CN103337603A - Porous battery diaphragm material and manufacturing method and application of porous battery diaphragm material - Google Patents
Porous battery diaphragm material and manufacturing method and application of porous battery diaphragm material Download PDFInfo
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- CN103337603A CN103337603A CN2013102959263A CN201310295926A CN103337603A CN 103337603 A CN103337603 A CN 103337603A CN 2013102959263 A CN2013102959263 A CN 2013102959263A CN 201310295926 A CN201310295926 A CN 201310295926A CN 103337603 A CN103337603 A CN 103337603A
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Abstract
The invention relates to a porous battery diaphragm material, and a manufacturing method and an application of the porous battery diaphragm material. The manufacturing method comprises the following steps of (1) cutting a star-shaped or crossed bi-component composite fiber and/or a single-component synthetic fiber with the diameter of 3-15 micrometers into staple fibers which are 2-15mm in length for use with a disc fiber cutter, (2) performing beating and defibering treatment on the cut staple fibers, cellulosic fibers and inorganic fibers to prepare high-concentration fiber stuff, taking water as a dispersing medium and alkane sulfonate as a dispersing agent, (3) performing hydraulic single-net double-layer inclined wire forming with a center spreader, and (4) preparing the porous battery diaphragm material with hot air at 130-220 DEG C after dehydration and squeezing. The material has excellent performance, and can serve as a battery diaphragm, a capacitor diaphragm, a high-temperature insulation membrane and a high-temperature filter material after treatment such as sulphonation treatment, grafting treatment, high-temperature pressing and coating treatment.
Description
Technical field
The present invention relates to porous battery diaphragm material preparing technical field, particularly a kind of porous battery diaphragm material and manufacture method and application.
Background technology
Be accompanied by the fast development of IT electronic industry, new-energy automobile, energy storage industry, secondary power supply just is being vigorous growth trend.Battery diaphragm is as one of critical material of secondary power supply, and it acts on ever more important, so the manufacturing of battery diaphragm material causes that also people more and more pay attention to.
The secondary battery membrane material manufacturing method mainly comprises phase inversion, leaching, pulling method, the combing of fiber dry method, the moulding of fiber wet papermaking etc. at present, wherein phase inversion, leaching, pulling method are mainly used to make lithium ion battery separator, this class battery diaphragm is two-dimensional structure, defectives such as temperature tolerance difference and thermal contraction are big, poor stability, porosity are low, electrolyte impregnability difference are in the defective of guaranteeing to exist aspect lithium ion battery security and useful life self.Dry method combing moulding is mainly used to make the alkaline secondary cell barrier film, there is poor, the skewness of fiber dispersion in this class battery diaphragm, can't satisfy the instructions for use of power type, high power capacity, high magnification alkaline battery, easily cause problems such as battery consistency is poor, short circuit ratio height.Adopt wet papermaking technology production porous battery diaphragm material, the extraordinary application requirements that satisfies alkaline battery, lithium ion battery, ultracapacitor, high-temperature insulation electronic component and high temperature filtration of diaphragm material that these class methods are produced, but because problems such as material selection, though the wet papermaking of employing technology production porous battery diaphragm material is arranged at present, mostly be to adopt the moulding of single net individual layer, MULTILAYER COMPOSITE then, or adopt two nets two-layered, formed, can cause problems such as equipment investment, comprehensive production cost be higher like this.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art and shortcoming, and the manufacture method of the porous battery diaphragm material that a kind of technology is simple, reasonable, low, the comprehensive production cost of equipment investment is low is provided.
Another purpose of the present invention is to provide a kind of porous battery diaphragm material of being made by said method.
Still a further object of the present invention is to provide with above-mentioned porous battery diaphragm material, after handling as modes such as sulfonation processing, grafting processing, high temperature compacting and coating processing, can be used as alkaline battery separator, lithium ion battery separator, ultracapacitor barrier film, high-temperature insulation film and high-temperature-resistant filtering material and carry out extensive use.
Purpose of the present invention is achieved through the following technical solutions: a kind of manufacture method of porous battery diaphragm material is characterized in that comprising the steps:
(1) selecting fibre diameter for use is 3 μ m～15 μ m " rice " fonts or " ten " font bicomponent composite fibre and/or one pack system synthetic fibers, and adopting the disc type fibre cutting machine to be cut into length is that the short fiber of 2mm～15mm is standby;
(2) short fiber of well cutting and/or cellulose fibre and/or inorfil being discongested processing through making beating, be prepared into the high concentration fibre stuff, is decentralized medium with water, and alkylsulfonate is dispersant;
(3) adopt the double-deck tiltedly net forming of the single net of center pulp distributor waterpower formula;
(4) after the dehydration squeezing, the porous battery diaphragm material is made in oven dry in 130 ℃～220 ℃ hot blast air.
