CN108232086A - A kind of once-forming lithium ion battery separator and its preparation method and application - Google Patents

A kind of once-forming lithium ion battery separator and its preparation method and application Download PDF

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Publication number
CN108232086A
CN108232086A CN201711442896.9A CN201711442896A CN108232086A CN 108232086 A CN108232086 A CN 108232086A CN 201711442896 A CN201711442896 A CN 201711442896A CN 108232086 A CN108232086 A CN 108232086A
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China
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nanofiber
quantification
layer
supporting layer
slurry
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CN108232086B (en
Inventor
胡健
龙金
姚运振
王宜
汪洋
蒙玲
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South China University of Technology SCUT
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GUANGZHOU HUACHUANG CHEMICAL MATERIAL TECHNOLOGY DEVELOPMENT Co Ltd
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Cell Separators (AREA)

Abstract

The present invention relates to a kind of once-forming lithium ion battery separators and its preparation method and application, the battery diaphragm is included or is made of supporting layer and packing layer, wherein, the supporting layer includes or by ultra-fine trunk fiber, at least two in thermoplastic binder fiber and the first nanofiber are made, described filler layer is included or is made of at least one of inorganic filler and third nanofiber, the lithium ion battery separator thickness is at 19 31 μm, maximum diameter of hole is not more than 1 μm, 300 DEG C of processing 1h percent thermal shrinkages are less than 3%, high temperature lower diaphragm plate still has some strength, ensure the stability and isolation of packing layer rigid structure under high temperature, meet diaphragm heat-resisting, requirement in terms of hole and intensity, excellent combination property.

