CN101872852B - Preparation method of cell diaphragm based on aramid fiber - Google Patents
Preparation method of cell diaphragm based on aramid fiber Download PDFInfo
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- CN101872852B CN101872852B CN2010102047659A CN201010204765A CN101872852B CN 101872852 B CN101872852 B CN 101872852B CN 2010102047659 A CN2010102047659 A CN 2010102047659A CN 201010204765 A CN201010204765 A CN 201010204765A CN 101872852 B CN101872852 B CN 101872852B
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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 invention discloses a preparation method of a cell diaphragm based on aramid fiber. The cell diaphragm is prepared by taking ultrashort aramid fiber as a main material and matching with aramid fiber fibrid, and the specific requirements onof air permeability and porosity of the cell diaphragm can be met through regulating a fiber formula and a molding process. The cell diaphragm can realize the mechanical isolation function of the anode and cathode of a cell, simultaneously ensures low resistance and higher ion conductivity and has enough electrochemicalmechanical stability. Compared with the traditional plastic diaphragm, the cell diaphragm prepared by the method has more excellent comprehensive performances, i.e. the advantages of excellent high temperature resistance, high strength, fatigue resistance, low deformation, frlame retardant property, chemical corrosion resistance, low specific gravity and the like. The cell diaphragm can be widely applied to manufacturing of various ion cells.
Description
Technical field
The present invention relates to the membrane technique of ion battery, relate in particular to a kind of preparation method of the battery diaphragm based on aramid fiber.
Background technology
Since company of early 1990s Sony (SONY) succeeded in developing lithium ion battery, lithium ion battery was high with its energy density, have extended cycle life and excellent electric performance such as voltage height and obtained development rapidly.Be widely used in electronic product fields such as mobile phone, portable computer, camera, video camera at present, and application is still among expanding constantly.Lithium ion battery is made up of both positive and negative polarity, electrolyte and barrier film.Wherein, a critical function of barrier film is to isolate both positive and negative polarity and stop the interior electronics of battery to pass, and can allow passing through of ion simultaneously, thereby accomplish the quick transmission of lithium ion between both positive and negative polarity in the charge discharge process.The quality of membrane properties directly affects the discharge capacity of battery and recycles the life-span.
At present, barrier film with the preparation method of microporous barrier can be divided into dry method (fusion drawn, MSCS) and wet method (thermic is separated, TIPS) two kinds of technology.Above-mentioned two kinds of methods comprise that all at least one orientation step makes film generation hole and improves hot strength.In the fusion drawn method film-forming process; The factor that influences membrane structure has process conditions such as fusion draw ratio, extrusion temperature and heat treatment temperature; Degree of molecular orientation receives the influence of fusion draw ratio and extrusion temperature; Thin film crystallization property receives the influence of fusion draw ratio and heat treatment temperature, easy-regulating not in the film-forming process.And the film-forming process of thermally induced phase separation is regulated and control easily, can control aperture, pore-size distribution and porosity preferably, but needs a large amount of solvents in the preparation process, causes environmental pollution easily, compares the technology relative complex with the fusion drawn method.Above-mentioned two kinds of pattern-making materials are polyolefin plastics such as polyethylene, polypropylene, its thermal endurance is relatively poor, have had a strong impact on the application of battery diaphragm in wide spectrum more.
Can know that to sum up the preparation method of existing battery diaphragm obviously exists inconvenience and defective, so be necessary to improve on reality is used.
Summary of the invention
To above-mentioned defective, the object of the present invention is to provide a kind of preparation method of the battery diaphragm based on aramid fiber, this battery diaphragm is main with ultrashort aramid fiber, manufacturing paper with pulp with addition of aramid fiber fibrid forms; The battery diaphragm that said preparation method makes has more excellent comprehensive performance, advantages such as promptly excellent heat resistance, high strength, fatigue performance, low distortion, fire resistant flame retardant performance, resistance to chemical corrosion.
The existing aramid fiber short fibre (structural fibers) that generally adopts adds aramid fiber fibrid (bondable fibers); And under high temperature, high pressure the manufacturing technology of the rolling aramid fiber paper that forms; If directly apply to battery diaphragm, it exists, and gas permeability is low, the aperture is big, the unequal defective of pore-size distribution.The present invention then adopts ultrashort aramid fiber, and handles through the fibrillation of making beating, adjusts the proportioning and the hot rolling technology of aramid fiber fibrid simultaneously, makes the air permeability of aramid fiber paper and porosity suitable with plastic diaphragms, has reached the instructions for use of battery diaphragm.
