CN102218871A - Preparation method of modified diaphragm for lithium-ion secondary battery as well as product and preparation device thereof - Google Patents
Preparation method of modified diaphragm for lithium-ion secondary battery as well as product and preparation device thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a modified diaphragm for a lithium-ion secondary battery as well as a prepared modified diaphragm and a preparation device and is aimed to solve the problem of lithium battery modified diaphragms in the prior art. The method concretely comprises the following steps of: (1), evenly dispersing special fiber or oxide and a binder into an organic solvent to prepare composite mixed liquid, and adding a cosolvent into the organic solvent; (2) evenly spraying the composite mixed liquid obtained in the step (1) on a polyolefin base membrane to form a primary composite membrane through an electrostatic spinning method; and (3), drying the primary composite membrane obtained in the step (2) and recycling the solvent, and then finally obtaining the finished product. The preparation method is convenient to operate and environmental friendly, can realize large-scale production and has strong feasibility.
Description
Technical field
The present invention relates to the lithium ion battery production technical field, particularly a kind of lithium rechargeable battery is with preparation method and the modified diaphragm that makes and the preparation facilities of modified diaphragm.
Background technology
In recent years, because the pressure of environmental pollution and energy shortage forces various countries to strive to find the energy of new green, environmental protection, sustainable development.The green high-capacity environment-protecting lithium ion battery that occurs the nineties in 20th century because its energy density height, have extended cycle life, the operating voltage advantages of higher, make it become one of electrical source of power that attracts most attention.Lithium ion battery separator is as one of core material of battery, and the characteristics such as interfacial structure, internal resistance, cycle performance and security performance of battery are had significant effects, and the barrier film of excellent performance has important effect to the combination property that improves battery.
Polyolefine material has excellent mechanical property, chemical stability and relatively inexpensive characteristics, so polyethylene (PE), and polypropylene MIcroporous polyolefin films such as (PP) is present commercial lithium ion battery separator.Generally speaking, this microporous barrier has gas permeability and liquid permeability preferably, can satisfy the instructions for use of battery.(wherein PE microporous barrier closed temperature is lower than 140 degree but the fusing point of PE microporous barrier, PP microporous barrier or PP-PE composite micro porous film is all lower, and PP microporous barrier closed temperature also is no more than 170 degree), when battery under higher temperature, when surpassing the fail temperature of PP or PE, polyolefine material can melt fully, destroy, cause positive and negative pole material direct short-circuit, thereby cause that battery catches fire and even explodes.This application to lithium ion battery has caused bigger hidden danger, and therefore, the high-temperature stability that further improves existing barrier film on the basis that does not reduce existing membrane properties becomes the new technological challenge in lithium battery field.
Japan Patent JP-A-63-308866 discloses by lamination and has comprised that the single thin film acquisition of low melting point PE and high-melting-point PP has the method for the microporous membrane of high strength and hot properties.Yet the barrier film internal resistance is bigger because of lamination raises, and is bigger to multiplying power, the power-performance influence of battery.
Japan Patent JP-A-10-298325 has proposed a kind of perforated membrane that has excellent balance between shutdown characteristic (SD characteristic) and hear resistance.Yet this invention uses polynorbornene not only to increase cost, but also because perforated membrane is synthetic by special reaction, therefore has byproduct, causes that the impurity content of battery rises after the fluid injection, directly influences the cycle life of battery.Simultaneously, owing to be difficult to fully control reaction condition, make polynorbornene may 2 single gelinites crosslinked, so the hear resistance of perforated membrane and mechanical strength may be relatively poor.
The invention of publication number CN1512607A, disclose a kind of perforated membrane, contained the battery separator of this film and with the nonaqueous electrolyte battery of this dividing plate, this perforated membrane contains ethylene-propylene-ethylidene norbornene terpolymer, by three's alternating current function raising intensity and heat resistance.But it is same because used ultra-high molecular weight polyethylene and ENB to improve cost; and be that the traditional thermoplastic PE/PP of employing is main; percent thermal shrinkage is relatively large; can not fundamentally well solve the equilibrium relation of shutting down between characteristic and the heat resistance; from its described content, adopt the super high molecular weight material also can cause electrostatic phenomenon simultaneously.
The disclosure of the Invention of publication number CN101209609A a kind of polyolefin composite thin film and its production and use.But this method be by solvent evaporation method in the polyolefin surfaces coating, the hole penetrability that solvent evaporates forms is poor, even the pore size distribution that forms is also inhomogeneous, causes the gas permeability of battery poor, thereby has greatly influenced the performance of battery.