Wherein said " rice " font or " ten " font bicomponent composite fibre are one or more in the fibers such as PP/PE, PET/PP, PA/PP, PET/PA; Described one pack system synthetic fibers are one or more in polypropylene fibre, polyester fiber, aramid fiber, the polyimide fiber; Described cellulose fibre is the nano-scale fiber cellulose fiber; Described inorfil is one or more in Zirconium oxide fibre, alumina fibre, the magnesia fibers.
In mass fraction, wherein bicomponent composite fibre is 10%～100%; The one pack system synthetic fibers are 0～100%; Cellulose fibre is 0～100%; Inorfil is 0～25%.
The porous battery diaphragm material that is obtained by above-mentioned manufacture method, after handling as modes such as sulfonation processing, grafting processing, high temperature compacting and coating processing, can be used as alkaline battery separator, lithium ion battery separator, ultracapacitor barrier film, high-temperature insulation film and high-temperature-resistant filtering material and carry out extensive use.
The present invention has following beneficial effect:
(1) the porous battery diaphragm material that adopts the present invention to make, have excellent chemical stability and very large specific area, because in the fiber material that the present invention adopts bicomponent composite fibre is arranged, utilize the low melting point in the fiber partly to carry out adhesion between fiber, adhesive-free adds in the manufacture process, and again because the structure of bicomponent composite fibre is " rice " font or " ten " font, significantly reduced the area of adhesion point between fiber like this.
(2) the porous battery diaphragm material that adopts the present invention to make, it has uniform pore size distribution, and it is three-dimensional netted that pore structure is, because the present invention adopts the double-deck tiltedly advanced wet papermaking technology of net forming of single net, again because fiber is discongested the short fiber of processing for process, the uniformity that has effectively guaranteed fiber is disperseed, cross-distribution, uniformity and the tridimensional network in hole have effectively been guaranteed, and effectively improved the intensity of porous battery diaphragm material, overcome the minimum living liquid rate of present manufacturing lithium ion battery separator like this, low porosity, the shortcoming that high short circuit ratio etc. are fatal effectively raises fail safe and the cycle performance of lithium ion battery.
(3) the porous battery diaphragm material that adopts the present invention to make, has outstanding high temperature resistance, this is because material of the present invention contains polyester composition fiber, cellulose fibre or inorfil in constituting, these fibers have played the skeleton supporting role, the battery diaphragm of the porous battery diaphragm material manufacturing that therefore makes is compared additive method and is had the good temperature resistance energy, has remarkable advantages aspect the high temperature safe performance that guarantees battery.
Description of drawings
The porous battery diaphragm material structure chart for the preparation of alkaline battery separator that Fig. 1 makes for the present invention.
The lithium ion battery separator structure chart that the porous battery diaphragm material that Fig. 2 makes for the present invention prepares.
The ultracapacitor membrane configuration figure that the porous battery diaphragm material that Fig. 3 makes for the present invention prepares.
The resistance to elevated temperatures figure of the lithium ion battery separator that the porous battery diaphragm material that Fig. 4 makes for the present invention prepares.
The discharge performance figure of the lithium ion battery separator that the porous battery diaphragm material that Fig. 5 makes for the present invention prepares.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) with fibre diameter is " rice " type PP/PE bicomponent composite fibre of 11 μ m, adopts the disc type fibre cutting machine to be cut into the short fiber that length is 5mm.
(2) short fiber of step (1) preparation being discongested processing through high speed rotary-cut making beating, be prepared into concentration and be 5% fibre stuff, is decentralized medium with water, and dodecyl sodium sulfate is dispersant.
(3) fibre stuff that step (2) is made by the isobaric starching of center pulp distributor, through the oblique net head box of waterpower formula, carries out the double-deck tiltedly net forming of list net.
(4) after the dehydration squeezing, dry in the drying tunnel of 135 ℃ of hot-airs, being prepared into surface density is 60g/m
2The porous battery diaphragm material, its structure is seen Fig. 1.