The invention discloses a kind of preparation method of the battery diaphragm based on aramid fiber; This battery diaphragm is applied in the ion battery (being preferably lithium ion battery); Be made up of ultrashort aramid fiber (the 1414 or 1313) fiber of 65～97 weight portions and aramid fiber (the 1414 or 1313) fibrid of 3～35 weight portions, wherein the fibre length of ultrashort aramid fiber is less than 1.5mm (millimeter).Preparation method of the present invention mainly comprises steps such as batching slurrying, the shaping of manufacturing paper with pulp, dry also preheating, high temperature hot rolling.
In batching slurrying step; The Fanglun l414 fiber or the aramid fiber 1313 fiber of 65～97 weight portions are prescinded, discongest and pull an oar; Dilute with water by weight; Making the pulping beating degree is the slurry A of 10～70 ° of SR, and Fanglun l414 or 1313 fibers are changed into the ultrashort aramid fiber of fibre length less than 1.5mm by fento among the said slurry A.The Fanglun l414 fibrid of 3～35 weight portions or aramid fiber 1313 fibrid are discongested and pulled an oar, dilute with water by weight, making the pulping beating degree is the slurry B of 10～75 ° of SR.At last two kinds of slurry A and B are mixed in joining stock tank, and then form the liquid slurry that can be added into the former flow box.
According to one side of the present invention; To Fanglun l414 fiber or aramid fiber 1313 fiber filament after prescinding; Available trough-style pulp beater or mill or big tapering jordan are pulled an oar; Control beating pressure and concentration, final 10～70 ° of SR of pulping beating degree, fibre length is less than the ultrashort aramid fiber of 1.5mm.According to another aspect of the present invention,, pull an oar control beating pressure and concentration, final 10～75 ° of SR of pulping beating degree to Fanglun l414 fibrid or aramid fiber 1313 fibrid with trough-style pulp beater or mill or big tapering jordan.
In the preparation method of battery diaphragm of the present invention, because of the hydrophobicity of aramid fiber and aramid fiber fibrid, extremely difficult dispersion the in water.In order to promote the dispersion of above-mentioned fiber in water; The anti flocculant that can in said liquid slurry, add 0～10 weight portion; Increase the resistance of motion of fiber in slurry; The winding, the wadding that delay fiber gather, and the suspended dispersed of fiber in water is improved, thereby reach the purpose that improves battery diaphragm evenness.The used anti flocculant of the present invention is preferably polyethylene glycol oxide.Said anti flocculant uses separately, looks model, specification, the film former type adjustment consumption of synthetic fibers slurry viscosity and film.
In the forming step of manufacturing paper with pulp, adopt forming device for cylinder machine, with the moulding of manufacturing paper with pulp of slurry wet method.Said forming device for cylinder machine is many forming device for cylinder machine or single forming device for cylinder machine, regulates the approach flow pressure head through slurry-stablizing case, in head box, starch to be evenly distributed on the forming net, and unnecessary slurry through overflow to destroying the forebay.
In the drying and preheating step, adopt drying tunnel formula drying device or many drying cylinders formula drying device, the former dried blank is loose, and the dried blank of the latter is tightr.Drying tunnel formula drying device divides many warm areas; Wet blank moves in drying tunnel by conveyer belt; Arrive the posterior segment of drying tunnel, the moisture in the blank can all exclude, and steam is discharged through the dehumidifier blower fan; And at the latter end of drying tunnel, temperature can reach the melt temperature of bondable fibers (aramid fiber fibrid) in the drying tunnel.
In the high temperature hot-rolled step, hot rolling near fibrid condensation temperature point time the, hot rolling near fibrid condensation temperature point the time; Through the hot-rolling mill single hot-roll forming; Control hot rolling linear pressure 10～120kg/cm (kg/cm), the roller surface temperature is that the hot rolling temperature is 130～300 ℃, rolling speed is 3～30m/min (meter/minute); Make between two kinds of fibers organically to engage, formed the intensity that battery diaphragm possessed.Adopt spacing hot rolling mode, control tunica fibrosa thickness is at 0.03～0.06mm, and density is at 0.30～0.65g/cm
3Between (gram/cubic centimetre), the porosity ranges that forms tunica fibrosa like this is 28～75%, air permeability Gurley value 1～25s (second).Said Gurley is used for characterizing air permeability, is the time that sample was consumed with the certain area of gas permeation of certain pressure certain volume, unit second.The aramid fiber battery diaphragm that is rolled into through the above-mentioned elevated temperature heat follow-up works such as shaping of can also cutting edge.