Except the PP-PE microporous barrier, Degussa has been made and has been used the special mixture high flexibility non woven cloth in polymer SEPARION that is made up of aluminium oxide, zirconia and silica.Its fusing point is higher than 250 ℃, has comparatively good cryogenic property simultaneously, but this barrier film mechanical strength is relatively poor, and fracture causes potential safety hazard easily in assembling process, does not obtain large-scale application at present as yet.
All there is defective separately in the made barrier film of said method, can't really substitute existing PP-PE system microporous barrier, realizes the scale volume production.
Summary of the invention
One of purpose of the present invention is existing lithium battery modified diaphragm technology above shortcomings, provide a kind of easy to operate, can accomplish scale production, lithium rechargeable battery that environmental protection, feasibility are strong is with the preparation method of modified diaphragm.
Two of purpose of the present invention is to provide the lithium rechargeable battery that makes by said method modified diaphragm, and it has outstanding high temperature resistance and mechanical property, and the surface pore is even, good permeability.
Three of purpose of the present invention is to provide a kind of device of lithium rechargeable battery with modified diaphragm that be used to prepare.
The technical solution adopted for the present invention to solve the technical problems is: a kind of lithium rechargeable battery preparation method of modified diaphragm, and described preparation method may further comprise the steps:
Step is 1.: with special fibre, or with oxide and binding agent, be dispersed in and make compound mixed liquor in the organic solvent, jitter time is 0.5 ~ 60 hour, is added with cosolvent in the described organic solvent; Step is 2.: the compound mixed liquor that 1. step is obtained by method of electrostatic spinning evenly is sprayed at and is compounded to form elementary composite membrane on the polyolefin base membrane, and spinning temperature is 30 ~ 95 ℃;
Step is 3.: the elementary composite membrane that 2. step is obtained is dried and solvent recovery is handled, and described oven dry and solvent recovery are treated to from the elementary composite membrane logical 80 ~ 120 ℃ of hot blasts of the elementary composite membrane of direction and handled 1 ~ 20 minute, at last finished product.
The present invention with commercial applications widely polyalkene diaphragm and compound mixed liquor and basement membrane are carried out the electrostatic spinning Combined Processing as basement membrane by method of electrostatic spinning, by solvent oven dry and solvent recovery processing, make finished product at last.Characteristics such as method of electrostatic spinning is a kind of important method for preparing superfine fibre, and made fiber is thin, reference area is big, be evenly distributed, spinning equipment is simple simultaneously, and these advantages make it have broad application prospects at lithium battery diaphragm.The finished product thickness of modified diaphragm of the present invention is at 6.5mm ~ 75mm.
As preferably, by the weight percent meter that accounts for compound mixed liquor: special fibre is 1 ~ 50%, and organic solvent is 1 ~ 80%, and cosolvent is 1 ~ 20%.Special fibre more preferably 20 ~ 30%, organic solvent more preferably 60 ~ 80%, cosolvent more preferably 2 ~ 10%.
As preferably, by the weight percent meter that accounts for compound mixed liquor: oxide is 1 ~ 50%, and binding agent is 2 ~ 15%, and organic solvent is 20 ~ 80%, and cosolvent is 1 ~ 20%.Oxide more preferably 3 ~ 25%, organic solvent more preferably 65 ~ 80%, cosolvent more preferably 1 ~ 10%.
As preferably, described special fibre is selected from one or more the combination in tetrafluoro-hexafluoroethylene copolymer fiber, Saran, ethylene-chlorinated copolymer fibre, Fanglun 1313, polyimide fiber, PPSU nylon, polyamide-imide fiber, PBI fibre, phenolic fibre, aromatic polyamide fibre and the pre-oxidized polyacrylonitrile fiber.
The preferred polyimide fiber of described special fibre is as poly-BMI or norbornene capped polyimides resin.
Special fibre has special physicochemical structure, performance and purposes, or has the chemical fibre of specific function.Special fibre has different properties respectively, as be able to bear strong corrosion, low wearing and tearing, high temperature resistant, radiation hardness, anti-combustion, high voltage withstanding, high strength and modulus, high resiliency, counter-infiltration, high efficiency filter, absorption, ion-exchange, leaded light, conduction and multiple medical science function.These fibers mostly are applied to industry, national defence, medical treatment, environmental protection and most advanced branches of science each side.
