives on guipure, forms woven cloths shape nanofiber compound barrier film;
(3), stripping process:
On described reception guipure, nanofiber compound barrier film forms continuously, adopts stripping off device to peel off continuously, and barrier film bead cutter excision burr make compound nanofiber diaphragm for lithium ion power battery.
Further, described upper strata, lower floor's mass content are independently 32～35.5% separately, and described middle level is 29.5～33%.
The compound nanofiber diaphragm for lithium ion power battery of the present embodiment is three-decker, wherein,
1. the melt temperature of upper strata PET extruder and melt (unit ℃):
| One district | 2nd district | 3rd district | 4th district | 5th district | 6th district | 7th district |
| 245～285 | 265～320 | 285～330 | 285～335 | 285～340 | 260～320 | 260～300 |
2. the melt temperature of middle level PET extruder and melt (unit ℃):
| One district | 2nd district | 3rd district | 4th district | 5th district | 6th district | 7th district |
| 245～285 | 265～320 | 285～330 | 285～335 | 285～340 | 260～320 | 260～300 |
3. the melt temperature of the PET of lower floor extruder and melt (unit ℃):
| One district | 2nd district | 3rd district | 4th district | 5th district | 6th district | 7th district |
| 245～285 | 265～320 | 285～330 | 285～335 | 285～340 | 260～320 | 260～300 |
Wherein, the mean temperature in the PET melt chamber is 260～330 ℃; The temperature of filter is 260～340 ℃.
Other schemes of the present embodiment are all identical with embodiment 1.
Claims (6)
1. compound nanofiber diaphragm for lithium ion power battery is characterized in that: described compound nanofiber diaphragm for lithium ion power battery comprise the upper strata, at the middle and upper levels, middle level, middle lower floor and lower floor; Described the upper, middle and lower are the PET nanofiber layer, described is the PE nanofiber layer with middle lower floor at the middle and upper levels, and described middle lower floor covers in described lower floor, and described middle level covers in described middle lower floor, described covering at the middle and upper levels on described middle level, described upper strata cover describedly goes up at the middle and upper levels;
In described compound nanofiber diaphragm for lithium ion power battery, described upper strata, middle level, lower floor's mass content are independently 17 ~ 21% separately, and described is 19.5 ~ 23.5% with middle lower floor at the middle and upper levels;
Described the upper and lower include PET, SEBS, PS-g-ECMA and nano-TiO
2, in described PS-g-ECMA, PE:CMA:PS=59.5:10.5:30, the ratio of quality and the number of copies of four components is: PET15 part, 1 ~ 1.5 part of SEBS, PS-g-ECMA2 ~ 2.5 part, nano-TiO
21 ~ 1.5 part;
Described middle level comprises PET, SEBS, PS-g-ECMA and nano-TiO
2, in described PS-g-ECMA, PE:CMA:PS=59.5:10.5:30, the ratio of quality and the number of copies of four components is: PET15 part, 1 ~ 1.5 part of SEBS, PS-g-ECMA1.5 ~ 2.5 part, nano-TiO
21 ~ 1.5 part;
Describedly include PE, PS-g-ECMA and nano-TiO with middle lower floor at the middle and upper levels
2, in described PS-g-ECMA, PE:CMA:PS=59.5:10.5:30, the ratio of quality and the number of copies of three components is: PE18 part, PS-g-ECMA1.5 ~ 3 part, nano-TiO
20.5 ~ 1.5 parts.
2. compound nanofiber diaphragm for lithium ion power battery, it is characterized in that: described compound nanofiber diaphragm for lithium ion power battery comprises upper strata, lower floor and the middle level between upper strata and lower floor; Described the upper and lower are the PET nanofiber layer, and described middle level is the PE nanofiber layer, and described middle level covers in described lower floor, and described upper strata covers on described middle level;
In described compound nanofiber diaphragm for lithium ion power battery, described upper strata, lower floor's mass content are independently 31 ~ 37% separately, and described middle level is 28 ~ 36%;
Described the upper and lower include PET, SEBS, PS-g-ECMA and nano-TiO
2, in described PS-g-ECMA, PE:CMA:PS=59.5:10.5:30, the ratio of quality and the number of copies of four components is: PET28 part, 1 ~ 2 part of SEBS, PS-g-ECMA2 ~ 4 part, nano-TiO
21 ~ 2 part;
Described middle level comprises PE, PS-g-ECMA and nano-TiO
2, in described PS-g-ECMA, PE:CMA:PS=59.5:10.5:30, the ratio of quality and the number of copies of three components is: PE28 part, PS-g-ECMA2 ~ 4 part, nano-TiO
21 ~ 2 part.
