CN103762325B - A kind of production technology of novel low-cost lithium ion battery PE barrier film - Google Patents
A kind of production technology of novel low-cost lithium ion battery PE barrier film Download PDFInfo
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- CN103762325B CN103762325B CN201410013991.7A CN201410013991A CN103762325B CN 103762325 B CN103762325 B CN 103762325B CN 201410013991 A CN201410013991 A CN 201410013991A CN 103762325 B CN103762325 B CN 103762325B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The production technology that the invention discloses a kind of low cost lithium ion battery PE barrier film, belongs to battery diaphragm field. Its production technology comprises: first polyethylene and organic solvent are evenly mixed, obtain mixture; Mixture is extruded respectively, obtained oil-containing film after metering, slab, oil-containing film after biaxial tension is sent in vacuum drying chamber, design temperature and negative pressure make the organic solvent volatilization in oil-containing film, obtain dry perforated membrane Primary product, after the organic solvent that evaporates is cooling, enter exhaust gas adsorption device, select adsorbent to adsorb organic solvent, adsorb rear parsing, desorb waste gas enters layering groove after condensation, and the organic solvent of separating enters feed proportioning system and recycles. The method has been avoided the lock out operation of solvent extraction in traditional wet processing and extraction mixed liquor, and waste gas system recovered solvent can also continue to enter feed proportioning system and recycle, and has reduced widely production cost.
Description
Technical field
The invention belongs to battery diaphragm field, be specifically related to a kind of production technology of novel low-cost lithium ion battery PE barrier film.
Background technology
In recent years, lithium ion battery is as high-energy-density power supply, and its range of application is constantly expanded, and is extensively applied to portableThe field barrier films such as electronic installation, electric tool, electric automobile, energy-accumulating power station are one of important raw material of battery, therefore, and lithiumThe safety issue of ion battery receives much concern always. Barrier film is as a part important in lithium ion battery, and its effect is by justThe utmost point and negative material separate, and allow that ion passes through, and stop electronics to pass through, and the performance of lithium battery diaphragm has determined the interface knot of batteryStructure, internal resistance etc., directly affect the characteristic such as capacity, circulation and security performance of battery, and the barrier film of excellent performance is to improving batteryCombination property there is important effect. The Main Function of barrier film is that the positive and negative electrode of battery is separated, and prevents the two poles of the earth contactAnd short circuit has the function that can make electrolyte ion pass through in addition.
The production method of lithium ion battery separator mainly contains dry method and wet method, the application of Cangzhou Mingzhu Plastic Co., Ltd. at presentPatent of invention CN201010107854.1 a kind of method that wet method is prepared lithium ion battery separator is disclosed, the method obtainsThe first-time qualification rate of product is not high, in addition, also comprises dividing of solvent extraction and extraction mixed liquor in traditional wet processingFrom operating procedure, obviously increase the input of production cost.
Summary of the invention
In order to solve above-mentioned problems of the prior art, the present invention proposes a kind of novel low-cost lithium ion battery PE barrier filmPreparation method, the method need in traditional wet processing, not carry out solvent extraction and extraction mixed liquor lock out operation,And waste gas system recovered solvent can also continue to enter feed proportioning system to be recycled, and greatly reduces production cost.
Technical solution of the present invention comprises:
A preparation method for novel low-cost lithium ion battery PE barrier film, comprises the following steps:
A, batching: take the polyethylene of 15～50 ﹪, the organic solvent of 50～85 ﹪ according to percentage by weight, it is fully mixedClose, obtain mixture A;
B, extrude, measure: the mixture A in step a is obtained to high-temperature fusant through extruder, and described high-temperature fusant is through accuratelyAfter metering, send in die head;
The high-temperature fusant that c, slab: step b sends in die head flows out from die head slit mouth, obtains slab after sharp cooling roll is cooling;
D, biaxial tension: the slab obtaining is carried out after preheating to high temperature bi-directional stretching in step c, obtain oil-containing film;
E, vacuum drying: the oil-containing film in steps d is sent in vacuum drying chamber, and design temperature and negative pressure make in oil-containing filmOrganic solvent volatilization, obtain dry perforated membrane Primary product, after the organic solvent that evaporates is cooling, enter exhaust gas adsorption device,Select adsorbent to adsorb organic solvent, adsorbed rear parsing, desorb waste gas enters layering groove after condensation, isolatesThe organic solvent coming enters feed proportioning system and recycles;
F, the horizontal expanding that draws: the perforated membrane Primary product in step e obtains barrier film after transverse stretching machine expanding;
G, thermal finalization, rolling: the barrier film after step f expanding is reeled through online winder after thermal finalization, removal stress, obtainsLithium ion battery PE barrier film.