Corrosion resistant fiber: tetrafluoro-hexafluoroethylene copolymer fiber, Saran, ethylene-chlorinated copolymer fibre, these fibers add can improve decay resistance; High-temperature fibre: Fanglun 1313, polyimide fiber, PPSU nylon, polyamide-imide fiber, PBI fibre, these fibers add can improve resistance to elevated temperatures; Flame-resistant fibre: phenolic fibre, aromatic polyamide fibre and pre-oxidized polyacrylonitrile fiber, these fibers add can improve the flame resistance energy.
As preferably, described oxide is selected from one or more the combination in aluminium oxide, magnesia, calcium oxide, the silica.The adding of oxide is used to increase the resistance to elevated temperatures of modified diaphragm of the present invention.
As preferably, described binding agent is selected from one or more the combination in Kynoar, polytetrafluoroethylene (PTFE), polytrifluorochloroethylene, polymethyl methacrylate, the fluorinated ethylene propylene copolymer.Preferred molecular weight is greater than Kynoar more than 150,000 or polytetrafluoroethylene (PTFE).
As preferably, described organic solvent is selected from one or more the combination in benzene,toluene,xylene, pentane, hexane, octane, cyclohexane, cyclohexanone, toluene cyclohexanone, chlorobenzene, dichloro-benzenes, carrene, methyl alcohol, ethanol, isopropyl alcohol, ether, expoxy propane, methyl acetate, ethyl acetate, propyl acetate, acetone, espeleton, methylisobutylketone, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, dimethyl formamide, dimethylacetylamide, the N-methyl pyrrolidone; Described cosolvent is selected from Sodium Benzoate, sodium salicylate, p-aminobenzoic acid, urea, nicotinic acid amide, acetamide, CaCl
2, one or more the combination among the LiCl.
As preferably, described polyolefin base membrane is selected from a kind of in PP monofilm, PP multilayer film, PE monofilm, PP/PE composite membrane, three layers of composite membrane of PP/PE/PP, and polyolefin-based film thickness is at 6 microns to 40 microns.Preferred 12 microns to 22 microns of polyolefin-based film thickness.
The lithium rechargeable battery modified diaphragm that a kind of lithium rechargeable battery makes with the preparation method of modified diaphragm.
A kind of device for preparing lithium rechargeable battery with modified diaphragm, described device comprises that barrier film transmits passage and oven dry and solvent recovery unit, barrier film transmits passage and is made up of the basement membrane transmission section of leading portion and the modified diaphragm transmission section of back segment, basement membrane transmits the section top and is provided with the electrostatic spinning apparatus with a plurality of shower nozzles, oven dry and solvent recovery unit are arranged at modified diaphragm and transmit the section front end, oven dry and solvent recovery unit are made up of the air channel of upper end and the solvent recovery jar of lower end, and modified diaphragm transmits the section front end and crosses the air channel.Electrostatic spinning apparatus is an electrostatic spinning machine, and electrostatic spinning apparatus has the such production efficiency height of a plurality of shower nozzles, is fit to large-scale production; It is vertically disposed that air channel and modified diaphragm transmit section, during ventilation, from top to bottom ventilates, and remains in unnecessary solvent on the modified diaphragm like this and can drop to the solvent recovery jar and be recovered, and simultaneously, ventilating again can be with the modified diaphragm drying.
Material of the present invention compared with prior art has the following advantages:
1. compare with the barrier film that adopts electrostatic spinning directly to make, the present invention passes through to select the polyalkene diaphragm of good mechanical performance as basement membrane, overcome direct shortcoming, increased the puncture intensity and the toughness of modified diaphragm in electrode surface composite diaphragm or nonwoven barrier film poor mechanical property;
2. compare with the composite diaphragm that adopts solvent evaporation method to make, the present invention has adopted the high-speed electrostatic spinning method, and it is inhomogeneous to have overcome the solvent method pore-forming, the shortcoming of gas permeability difference, thus increased the uniformity of modified diaphragm greatly.
3. the present invention has increased solvent recovery unit in the electrostatic spinning process, has improved the feature of environmental protection of producing;
The present invention has directly adopted the polyalkene diaphragm of commercialization maturation as basement membrane, be coated in special fibre or oxide-binding agent on the basement membrane equably by adopting method of electrostatic spinning, increased the solvent recovery unit of the economic feature of environmental protection simultaneously, the whole process of production feasibility is strong, is fit to large-scale industrial production.