3. compound nanofiber diaphragm for lithium ion power battery as claimed in claim 2, it is characterized in that: described upper strata, lower floor's mass content are independently 32 ~ 35.5% separately, and described middle level is 29.5 ~ 33%.
4. the manufacture method of a compound nanofiber diaphragm for lithium ion power battery as claimed in claim 1, it is characterized in that: described manufacture method comprises the following steps:
(1), raw material preparation: in described compound nanofiber diaphragm for lithium ion power battery, described upper strata, middle level, lower floor's mass content are independently 17 ~ 21% separately, and described is 19.5 ~ 23.5% with middle lower floor at the middle and upper levels;
Described the upper and lower include PET, SEBS, PS-g-ECMA and nano-TiO
2, in described PS-g-ECMA, PE:CMA:PS=59.5:10.5:30, the ratio of quality and the number of copies of four components is: PET15 part, 1 ~ 1.5 part of SEBS, PS-g-ECMA2 ~ 2.5 part, nano-TiO
21 ~ 1.5 part;
Described middle level comprises PET, SEBS, PS-g-ECMA and nano-TiO
2, in described PS-g-ECMA, PE:CMA:PS=59.5:10.5:30, the ratio of quality and the number of copies of four components is: PET15 part, 1 ~ 1.5 part of SEBS, PS-g-ECMA1.5 ~ 2.5 part, nano-TiO
21 ~ 1.5 part;
Describedly include PE, PS-g-ECMA and nano-TiO with middle lower floor at the middle and upper levels
2, in described PS-g-ECMA, PE:CMA:PS=59.5:10.5:30, the ratio of quality and the number of copies of three components is: PE18 part, PS-g-ECMA1.5 ~ 3 part, nano-TiO
20.5 ~ 1.5 parts;
(2), extrude operation: the compound that each layer prepares, send into five extruders through each layered material bucket, five layers of extruder are extruded through molten condition, filter through multi-bed filter and enter die head, melt is evenly extruded through the die lip mouth;
The melt of the molten condition that the die lip mouth is flowed out is introduced high pressure syringe pump, melt enters the electrostatic spinning spinning head, provide high-voltage dc voltage at the spinning head mouth, under the promotion of electric field action and syringe pump pressure, form and spray thread, directive by leaps and bounds receives on guipure, forms woven cloths shape nanofiber compound barrier film;
(3), stripping process:
On described reception guipure, nanofiber compound barrier film forms continuously, adopts stripping off device to peel off continuously, and barrier film bead cutter excision burr make compound nanofiber diaphragm for lithium ion power battery.
5. the manufacture method of a compound nanofiber diaphragm for lithium ion power battery as claimed in claim 3, it is characterized in that: described manufacture method comprises the following steps:
(1), raw material preparation: in described compound nanofiber diaphragm for lithium ion power battery, described upper strata, lower floor's mass content are independently 31 ~ 37% separately, and described middle level is 28 ~ 36%;
Described the upper and lower include PET, SEBS, PS-g-ECMA and nano-TiO
2, in described PS-g-ECMA, PE:CMA:PS=59.5:10.5:30, the ratio of quality and the number of copies of four components is: PET28 part, 1 ~ 2 part of SEBS, PS-g-ECMA2 ~ 4 part, nano-TiO
21 ~ 2 part;
Described middle level comprises PE, PS-g-ECMA and nano-TiO
2, in described PS-g-ECMA, PE:CMA:PS=59.5:10.5:30, the ratio of quality and the number of copies of three components is: PE28 part, PS-g-ECMA2 ~ 4 part, nano-TiO
21 ~ 2 part;
(2), extrude operation: the compound that each layer prepares, send into three extruders through each layered material bucket, three layers of extruder are extruded through molten condition, filter through multi-bed filter and enter die head, melt is evenly extruded through the die lip mouth;
The melt of the molten condition that the die lip mouth is flowed out is introduced high pressure syringe pump, melt enters the electrostatic spinning spinning head, provide high-voltage dc voltage at the spinning head mouth, under the promotion of electric field action and syringe pump pressure, form and spray thread, directive by leaps and bounds receives on guipure, forms woven cloths shape nanofiber compound barrier film;
(3), stripping process:
On described reception guipure, nanofiber compound barrier film forms continuously, adopts stripping off device to peel off continuously, and barrier film bead cutter excision burr make compound nanofiber diaphragm for lithium ion power battery.