The present invention is with having the battery diaphragm that resistant to elevated temperatures aramid fiber is processed; Overcome the not weakness of heatproof of existing plastic diaphragms; Simultaneously can be through the fiber prescription and the gas permeability and the porosity requirement of forming technology of adjustment blank to satisfy battery diaphragm; Avoided in the battery diaphragm manufacture process based on plastics, cooldown rate is to the influence of phase process; The motion of polymer solution concentration, molecular weight, solvent molecule and crystallizing power, nucleator are to the influence of membrane pore structure form; The system phase diagram of having avoided the interaction because of solvent and polymer to have influence on, and then the course that is separated of influence, promptly interacting is prone to that greatly then liquid-solid phase takes place and separates, and generates spherulitic crystal structure; Little then being prone to that interact taken place, and obtains alveolate texture.
Battery diaphragm of the present invention has reached the requirement of ion battery barrier film: have electronic isolation property, guarantee the mechanical isolation of both positive and negative polarity; Certain aperture and porosity are arranged, guarantee low resistance and high ionic conductivity, (for example lithium ion Li+) has good permeability to ion.Because electrolytical solvent is the organic compound of strong polarity, barrier film must corrode by electrolyte resistance, and enough chemistry and electrochemical stability are arranged; Good and have enough imbibition moisture-retaining capacity to the wettability of electrolyte; Have enough mechanical properties, comprise puncture intensity, hot strength etc.; Spatial stability and planarization are good; Thermal stability is with to automatically shut down protective value good.The battery diaphragm that the present invention is based on aramid fiber can be used in the manufacturing of various ion batteries fully.
Preparation method of the present invention is aramid fiber and aramid fiber fibrid, and through special wet-formed, the high temperature rolling and molding is processed diaphragm material, to different battery diaphragm thickness, can obtain the good barrier film of different performance.The adding of anti flocculant can fully disperse fiber in the technical process; Join than long aramid fiber and than the short Fanglun slurry cake or the ginseng of fibrid, can solve the battery diaphragm puncture intensity and the requirement of evenness of manufacturing paper with pulp preferably fibre length.
The present invention combines aramid fiber and fibrid advantage separately; Prepared a kind of Fanglun l414 fiber and Fanglun l414 fibrid or aramid fiber 1313 fibrid fiber is manufactured paper with pulp, or aramid fiber 1313 fiber and Fanglun l414 fibrid or the aramid fiber 1313 fibrid fiber all-in-one-piece battery diaphragm of manufacturing paper with pulp.Particularly according to the battery diaphragm of the proportioning of preferred group branch of the present invention preparation, the plastic diaphragms of producing compared to prior art, excellent in the performance of aspect of performances such as tearing strength, heatproof.
Excellent specific properties such as battery diaphragm of the present invention has that lightweight, softness, height ratio are strong, height ratio mould, high temperature resistant, endurance, fire-retardant, resist chemical, good radiation resistance, low thermal coefficient of expansion, Bc are good can be widely used in high-tech sectors such as electromechanics, Aeronautics and Astronautics.