In above-mentioned steps a, organic solvent is kerosene or decahydronaphthalene.
In above-mentioned steps b mixture A through diameter be that 96mm, draw ratio are 52, temperature is that the double screw extruder of 130 DEG C obtainsTo high-temperature fusant.
In above-mentioned steps c from die head slit mouth flow out high-temperature fusant successively through excess temperature be respectively 20 DEG C-30 DEG C-30 DEG C-After four sharp cooling rolls of 30 DEG C, obtain extruding slab; Extrude slab and enter bi-directional synchronization stretching-machine to obtain vertical Lapie be 5 times, horizontal drawingThan the oil-containing film that is 5 times.
In steps d, described biaxial tension can be both two-way step drawing, can be also that bi-directional synchronization stretches.
In above-mentioned steps e, described drying box temperature is 100 DEG C, negative pressure-below 80KPa, described adsorbent is active carbon fibreDimension.
In above-mentioned steps f, the horizontal Lapie of transverse stretching machine is 1.2 times, and transverse stretching machine temperature is 120 DEG C.
In above-mentioned steps g, heat setting temperature is 125 DEG C.
The useful technique effect that the present invention brings:
The present invention proposes a kind of preparation method of novel low-cost lithium ion battery PE barrier film, compared with prior art, at raw materialChoose, the present invention is taking polyethylene and organic solvent as raw material, organic solvent is selected kerosene or decahydronaphthalene, due to kerosene and tenHydrogen naphthalene boiling point is lower, is easy to evaporate in vacuum drying step; In preparation technology, compared with traditional wet processing,The method avoided the lock out operation of solvent extraction in traditional wet processing and extraction mixed liquor, and waste gas system reclaimsSolvent can also continue to enter feed proportioning system to be recycled, and has reduced widely production cost.
Detailed description of the invention
The present invention proposes a kind of preparation method of novel low-cost lithium ion battery PE barrier film, in order to make advantage of the present invention, skillArt scheme is more outstanding, below in conjunction with detailed description of the invention, the present invention is done to further clear, complete explanation.
The selected raw material of the present invention all can be bought and be obtained by commercial channel, does as follows below to the character of the selected raw material of part of the present inventionIllustrate:
Polyethylene: be a kind of thermoplastic resin that ethene makes through polymerization, industrial, also comprise ethene and a small amount of alpha-olefinCopolymer, polyethylene odorless, nontoxic, feel ceraceous, have good resistance to low temperature, and chemical stability is good, resistance to great majorityThe erosion of soda acid, is insoluble to common solvent under normal temperature, and water imbibition is little, and electrical insulation capability is excellent; Polyethylene of the present invention comprises molecular weightBe 100～1,500,000 ultra-high molecular weight polyethylene and molecular weight lower than 1,000,000 high density polyethylene (HDPE).
The present invention, a kind of preparation method of novel low-cost lithium ion battery PE barrier film, comprises the following steps:
Step 1, batching step: take the polyethylene of 15～50 ﹪, the organic solvent of 50～85 ﹪ according to percentage by weight, thisThe preferred kerosene of invention organic solvent or decahydronaphthalene, fully mix polyethylene and kerosene or decahydronaphthalene, obtains mixture A;
Step 2, extrude, metrology steps: be that 96mm, draw ratio are 52, temperature by mixture A in step 1 through diameterThe double screw extruder that is 130 DEG C obtains high-temperature fusant, and high-temperature fusant is sent in die head after Melt Pump accurate-metering;
Step 3, slab step: the high-temperature fusant that step 2 is sent in die head flows out from die head slit mouth, flows from die head slit mouthAfter four sharp cooling rolls that the high-temperature fusant going out is respectively 20 DEG C-30 DEG C-30 DEG C-30 DEG C through excess temperature successively, obtain extruding slab;Extrude slab and enter bi-directional synchronization stretching-machine to obtain vertical Lapie be 4.5 times, horizontal Lapie is the oil-containing film of 5 times;
Step 4, vacuum drying step: the oil-containing film in step 3 is sent in vacuum drying chamber, and design temperature is 100 DEG C,Negative pressure-below 80KPa, make the volatilization of organic solvent in oil-containing film, obtain dry perforated membrane Primary product, evaporateAfter organic solvent is cooling, enter exhaust gas adsorption device, select adsorbent to adsorb organic solvent, adsorbed rear parsing, separateWaste suction gas enters layering groove after condensation, and the organic solvent of separating enters feed proportioning system and recycles;
Step 5, the horizontal expanding that draws: the perforated membrane Primary product in step 4 obtains barrier film after transverse stretching machine expanding, transverse stretching machineHorizontal Lapie is 1.2 times, and transverse stretching machine temperature is 120 DEG C;
Step 6, thermal finalization, rolling: the barrier film after step 5 expanding is 125 DEG C in temperature to carry out thermal finalization, remove warp after stressOnline winder is reeled, and obtains lithium ion battery PE barrier film.