6. the manufacture method of compound nanofiber diaphragm for lithium ion power battery as claimed in claim 5, it is characterized in that: described upper strata, lower floor's mass content are independently 32 ~ 35.5% separately, and described middle level is 29.5 ~ 33%.
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| CN102629679B (en) * | 2012-04-28 | 2018-04-20 | 中国科学院理化技术研究所 | Nanofiber lithium ion battery separator material with composite construction and preparation method thereof |
| CN103219483B (en) * | 2013-04-27 | 2015-05-27 | 中材科技股份有限公司 | Composite lithium battery diaphragm and preparation method thereof |
| CN104659413B (en) * | 2013-11-18 | 2017-04-05 | 北京化工大学 | A kind of preparation of Radiation Crosslinked Polymers gel electrolyte framework material |
| CN103824988B (en) * | 2014-02-24 | 2016-05-04 | 东华大学 | A kind of composite nano fiber lithium battery diaphragm and preparation method thereof |
| CN104393337B (en) * | 2014-12-10 | 2017-02-22 | 天津力神电池股份有限公司 | Lithium ion battery gel electrolyte with multi-stage structure and preparation method thereof |
| CN104766938B (en) * | 2015-02-10 | 2018-04-27 | 龙岩紫荆创新研究院 | A kind of compound lithium ion battery separator and preparation method thereof |
| CN105552434B (en) * | 2015-12-17 | 2019-02-05 | 北京科技大学 | A kind of preparation method of the full solid state polymer electrolyte film of three-decker |
| CN109950665B (en) * | 2017-12-21 | 2021-11-23 | 中南大学 | Lithium-air battery extension interlayer melt spinning preparation process |
| CN108258299B (en) * | 2018-01-10 | 2020-04-17 | 深圳市正翔电池能源有限公司 | Lithium ion power battery |
| CN114335889B (en) | 2018-04-11 | 2024-04-05 | 宁德新能源科技有限公司 | Isolation diaphragm and energy storage device |
| CN110802902A (en) * | 2019-11-06 | 2020-02-18 | 天华新材料科技（荆门）股份有限公司 | Composite film applied to explosive packaging and preparation method thereof |
| CN116404358B (en) * | 2023-06-01 | 2023-09-29 | 合肥长阳新能源科技有限公司 | Battery separator, preparation method thereof and lithium ion battery |
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| CN101000952A (en) * | 2006-11-02 | 2007-07-18 | 许贵斌 | Polyalkylene microporous diaphragm for lithiam ion battery and manufacturing method thereof |
| JP2008258073A (en) * | 2007-04-06 | 2008-10-23 | Ntt Facilities Inc | Separator for lithium ion secondary battery, lithium ion secondary battery using it, and manufacturing method of lithium ion secondary battery |
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| CN101000952A (en) * | 2006-11-02 | 2007-07-18 | 许贵斌 | Polyalkylene microporous diaphragm for lithiam ion battery and manufacturing method thereof |
| JP2008258073A (en) * | 2007-04-06 | 2008-10-23 | Ntt Facilities Inc | Separator for lithium ion secondary battery, lithium ion secondary battery using it, and manufacturing method of lithium ion secondary battery |
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