Description of drawings
Fig. 1 is the schematic representation of apparatus of preparation lithium rechargeable battery of the present invention with modified diaphragm;
Fig. 2 is that embodiment 1 made modified diaphragm and polyolefin base membrane electron-microscope scanning (SEM) schemed;
Fig. 3 is that embodiment 2 made modified diaphragm and polyolefin base membrane electron-microscope scannings (SEM) are schemed;
Fig. 4 is that embodiment 3 made modified diaphragm and three layers of barrier film thermal contraction of commercialization PP/PE/PP contrast.
Among the figure: 1, basement membrane transmits section, and 2, modified diaphragm transmits section, 3, electrostatic spinning apparatus, 4, the air channel, 5, the solvent recovery jar, 6, deflector roll.
The specific embodiment
Below by specific embodiment, and in conjunction with the accompanying drawings, technical scheme of the present invention is described in further detail.
A kind of device for preparing lithium rechargeable battery with modified diaphragm as shown in Figure 1, described device comprises that barrier film transmits passage and oven dry and solvent recovery unit, barrier film transmits passage and is made up of the basement membrane transmission section 1 of leading portion and the modified diaphragm transmission section 2 of back segment, the modified diaphragm transmission section 2 that basement membrane transmits section 1 and back segment all is to be made of deflector roll 6, basement membrane transmits section 1 top and is provided with the electrostatic spinning apparatus 3 with a plurality of shower nozzles, electrostatic spinning apparatus 3 is an electrostatic spinning machine, oven dry and solvent recovery unit are arranged at modified diaphragm and transmit section 2 front ends, oven dry and solvent recovery unit are made up of the air channel 4 of upper end and the solvent recovery jar 5 of lower end, and modified diaphragm transmits section 2 front ends and crosses air channel 4.
Following embodiment of the present invention has adopted this device.
Embodiment 1:
The first step selects individual layer PP barrier film as basement membrane, and its thickness is 22 microns, basement membrane is mounted to basement membrane transmits on the section;
Second step placed 800 gram DMAC(N, N-dimethylacetylamide with the 190 high-purity poly-BMIs of gram (special fibre)) in, add 10 gram LiCl again as cosolvent, stirred 10 hours by the high-speed stirred dispersion machine, make compound mixed liquor;
The 3rd step was heated to 85 ℃ spinning temperature with compound mixed liquor, formed liquid crystal solution this moment, and compound mixed liquor is put into the spray fiber tube of electrostatic spinning apparatus, by the many shower nozzles of high speed compound mixed liquor evenly was sprayed on the basement membrane, formed elementary composite membrane;
The 4th goes on foot elementary composite membrane enters oven dry and solvent recovery unit, and the logical 80 ℃ of hot blasts in the air channel of oven dry and solvent recovery unit were handled 20 minutes, and solvent recovery gets finished product at last to the solvent recovery jar.
Modified diaphragm that present embodiment is made and the contrast of polyolefin base membrane surface topography are as shown in Figure 2.
Embodiment 2:
The first step selects three layers of PP/PE/PP barrier film as basement membrane, and basement membrane thickness is 25 microns, basement membrane is mounted to basement membrane transmits on the section;
Second step placed 1000 gram N-methyl pyrrolidones with 200 gram polytetrafluoroethylene (PTFE), add 100 gram Sodium Benzoates again as cosolvent, high-speed stirred is after 3 hours, and then adds 900 gram high purity aluminium oxide powder, stirred 5 hours by the high-speed stirred dispersion machine, make compound mixed liquor;
The 3rd step was heated to 95 ℃ spinning temperature with compound mixed liquor, and compound mixed liquor is put into the spray fiber tube of electrostatic spinning apparatus, by the many shower nozzles of high speed compound mixed liquor evenly was sprayed on the basement membrane, formed elementary composite membrane;
The 4th goes on foot elementary composite membrane enters oven dry and solvent recovery unit, and the logical 120 ℃ of hot blasts in the air channel of oven dry and solvent recovery unit were handled 10 minutes, were recycled in the solvent recovery jar, got finished product at last.
Modified diaphragm that present embodiment is made and the contrast of membrane surface pattern are as shown in Figure 3.
Embodiment 3:
The first step selects individual layer PE barrier film as basement membrane, and its thickness is 21.6 microns, basement membrane is mounted to basement membrane transmits on the section;
Second step placed 1000 gram N-methyl pyrrolidone/methyl alcohol (mass ratio is 1:1) mixed solvents with 90 gram Kynoar, added 50 gram CaCl again
2As cosolvent, high-speed stirred is after 2 hours, and then adds the mixed-powder of 900 gram high purity aluminium oxides and calcium oxide, by high-speed stirred dispersion machine stirring 8 hours, makes compound mixed liquor.