Further do in conjunction with specific embodiments following explanation:
Embodiment 1:
A preparation method for novel low-cost lithium ion battery PE barrier film, comprises the following steps:
Step 1, batching: take respectively polyethylene powder and the 396.67Kg decahydronaphthalene of 70Kg, and together pour it into stirred tankInterior (agitator type is two ribbon forms) fully stirs, and obtains mixture A, for subsequent use;
Step 2, extrude, metrology steps: mixture A is 96mm by diameter, and draw ratio is 52, and temperature is 130 DEG C twoScrew extruder obtains even high-temperature fusant, and high-temperature fusant enters in die head respectively after Melt Pump accurate-metering;
Step 3, slab step: the high-temperature fusant flowing out from die head slit mouth is respectively 20 DEG C-30 DEG C-30 DEG C through excess temperature successivelyAfter four sharp cooling rolls of-30 DEG C, obtain extruding slab;
Step 4, stretching step: extrude slab and enter bi-directional synchronization stretching-machine to obtain vertical Lapie be 4.5 times, horizontal Lapie is 5 timesOil-containing film, preheat temperature is 120 DEG C, 125 DEG C of draft temperatures, cooling and shaping temperature is 30 DEG C;
Step 5, vacuum drying step: the oil-containing film after stretching enters in vacuum drying chamber, drying box temperature is 100 DEG C, negativePressure-controlled-below 80KPa, the volatilization of decahydronaphthalene in film, obtains dry perforated membrane Primary product, the decahydronaphthalene evaporatingAfter surface cooler is cooled to 60 DEG C, enter into exhaust gas adsorption device, adopt activated carbon fiber as adsorbent, decahydronaphthalene to be adsorbed,The saturated vapor that passes into subsequently 0.1MPa gets off decahydronaphthalene from carbon fiber surface desorb, desorb waste gas enters layering after condensationGroove, the decahydronaphthalene of separating enters feed proportioning system and recycles;
Step 6, the horizontal expanding step of drawing: the dry perforated membrane Primary product obtaining obtains barrier film, horizontal stroke after transverse stretching machine expandingThe horizontal Lapie of machine drawing is 1.2 times, and transverse stretching machine temperature is 120 DEG C;
Step 7: thermal finalization, rolling step: the barrier film after expanding is removed the thermal stress of barrier film inside after high temperature heat setting device,125 DEG C of heat setting temperatures, three layers of barrier film removing after stress are reeled and are obtained lithium ion battery PE barrier film through online winder.