Embodiment
In order to make the object of the invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
Material source:
The Fanglun l414 fiber: Japanese Supreme Being people company produces;
The Fanglun l414 fibrid: Japanese Supreme Being people company produces;
The aramid fiber 1313 fiber: Guangdong newly can produce;
The aramid fiber 1313 fibrid: Chengdu dragon nation produces;
[embodiment 1]
Prepare present embodiment 1 battery diaphragm in following ratio:
Fanglun l414 fiber (less than 1.5mm) 75 weight portions
Fanglun l414 fibrid 25 weight portions
With the Fanglun l414 fiber of above-mentioned content by 1% weight concentration after the waterpower fluffer is discongested, further pull an oar final 10～70 ° of SR slurries of pulping beating degree A through mill.With above-mentioned content Fanglun l414 fibrid by in the waterpower fluffer, discongesting; And further pull an oar through mill; Finally process 10～75 ° of SR slurries of beating degree B; Then slurries A and slurries B are added water in dosing chamber and mix, thereby form the slurry that can be added into the former flow box, in slurry-stablizing case, add an amount of polyethylene glycol oxide.Regulate slurries online pressure head through slurry-stablizing case, slurries are evenly distributed on the forming net in head box, unnecessary slurries through overflow to destroying the forebay.When slurries when forming net moves, by the effect of couch roll, most of water leaches from slurry; The wet pulp base leaves the former wire side, through woollen blanket, further sloughs moisture through vacuum tank to wet pressing; Get into drying section, remaining moisture is removed in baking, with after the hot-rolling mill single hot-roll forming; Control hot rolling linear pressure is 10～120kg/cm, in 150～300 ℃ of scopes of control hot-rolled temperature.Battery diaphragm after the hot rolling makes the density of battery diaphragm, the surface characteristic of battery diaphragm, the deflection of battery diaphragm reach gratifying effect through the further integer of calender.Obtain the result and see table 1:
Table 1
[embodiment 2]
Prepare present embodiment 2 battery diaphragms by following weight portion:
Fanglun l414 fiber (less than 1.5mm) 97 weight portions
Fanglun l414 fibrid 3 weight portions
The preparation method of battery diaphragm is identical with embodiment 1, and the result who obtains sees table 2:
Table 2
[embodiment 3]
Prepare present embodiment 3 battery diaphragms by following weight portion:
Fanglun l414 fiber (less than 1.5mm) 65 weight portions
Fanglun l414 fibrid 35 weight portions
The preparation method of battery diaphragm is identical with embodiment 1, and the test result that obtains is seen table 3:
Table 3
[embodiment 4]
Prepare present embodiment 4 battery diaphragms in following ratio:
Fanglun l414 fiber (less than 1.5mm) 25 weight portions
Fanglun l414 fibrid 75 weight portions
The preparation method of battery diaphragm is identical with embodiment 1, and the test result that obtains is seen table 4:
Table 4
[embodiment 5]
Prepare present embodiment 5 battery diaphragms by following weight portion:
Fanglun l414 fiber (less than 1.5mm) 75 weight portions
Aramid fiber 1313 fibrid 25 weight portions
To embodiment 1, substitute the Fanglun l414 fibrid with the aramid fiber 1313 fibrid, all the other steps are undertaken by embodiment 1 identical preparation method, and resulting test result is seen table 5:
Table 5
[embodiment 6]
Prepare present embodiment 6 battery diaphragms by following weight portion:
Aramid fiber 1313 fiber (less than 1.5mm) 80 weight portions
Fanglun l414 fibrid 20 weight portions
To embodiment 1, substitute the Fanglun l414 fiber with the aramid fiber 1313 fiber, all the other steps are undertaken by embodiment 1 identical preparation method, and resulting test result is seen table 6:
Table 6
[embodiment 7]
Prepare present embodiment 6 battery diaphragms by following weight portion:
Aramid fiber 1313 fiber (less than 1.5mm) 70 weight portions
Aramid fiber 1313 fibrid 30 weight portions
To embodiment 1, substitute the Fanglun l414 fiber with the aramid fiber 1313 fiber, and replace the Fanglun l414 fibrid with the aramid fiber 1313 fibrid, all the other steps are undertaken by embodiment 1 identical preparation method, and resulting test result is seen table 7:
Table 7
The invention is not restricted to above execution mode, can be according to the dependence of parameters such as ginseng mixing ratio, hot rolling technology with battery diaphragm physical mechanical strength index, change proportioning and parameter are processed the product type and the specification that can satisfy user's specific (special) requirements; Those skilled in the art can also make various changes and distortion, under the prerequisite that does not break away from spirit of the present invention, all fall within the scope of the invention.