The 3rd step was heated to 70 ℃ spinning temperature with compound mixed liquor, and compound mixed liquor is put into the spray fiber tube of electrostatic spinning apparatus, by the many shower nozzles of high speed compound mixed liquor evenly was sprayed on the basement membrane, formed elementary composite membrane;
The 4th goes on foot elementary composite membrane enters oven dry and solvent recovery unit, and the logical 100 ℃ of hot blasts in the air channel of oven dry and solvent recovery unit were handled 15 minutes, and solvent recovery gets finished product at last to the solvent recovery jar.
Modified diaphragm that embodiment 3 is made and lithium ion battery applications comparatively widely three layers of PP/PE/PP basement membrane vertical resistance to elevated temperatures as shown in Figure 4.
Embodiment 4:
The first step selects the PP/PE composite membrane as basement membrane, and its thickness is 40 microns, basement membrane is mounted to basement membrane transmits on the section;
Second step placed 790 gram benzene with 10 gram tetrafluoro-hexafluoroethylene copolymer fibers (special fibre), added 200 gram CaCl again
2With the LiCl mixture as cosolvent, stirred 0.5 hour by the high-speed stirred dispersion machine, make compound mixed liquor;
The 3rd step was heated to 30 ℃ spinning temperature with compound mixed liquor, formed liquid crystal solution this moment, and compound mixed liquor is put into the spray fiber tube of electrostatic spinning apparatus, by the many shower nozzles of high speed compound mixed liquor evenly was sprayed on the basement membrane, formed elementary composite membrane;
The 4th goes on foot elementary composite membrane enters oven dry and solvent recovery unit, and the logical 120 ℃ of hot blasts in the air channel of oven dry and solvent recovery unit were handled 1 minute, and solvent recovery gets finished product at last to the solvent recovery jar.
Embodiment 5:
The first step selects individual layer PP barrier film as basement membrane, and its thickness is 6 microns, basement membrane is mounted to basement membrane transmits on the section;
Second step placed 400 gram N-methyl pyrrolidones with 500 gram phenolic fibres and Fanglun 1313 mixture (special fibre), add 100 gram sodium salicylates again as cosolvent, stirred 60 hours by the high-speed stirred dispersion machine, make compound mixed liquor;
The 3rd step was heated to 70 ℃ spinning temperature with compound mixed liquor, formed liquid crystal solution this moment, and compound mixed liquor is put into the spray fiber tube of electrostatic spinning apparatus, by the many shower nozzles of high speed compound mixed liquor evenly was sprayed on the basement membrane, formed elementary composite membrane;
The 4th goes on foot elementary composite membrane enters oven dry and solvent recovery unit, and the logical 100 ℃ of hot blasts in the air channel of oven dry and solvent recovery unit were handled 8 minutes, and solvent recovery gets finished product at last to the solvent recovery jar.
Embodiment 6:
The first step selects individual layer PE barrier film as basement membrane, and its thickness is 12 microns, basement membrane is mounted to basement membrane transmits on the section;
The mixture of second step with 150 gram Kynoar and fluorinated ethylene propylene copolymer places 800 gram dimethylacetylamides, add 40 gram acetamides again as cosolvent, after the high-speed stirred 1 hour, and then add 10 the gram high purity aluminium oxides, stirred 5 hours by the high-speed stirred dispersion machine, make compound mixed liquor.
The 3rd step was heated to 90 ℃ spinning temperature with compound mixed liquor, and compound mixed liquor is put into the spray fiber tube of electrostatic spinning apparatus, by the many shower nozzles of high speed compound mixed liquor evenly was sprayed on the basement membrane, formed elementary composite membrane;
The 4th goes on foot elementary composite membrane enters oven dry and solvent recovery unit, and the logical 100 ℃ of hot blasts in the air channel of oven dry and solvent recovery unit were handled 20 minutes, and solvent recovery gets finished product at last to the solvent recovery jar.
Because technical scheme of the present invention is more, not do one by one at this and enumerate, the technical scheme of claims record of the present invention all can be implemented.
Above-described embodiment is a kind of preferable scheme of the present invention, is not that the present invention is done any pro forma restriction, also has other variant and remodeling under the prerequisite that does not exceed the technical scheme that claim puts down in writing.