Embodiment 2:
Step 1, batching: take respectively polyethylene powder and the 70Kg decahydronaphthalene of 70Kg, and it is together poured in stirred tank and (stirredMix device form for two ribbon forms) fully stir, obtain mixture A, for subsequent use;
Step 2, extrude, metrology steps: mixture A is 96mm by diameter, and draw ratio is 52, and temperature is 130 DEG C twoScrew extruder obtains even high-temperature fusant, and high-temperature fusant enters in die head respectively after Melt Pump accurate-metering;
Step 3, slab step: the high-temperature fusant flowing out from die head slit mouth is respectively 20 DEG C-30 DEG C-30 DEG C through excess temperature successivelyAfter four sharp cooling rolls of-30 DEG C, obtain extruding slab;
Step 4, stretching step: extrude slab and enter bi-directional synchronization stretching-machine to obtain vertical Lapie be 4.5 times, horizontal Lapie is 5 timesOil-containing film, preheat temperature is 120 DEG C, 125 DEG C of draft temperatures, cooling and shaping temperature is 30 DEG C;
Step 5, vacuum drying step: the oil-containing film after stretching enters in vacuum drying chamber, drying box temperature is 100 DEG C, negativePressure-controlled-below 80KPa, the volatilization of decahydronaphthalene in film, obtains dry perforated membrane Primary product, the decahydronaphthalene evaporatingAfter surface cooler is cooled to 60 DEG C, enter into exhaust gas adsorption device, adopt activated carbon fiber as adsorbent, decahydronaphthalene to be adsorbed,The saturated vapor that passes into subsequently 0.1MPa gets off decahydronaphthalene from carbon fiber surface desorb, desorb waste gas enters layering after condensationGroove, the decahydronaphthalene of separating enters feed proportioning system and recycles;
Step 6, the horizontal expanding step of drawing: the dry perforated membrane Primary product obtaining obtains barrier film, horizontal stroke after transverse stretching machine expandingThe horizontal Lapie of machine drawing is 1.2 times, and transverse stretching machine temperature is 120 DEG C;
Step 7: thermal finalization, rolling step: the barrier film after expanding is removed the thermal stress of barrier film inside after high temperature heat setting device,125 DEG C of heat setting temperatures, three layers of barrier film removing after stress are reeled and are obtained lithium ion battery PE barrier film through online winder.
Embodiment 3:
Step 1, batching: take respectively polyethylene powder and the 330Kg decahydronaphthalene of 70Kg, and it is together poured in stirred tank and (stirredMix device form for two ribbon forms) fully stir, obtain mixture A, for subsequent use;
Step 2, extrude, metrology steps: mixture A is 96mm by diameter, and draw ratio is 52, and temperature is 130 DEG C twoScrew extruder obtains even high-temperature fusant, and high-temperature fusant enters in die head respectively after Melt Pump accurate-metering;
Step 3, slab step: the high-temperature fusant flowing out from die head slit mouth is respectively 20 DEG C-30 DEG C-30 DEG C through excess temperature successivelyAfter four sharp cooling rolls of-30 DEG C, obtain extruding slab;
Step 4, stretching step: extrude slab and enter bi-directional synchronization stretching-machine to obtain vertical Lapie be 4.5 times, horizontal Lapie is 5 timesOil-containing film, preheat temperature is 120 DEG C, 125 DEG C of draft temperatures, cooling and shaping temperature is 30 DEG C;
Step 5, vacuum drying step: the oil-containing film after stretching enters in vacuum drying chamber, drying box temperature is 100 DEG C, negativePressure-controlled-below 80KPa, the volatilization of decahydronaphthalene in film, obtains dry perforated membrane Primary product, the decahydronaphthalene evaporatingAfter surface cooler is cooled to 60 DEG C, enter into exhaust gas adsorption device, adopt activated carbon fiber as adsorbent, decahydronaphthalene to be adsorbed,The saturated vapor that passes into subsequently 0.1MPa gets off decahydronaphthalene from carbon fiber surface desorb, desorb waste gas enters layering after condensationGroove, the decahydronaphthalene of separating enters feed proportioning system and recycles;
Step 6, the horizontal expanding step of drawing: the dry perforated membrane Primary product obtaining obtains barrier film, horizontal stroke after transverse stretching machine expandingThe horizontal Lapie of machine drawing is 1.2 times, and transverse stretching machine temperature is 120 DEG C;
Step 7: thermal finalization, rolling step: the barrier film after expanding is removed the thermal stress of barrier film inside after high temperature heat setting device,125 DEG C of heat setting temperatures, three layers of barrier film removing after stress are reeled and are obtained lithium ion battery PE barrier film through online winder.
Embodiment 4:
Difference from Example 1 is: in step 5, organic solvent is kerosene.
Should be understood that, those of ordinary skill in the art, under enlightenment of the present invention, is not departing from the claims in the present invention instituteIn the scope situation of protection, can also make the various deformation such as replacement, simple combination, request protection domain of the present invention should be with instituteAttached claim is as the criterion.