Description

A kind of once-forming lithium ion battery separator and its preparation method and application
Technical field
The present invention relates to battery technology fields, and in particular to a kind of once-forming lithium ion battery separator and its preparation side Method and application.
Background technology
With the increase of lithium ion battery energy density and the increase of battery volume and weight, thermal diffusivity and stabilization Property be deteriorated, be more easy to occur thermal runaway phenomenon, under the high temperature conditions diaphragm shrink and fuse, cause positive and negative anodes contact and it is rapid Big calorimetric is gathered, inside battery hyperbar is generated, causes cells burst or explosion.Diaphragm is the key technology for preventing battery short circuit Material, battery short circuit will substantially accelerate the decomposition caused heat release of battery material, thus improve diaphragm thermal stability and fusing-off temperature for Cell safety is most important.
At present, lithium ion battery separator is mainly two major class of polyolefin stretched film and non-woven fabrics.Polyolefin stretched film is (as gathered Ethylene (PE) or polypropylene (PP) film) technical maturity is high, there is excellent mechanical property, chemical stability and relatively inexpensive Advantage is mainstream diaphragm currently on the market.However polyolefine material heat resistance is limited, suitable operating temperature is less than 150 ℃.Refractory ceramics coating is carried out on polyalkene diaphragm, the thermal stability of diaphragm is can effectively improve, however is surveyed at 300 DEG C It takes temperature bright, the skeleton of ceramic particle also exists, but diaphragm intensity completely loses, and only can not effectively improve diaphragm with ceramic coated High temperature resistance.Non-woven fabrics is the three dimensional pore structures material formed using the accumulation of fiber non-directional, has raw material can be flexible Selection and structure can flexible design characteristic, nonwoven cloth diaphragm in heat-resisting quantity, fast charging and discharging performance and service life with For polyalkene diaphragm compared to more advantage, but nonwoven cloth diaphragm intensity is low, there are macropores, it is possible to cause battery micro-short circuit.
Inorganic filler has excellent thermal stability, and the coating inorganic particle usually on polyolefin or non-woven fabrics base material can Improve thermal stability.The patent application (publication number US20060024569) of German goldschmidt chemical corporation proposes to use polymer fiber Non-woven fabrics barrier film base material is made, base material individual layer is manufactured paper with pulp, and two-sided largely being impregnated or coated with filler grain prepares composite diaphragm, and diaphragm makes It it is 200 DEG C with temperature.But the diaphragm is due to the structure of base material and the limitation of composition, even if double spread or dipping filler grain, Still inevitably there are macropores and the caducous problem of filler grain；In addition, after tested, the diaphragm of the patent is at 300 DEG C 1h, base material fusing are handled, diaphragm intensity completely loses, it is impossible to ensure the isolation performance of 300 DEG C of lower diaphragm plates.South China Science ＆ Engineering University Patent application (publication number CN104157812A) proposes, using papermaking and coating technique prepare the lithium ion battery of three-decker every Film, but the diaphragm compacted zone, using part non-nano synthetic fibers, it is small that the thermal stability of diaphragm is only capable of doing percent thermal shrinkage at 110 DEG C In 1.0%, the requirement to high temp resistance lithium ion cell diaphragm can not be met；Inorganic coat increases preparation section, cost, And it is easily damaged by the coating of adhesive absorption, inevitably there is particle obscission.SUMITOMO CHEMICAL Chemical Co., Ltd. it is special Profit application (publication number CN106914384A) proposition coats refractory coating on polyolefin base material, and heat-resisting paint is by nothings such as aluminium oxide Machine filler is dispersed in NMP (N- methyl-pyrrolidons) solution of aramid fiber and prepares, although this method can effectively promote diaphragm Heat resistance, but painting process is increased, and using organic solvent, accordingly increased production cost and environment, safety Control cost.
Invention content
The purpose of the present invention is to provide a kind of once-forming lithium ion battery separators and its preparation method and application, should Diaphragm is compacted by the once-forming acquisition of multilayer inclined wire, even structure, and simple production process is pin-free, is no more than 30 μ in thickness Under the premise of m, tensile strength still may be up to 1506N/mm, and the percent thermal shrinkage at 110 DEG C is 0, and handling 1h at 300 DEG C still has There is preferable intensity to keep, the percent thermal shrinkage at 300 DEG C is still less than 3%, outside the requirement in terms of meeting hole and intensity, especially It is with particularly preferred heat resistance, excellent combination property.
The above-mentioned purpose of the present invention is achieved through the following technical solutions.
First, the present invention provides a kind of once-forming lithium ion battery separator, and it includes or by supporting layer and packing layers Composition, wherein, the supporting layer include or by ultra-fine trunk fiber, thermoplastic binder fiber and the first nanofiber at least Two kinds are made, and described filler layer is included or is made of at least one of inorganic filler and third nanofiber.