(5) the porous battery diaphragm material that makes being carried out the sulfonation of sulfur trioxide gas phase handles, make alkaline battery separator, method of operation is handled in concrete sulfonation: continuously be transported in sulfonation reactor with expansion mode the porous battery diaphragm material that makes, adopting concentration is that 90% sulfur trioxide gas carries out gas phase xanthation and handles, the sulfonating reaction temperature is 80 ℃, and speed is 15m/min; Material after the sulfonation is transported in the alkaline bath, and the KOH concentration of lye is 1% in the groove, and alkali cleaning speed is 15m/min; Behind rinsed with deionized water and press dewatering, to dry, bake out temperature is controlled to be 100 ℃; Material after the oven dry is after thickness adjustment equipment is adjusted, and obtaining surface density is 63g/m
2, thickness is the product of 0.15mm, the products obtained therefrom performance index relatively see Table 1 with external like product.
Table 1: alkaline battery separator performance comparison sheet
Embodiment 2
(1) with fibre diameter is " ten " type PET/PP bicomponent composite fibre and the one pack system polyester fiber of 3 μ m, adopts the disc type fibre cutting machine to be cut into the short fiber that length is 5mm.
(2) short fiber PET/PP composite fibre, polyester fiber and nano-cellulose fiber, the alumina fibre that step (1) is prepared, with the absolute dry mass of fiber, be 40: 35: 10 by mass fraction: 5 evenly mix, discongest processing through high speed rotary-cut making beating, be prepared into concentration and be 2% fibre stuff, be decentralized medium with water, neopelex is dispersant.
(3) fibre stuff that step (2) is made by the isobaric starching of center pulp distributor, through the oblique net head box of waterpower formula, carries out the double-deck tiltedly net forming of list net.
(4) after the dehydration squeezing, dry in the drying tunnel of 170 ℃ of hot-airs, being prepared into surface density is 13g/m
2Porous lithium ion cell barrier film basis material.
(5) basis material that makes is suppressed fast through 200 ℃ high temperature earlier, its thickness is adjusted into 20 μ m, service quality concentration is that 30% nano aluminium oxide water-based coating fluid is coated with making material then, speed is 10m/min, the coating layer thickness single face is 4 μ m, after 80 ℃ of oven dry, make lithium ion battery separator, its structure sees that Fig. 2, performance relatively see Table 2, resistance to elevated temperatures sees that Fig. 4, discharge performance see Fig. 5.
Table 2: lithium ion battery separator performance comparison sheet
Embodiment 3
Concrete implementation step is as follows:
(1) with fibre diameter is " rice " type PET/PP bicomponent composite fibre and the one pack system polyester fiber of 3 μ m, adopts the disc type fibre cutting machine to be cut into the short fiber that length is 5mm.
(2) with the PET/PP composite short fiber of well cutting, polyester staple fibers peacekeeping nano-cellulose fiber with the absolute dry mass of fiber, be evenly to mix at 10: 10: 80 by mass fraction, discongest processing through high speed rotary-cut making beating, be prepared into concentration and be 1% fibre stuff, be decentralized medium with water, neopelex is dispersant.
(3) fibre stuff that step (2) is made by the isobaric starching of center pulp distributor, through the oblique net head box of waterpower formula, carries out the double-deck tiltedly net forming of list net.
(4) after the dehydration squeezing, dry in the drying tunnel of 170 ℃ of hot-airs, being prepared into surface density is 18g/m
2Porous ultracapacitor diaphragm material.
(5) material that makes is carried out the adjustment of thickness degree through the pressure rolling of high temperature calendering machine, the calender surface temperature of calendering machine is 220 ℃, and pressure is 25MPa, the calendering machine speed of service is 20m/min, the material thickness that makes is adjusted into 30 μ m, makes the ultracapacitor barrier film, its structure is seen Fig. 3.
Utilize the ultracapacitor separator product performance index of method for preparing relatively to see Table 3 with external like product.
Table 3: ultracapacitor membrane properties comparison sheet
Claims (3)
1. the preparation method of a porous battery diaphragm material is characterized in that comprising the steps:
(1) selecting fibre diameter for use is 3 μ m～15 μ m " rice " fonts or " ten " font bicomponent composite fibre and/or one pack system synthetic fibers, and adopting the disc type fibre cutting machine to be cut into length is that the short fiber of 2mm～15mm is standby;
(2) short fiber after the cutting that step 1 is obtained, and/or cellulose fibre, and/or inorfil discongests processing through making beating, is prepared into the high concentration fibre stuff, is decentralized medium with water, alkylsulfonate is dispersant;
(3) adopt the double-deck tiltedly net forming of the single net of center pulp distributor waterpower formula;
(4) after the dehydration squeezing, make the porous battery diaphragm material 130 ℃～220 ℃ hot blast air oven dry.