Claims (6)
1. a preparation method for low cost lithium ion battery PE barrier film, is characterized in that comprising the following steps:
A, batching: take the polyethylene of 15～50 ﹪, the organic solvent of 50～85 ﹪ according to percentage by weight, it is fully mixed, obtain mixture A, described organic solvent is kerosene or decahydronaphthalene;
B, extrude, measure: the mixture A in step a is obtained to high-temperature fusant through extruder, and described high-temperature fusant is sent in die head after accurate-metering;
The high-temperature fusant that c, slab: step b sends in die head flows out from die head slit mouth, obtains slab after sharp cooling roll is cooling;
D, biaxial tension: the slab obtaining is carried out after preheating to high temperature bi-directional stretching in step c, obtain the film containing organic solvent;
E, vacuum drying: the film containing organic solvent in steps d is sent in vacuum drying chamber, design temperature and negative pressure make the organic solvent volatilization in this film, obtain dry perforated membrane Primary product, after the organic solvent that evaporates is cooling, enter exhaust gas adsorption device, select adsorbent to adsorb organic solvent, adsorb rear desorb, desorb waste gas enters layering groove after condensation, the organic solvent of separating enters feed proportioning system and recycles, described drying box temperature is 100 DEG C, negative pressure-below 80KPa, described adsorbent is NACF;
F, the horizontal expanding that draws: the perforated membrane Primary product in step e obtains barrier film after transverse stretching machine expanding;
G, thermal finalization, rolling: the barrier film after step f expanding is reeled through online winder after thermal finalization, removal stress, obtains lithium ion battery PE barrier film.
2. preparation method according to claim 1, is characterized in that: in described step b mixture A through diameter be that 96mm, draw ratio are 52, temperature is that the double screw extruder of 130 DEG C obtains high-temperature fusant.
3. preparation method according to claim 1, is characterized in that: after four sharp cooling rolls that the high-temperature fusant flowing out from die head slit mouth in described step c is respectively 20 DEG C-30 DEG C-30 DEG C-30 DEG C through excess temperature successively, obtain extruding slab; Extrude slab and enter biaxial orientation stretching machine to obtain vertical Lapie be 4.5 times, horizontal Lapie is the film containing organic solvent of 5 times.
4. preparation method according to claim 1, is characterized in that: in steps d, described biaxial tension is that two-way step drawing or bi-directional synchronization stretch.
5. preparation method according to claim 1, is characterized in that: in described step f, the horizontal Lapie of transverse stretching machine is 1.2 times, and transverse stretching machine temperature is 120 DEG C.
6. preparation method according to claim 1, is characterized in that: in described step g, heat setting temperature is 125 DEG C.
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| CN104868188B (en) * | 2015-04-05 | 2017-08-25 | 铜仁学院 | A kind of useless film process reuse technology on lithium battery diaphragm production line |
| CN105655518B (en) * | 2015-09-07 | 2019-04-09 | 浙江南洋经中新材料有限公司 | A kind of preparation process of novel porous lithium battery diaphragm |
| CN107617294A (en) * | 2016-07-15 | 2018-01-23 | 中国石油化工股份有限公司 | A kind of preprocess method of the waste gas containing decahydronaphthalene |
| JP2018144480A (en) * | 2017-03-03 | 2018-09-20 | 住友化学株式会社 | Film production device and film production method |
| JP7055662B2 (en) * | 2017-03-03 | 2022-04-18 | 住友化学株式会社 | Film manufacturing equipment and film manufacturing method |
| CN108441976B (en) * | 2018-04-25 | 2020-10-27 | 青岛中科华联新材料股份有限公司 | Ultrahigh molecular weight polyethylene split fiber and preparation method thereof |
| CN111129395A (en) * | 2019-12-12 | 2020-05-08 | 中材锂膜有限公司 | Transverse stretching and shrinking shaping process after extraction of wet lithium battery diaphragm |
| CN113244766A (en) * | 2020-02-10 | 2021-08-13 | 新特能源股份有限公司 | Single crystal furnace tail gas purification and recovery system and method |
| CN113410533B (en) * | 2021-05-10 | 2023-05-02 | 杭州天易成环保设备股份有限公司 | White oil separation device for complete diaphragm of wet lithium battery by diffusion method |
| CN115312970A (en) * | 2022-08-15 | 2022-11-08 | 湖南创一工业新材料股份有限公司 | Preparation method of high-strength PET battery diaphragm |
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