Claims (7)
1. preparation method based on the battery diaphragm of aramid fiber, this battery diaphragm is applied to it is characterized in that in the ion battery that said battery diaphragm is made up of following component:
Ultrashort aramid fiber 65～97 weight portions;
Aramid fiber fibrid 3～35 weight portions;
Wherein, the fibre length of said ultrashort aramid fiber is less than 1.5mm; Said ultrashort aramid fiber is ultrashort Fanglun l414 fiber or ultrashort aramid fiber 1313 fiber; Said aramid fiber fibrid is Fanglun l414 fibrid or aramid fiber 1313 fibrid;
Said preparation method comprises the steps:
The aramid fiber that 1) will be equal to said ultrashort aramid fiber content prescinds, discongests and pulls an oar, and making the pulping beating degree is the slurry A of 10～70 ° of SR, and aramid fiber described in the said slurry A is changed into the ultrashort aramid fiber of fibre length less than 1.5mm by fento;
2) aramid fiber fibrid of above-mentioned content is discongested and pull an oar, making the pulping beating degree is the slurry B of 10～75 ° of SR;
3) said slurry A and slurry B are mixed the formation mixed slurry, and in said mixed slurry, add anti flocculant;
4) with the shaping of manufacturing paper with pulp of said mixed slurry;
5) dry and preheating;
6) the high temperature hot rolling obtains said battery diaphragm, and the hot rolling linear pressure of said high temperature hot rolling is 10～120kg/cm, and rolling speed is 3～30 meters/minute, and the temperature of said high temperature hot rolling is 130～300 ℃.
2. preparation method according to claim 1; It is characterized in that; Aramid fiber or step 2 described in the said step 1)) described in after aramid fiber fibrid discongested, pull an oar with trough-style pulp beater or mill or big tapering jordan, finally make said slurry A or slurry B.
3. preparation method according to claim 1 is characterized in that, adopts forming device for cylinder machine with the shaping of manufacturing paper with pulp of said mixed slurry wet method in the said step 4), and said forming device for cylinder machine is many forming device for cylinder machine or single forming device for cylinder machine.
4. according to each described preparation method of claim 1～3, it is characterized in that the air permeability Gurley of said battery diaphragm is 1～25 second.
5. according to each described preparation method of claim 1～3, it is characterized in that the porosity of said battery diaphragm is 28～75%.
6. according to each described preparation method of claim 1～3, it is characterized in that the thickness of said battery diaphragm is 0.03～0.06mm.
7. according to each described preparation method of claim 1～3, it is characterized in that the density of said battery diaphragm is 0.30～0.65g/cm
3
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102047659A CN101872852B (en) | 2010-06-21 | 2010-06-21 | Preparation method of cell diaphragm based on aramid fiber |
| PCT/CN2011/001015 WO2011160431A1 (en) | 2010-06-21 | 2011-06-20 | Battery diaphragm based on aramid fiber and preparation method of the same |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102047659A CN101872852B (en) | 2010-06-21 | 2010-06-21 | Preparation method of cell diaphragm based on aramid fiber |
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| CN101872852A CN101872852A (en) | 2010-10-27 |
| CN101872852B true CN101872852B (en) | 2012-09-26 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2011160431A1 (en) * | 2010-06-21 | 2011-12-29 | 深圳吴天龙邦复合材料有限公司 | Battery diaphragm based on aramid fiber and preparation method of the same |
| EP2923363B1 (en) * | 2012-11-23 | 2018-05-02 | Teijin Aramid B.V. | Electrical insulating paper |
| EP3041988B1 (en) * | 2013-09-06 | 2017-07-19 | Teijin Aramid B.V. | Separator paper for electrochemical cells |
| CN104577011B (en) * | 2014-12-25 | 2017-12-08 | 深圳昊天龙邦复合材料有限公司 | A kind of battery diaphragm reinforcing material |
| CN107724140A (en) * | 2017-11-14 | 2018-02-23 | 宁波日新恒力科技有限公司 | A kind of polyarylate fiber base battery barrier film and its preparation method and application |
| CN107910477B (en) * | 2017-11-14 | 2021-02-09 | 宁波日新恒力科技有限公司 | Preparation method of cellulose and polyarylate fiber-based battery diaphragm |
| CN109473604A (en) * | 2018-09-17 | 2019-03-15 | 湖北江升新材料有限公司 | A kind of high-temperature resistant aramid fiber applies the preparation method of cloth diaphragm |
| CN115207559B (en) * | 2022-06-28 | 2024-03-22 | 陈克复 | High-performance aramid fiber diaphragm and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108034A (en) * | 1985-11-04 | 1987-07-22 | 国家建筑材料工业局南京玻璃纤维研究设计院 | Fibreglass diaphragm for lithium cell |
| CN1670989A (en) * | 2004-03-19 | 2005-09-21 | 株式会社巴川制纸所 | Electronic component separator and method for producing the same |
| CN101611506A (en) * | 2007-03-15 | 2009-12-23 | 日立麦克赛尔株式会社 | Separator for electrochemical device, electrode for electrochemical device and electrochemical element |
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|---|---|
| CN101872852A (en) | 2010-10-27 |
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