Wherein said " rice " font or " ten " font bicomponent composite fibre are one or more in the fibers such as PP/PE, PET/PP, PA/PP, PET/PA; Described one pack system synthetic fibers are one or more in polypropylene fibre, polyester fiber, aramid fiber, the polyimide fiber; Described cellulose fibre is the nano-scale fiber cellulose fiber; Described inorfil is one or more in Zirconium oxide fibre, alumina fibre, the magnesia fibers.
In mass fraction, wherein bicomponent composite fibre is 10%～100%; The one pack system synthetic fibers are 0～100%; Cellulose fibre is 0～100%; Inorfil is 0～25%.
2. the porous battery diaphragm material that obtains of preparation method according to claim 1.
3. the application of the described porous battery diaphragm material of claim 2, it is characterized in that described porous battery diaphragm material after oversulfonate processing, grafting processing, high temperature compacting and coating processing mode are handled, as alkaline battery separator, lithium ion battery separator, ultracapacitor barrier film, high-temperature insulation film and high-temperature-resistant filtering material.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105789528A (en) * | 2014-12-24 | 2016-07-20 | 北京化工大学常州先进材料研究院 | Preparation method of PA/PP porous battery separator material |
| CN105789527A (en) * | 2014-12-23 | 2016-07-20 | 北京化工大学常州先进材料研究院 | Preparing method of PET/PP porous cell diaphragm material |
| CN105789526A (en) * | 2014-12-23 | 2016-07-20 | 北京化工大学常州先进材料研究院 | Preparation method of PP/PE porous battery separator material |
| CN105789529A (en) * | 2014-12-23 | 2016-07-20 | 北京化工大学常州先进材料研究院 | Preparation method of PET/PA porous battery separator material |
| TWI644798B (en) * | 2016-03-31 | 2018-12-21 | 特種東海製紙股份有限公司 | Paper capable of stable paper feeding |
| CN109378427A (en) * | 2018-09-17 | 2019-02-22 | 名添科技（深圳）有限公司 | A kind of non-woven fabrics basement membrane and preparation method thereof |
| CN110429227A (en) * | 2019-07-03 | 2019-11-08 | 莱州联友金浩新型材料有限公司 | A kind of preparation method of fibrous type lithium ion battery separator |
| CN112191051A (en) * | 2020-11-19 | 2021-01-08 | 河南科高新材料有限公司 | Static-free mask filtering membrane and preparation method thereof |
| CN113725557A (en) * | 2021-09-02 | 2021-11-30 | 深圳市星源材质科技股份有限公司 | Lithium ion battery diaphragm supporting layer and lithium ion battery diaphragm |
| CN114790665A (en) * | 2022-05-19 | 2022-07-26 | 株洲时代新材料科技股份有限公司 | Carbonization-free diaphragm paper and preparation method and application thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105789527A (en) * | 2014-12-23 | 2016-07-20 | 北京化工大学常州先进材料研究院 | Preparing method of PET/PP porous cell diaphragm material |
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| CN109378427A (en) * | 2018-09-17 | 2019-02-22 | 名添科技（深圳）有限公司 | A kind of non-woven fabrics basement membrane and preparation method thereof |
| CN110429227A (en) * | 2019-07-03 | 2019-11-08 | 莱州联友金浩新型材料有限公司 | A kind of preparation method of fibrous type lithium ion battery separator |
| CN112191051A (en) * | 2020-11-19 | 2021-01-08 | 河南科高新材料有限公司 | Static-free mask filtering membrane and preparation method thereof |
| CN113725557A (en) * | 2021-09-02 | 2021-11-30 | 深圳市星源材质科技股份有限公司 | Lithium ion battery diaphragm supporting layer and lithium ion battery diaphragm |
| CN113725557B (en) * | 2021-09-02 | 2024-04-09 | 深圳市星源材质科技股份有限公司 | Lithium ion battery diaphragm supporting layer and lithium ion battery diaphragm |
| CN114790665A (en) * | 2022-05-19 | 2022-07-26 | 株洲时代新材料科技股份有限公司 | Carbonization-free diaphragm paper and preparation method and application thereof |
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