Claims (10)
1. a lithium rechargeable battery is with the preparation method of modified diaphragm, and it is characterized in that: described preparation method may further comprise the steps:
Step is 1.: with special fibre, or with oxide and binding agent, be dispersed in and make compound mixed liquor in the organic solvent, jitter time is 0.5 ~ 60 hour, is added with cosolvent in the described organic solvent; Step is 2.: the compound mixed liquor that 1. step is obtained by method of electrostatic spinning evenly is sprayed at and is compounded to form elementary composite membrane on the polyolefin base membrane, and spinning temperature is 30 ~ 95 ℃;
Step is 3.: the elementary composite membrane that 2. step is obtained is dried and solvent recovery is handled, and described oven dry and solvent recovery are treated to from the elementary composite membrane logical 80 ~ 120 ℃ of hot blasts of the elementary composite membrane of direction and handled 1 ~ 20 minute, at last finished product.
2. lithium rechargeable battery according to claim 1 is characterized in that with the preparation method of modified diaphragm: by the weight percent meter that accounts for compound mixed liquor: special fibre is 1 ~ 50%, and organic solvent is 1 ~ 80%, and cosolvent is 1 ~ 20%.
3. lithium rechargeable battery according to claim 1 is characterized in that with the preparation method of modified diaphragm: by the weight percent meter that accounts for compound mixed liquor: oxide is 1 ~ 50%, and binding agent is 2 ~ 15%, and organic solvent is 20 ~ 80%, and cosolvent is 1 ~ 20%.
4. lithium rechargeable battery according to claim 1 and 2 is characterized in that with the preparation method of modified diaphragm: described special fibre is selected from one or more the combination in tetrafluoro-hexafluoroethylene copolymer fiber, Saran, ethylene-chlorinated copolymer fibre, Fanglun 1313, polyimide fiber, PPSU nylon, polyamide-imide fiber, PBI fibre, phenolic fibre, aromatic polyamide fibre and the pre-oxidized polyacrylonitrile fiber.
According to claim 1 or 3 described lithium rechargeable batteries with the preparation method of modified diaphragms, it is characterized in that: described oxide is selected from one or more the combination in aluminium oxide, magnesia, calcium oxide, the silica.
According to claim 1 or 3 described lithium rechargeable batteries with the preparation method of modified diaphragms, it is characterized in that: described binding agent is selected from one or more the combination in Kynoar, polytetrafluoroethylene (PTFE), polytrifluorochloroethylene, polymethyl methacrylate, the fluorinated ethylene propylene copolymer.
7. according to the preparation method of claim 1 or 2 or 3 described lithium rechargeable batteries usefulness modified diaphragms, it is characterized in that: described organic solvent is selected from benzene, toluene, dimethylbenzene, pentane, hexane, octane, cyclohexane, cyclohexanone, the toluene cyclohexanone, chlorobenzene, dichloro-benzenes, carrene, methyl alcohol, ethanol, isopropyl alcohol, ether, expoxy propane, methyl acetate, ethyl acetate, propyl acetate, acetone, espeleton, methylisobutylketone, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, dimethyl formamide, dimethylacetylamide, the combination of one or more in the N-methyl pyrrolidone; Described cosolvent is selected from Sodium Benzoate, sodium salicylate, p-aminobenzoic acid, urea, nicotinic acid amide, acetamide, CaCl
2, one or more the combination among the LiCl.
8. according to claim 1 or 2 or 3 described lithium rechargeable batteries preparation method with modified diaphragms, it is characterized in that: described polyolefin base membrane is selected from a kind of in PP monofilm, PP multilayer film, PE monofilm, PP/PE composite membrane, three layers of composite membrane of PP/PE/PP, and polyolefin-based film thickness is at 6 microns to 40 microns.
9. lithium rechargeable battery modified diaphragm that makes with the preparation method of modified diaphragm as claim 1 or 2 or 3 described lithium rechargeable batteries.
10. one kind prepares the device that lithium rechargeable battery is used modified diaphragm, it is characterized in that: described device comprises that barrier film transmits passage and oven dry and solvent recovery unit, barrier film transmits passage and is made up of the basement membrane transmission section of leading portion and the modified diaphragm transmission section of back segment, basement membrane transmits the section top and is provided with the electrostatic spinning apparatus with a plurality of shower nozzles, oven dry and solvent recovery unit are arranged at modified diaphragm and transmit the section front end, oven dry and solvent recovery unit are made up of the air channel of upper end and the solvent recovery jar of lower end, and modified diaphragm transmits the section front end and crosses the air channel.
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