Preferably, the thickness of the diaphragm is 19-31 μm, preferably 19-26 μm；Preferably, the diaphragm is quantification of 15-30g/m2, preferably 15-25g/m2, more preferably 19-22g/m2；Preferably, the average pore size of the diaphragm is less than 1 μm, Preferably 0.2-0.5 μm；Preferably, the maximum diameter of hole of the diaphragm is not more than 1 μm, preferably 0.7-1 μm；Preferably, it is described Percent thermal shrinkage≤2.8% at 300 DEG C of diaphragm.
Preferably, the quantification of 6-17g/m of the supporting layer2, preferably 8-14g/m2, more preferably 8-11g/m2, most preferably For 11g/m2；The quantification of 5-19g/m of described filler layer2, preferably 5-16g/m2, more preferably 5-9g/m2, it is further preferably 5-7g/ m2, most preferably 7g/m2。
Preferably, in the supporting layer, the quantification of 3-9g/m of the ultra-fine trunk fiber2, preferably 3-6g/m2, more Preferably 5g/m2；The quantification of 3-9g/m of the thermoplastic binder fiber2, preferably 3-6g/m2, more preferably 4g/m2；It is described The quantification of 0-11g/m of first nanofiber2, preferably 2-11g/m2, more preferably 2-8g/m2, it is further preferably 2-6g/m2, most Preferably 2g/m2。
Preferably, the supporting layer includes or by quantification of 3-9g/m2Ultra-fine trunk fiber, quantification of 3-9g/m2Heat Plasticity viscose fibre and quantification of 0-11g/m2The first nanofiber be made；
Preferably, the supporting layer includes or by quantification of 3-6g/m2Ultra-fine trunk fiber, quantification of 3-6g/m2Heat Plasticity viscose fibre and quantification of 2-11g/m2The first nanofiber be made；
Preferably, the supporting layer includes or by quantification of 5g/m2Ultra-fine trunk fiber, quantification of 4g/m2Thermoplasticity Viscose fibre and quantification of 2g/m2The first nanofiber be made；
Preferably, in described filler layer, the quantification of 5-19g/m of the inorganic particle2, preferably 5-16g/m2, it is more excellent It is selected as 5-10g/m2, it is further preferably 5-7g/m2, most preferably 7g/m2；The quantification of 0-11g/m of the third nanofiber2, it is excellent It is selected as 2-11g/m2, more preferably 2-8g/m2, in preferably 2-4g/m2, most preferably 0 or 2g/m2；
Preferably, described filler layer includes or by quantification of 5-19g/m2Inorganic particle and quantification of 0-11g/m2 Three nanofibers are made；
Preferably, described filler layer includes or by quantification of 5-7g/m2Inorganic particle and quantification of 0-11g/m2Third Nanofiber is made；
Preferably, described filler layer includes or by quantification of 5-7g/m2Inorganic particle and quantification of 2-11g/m2Third Nanofiber is made；
Preferably, described filler layer is by quantification of 5-7g/m2Inorganic particle be made；
Preferably, described filler layer is by quantification of 7g/m2Inorganic particle be made；
Preferably, described filler layer is by quantification of 7g/m2Inorganic particle and quantification of 2g/m2Third nanofiber system Into；
Preferably, the sum of quantitative of first nanofiber and third nanofiber is not less than 4g/m2；
Preferably, the quantification of 6-17g/m of the supporting layer2, the quantification of 5-19g/m of described filler layer2；
Preferably, the quantification of 8-14g/m of the supporting layer2, the quantification of 5-16g/m of described filler layer2；
Preferably, the quantification of 8-14g/m of the supporting layer2, the quantification of 5-9g/m of described filler layer2；
Preferably, the quantification of 8-11g/m of the supporting layer2, the quantification of 5-7g/m of described filler layer2；
Preferably, the quantification of 8-11g/m of the supporting layer2, the quantification of 5-7g/m of described filler layer2；
Preferably, the quantification of 11g/m of the supporting layer2, the quantification of 7g/m of described filler layer2。
Preferably, the ultra-fine trunk fiber, which is selected from, stretches dacron fibre (stretching PET), polypropylene It is one or more in nitrile fiber (PAN), Fypro (PA) and polypropylene fibre (PP), preferably stretch poly- terephthaldehyde Sour two ester fiber of second (stretching PET)；
Preferably, a diameter of 0.1-6 μm of the ultra-fine trunk fiber, preferably 0.5-4 μm, more preferably 0.5-3 μm, Most preferably 1-3 μm；Preferably, the fibre length of the ultra-fine trunk fiber be 1-6mm, preferably 2-4mm, most preferably 3mm。
Preferably, the thermoplastic binder fiber is selected from polyethylene fibre (PE), polypropylene fibre (PP), poly- pair non-stretched Polyethylene terephthalate fiber (non-stretched PET), two-component PP/PE fibers, two-component PET/PE fibers, two-component PET/PP are fine One or more in peacekeeping two-component PET/co-PET fibers, preferably non-stretched dacron fibre is (not Stretch PET)；
Preferably, a diameter of 0.1-8 μm of the thermoplastic binder fiber, preferably 0.5-6 μm, more preferably 1-5 μm, Most preferably 3-5 μm；Preferably, the fibre length that the thermoplasticity coheres fiber is 1-6mm, preferably 2-4mm.
Preferably, first nanofiber be selected from fibrillation poly(p-phenylene terephthalamide) (PPTA) nanofiber, Fibrillation tencel nanofiber, fibrillation polyparaphenylene Benzo-dioxazole (PBO) nanofiber, primary fibrosis polypropylene nitrile (PAN) One or more in nanofiber, polyimides (PI) nanofiber and nano-cellulose fiber, preferably fibrillation is gathered pair Phenylene terepthalamide's (PPTA) nanofiber or fibrillation tencel nanofiber；
Preferably, the beating degree of first nanofiber is 70-95 ° of SR, preferably 95 ° of SR；
Preferably, the third nanofiber is each independently selected from fibrillation poly(p-phenylene terephthalamide) (PPTA) Nanofiber, fibrillation tencel nanofiber, fibrillation polyparaphenylene Benzo-dioxazole (PBO) nanofiber and fibrillation poly- third It is one or more in alkene nitrile (PAN) nanofiber；
Preferably, the third nanofiber is fibrillation poly(p-phenylene terephthalamide) (PPTA) nanofiber, original Fibrillation polyparaphenylene Benzo-dioxazole (PBO) nanofiber or primary fibrosis polypropylene nitrile (PAN) nanofiber；
Preferably, the beating degree of the third nanofiber is 60-85 ° of SR, preferably 85 ° of SR.
Preferably, the inorganic filler be inorganic particle, the inorganic particle be selected from aluminium oxide, silica, Shui Mushi, It is one or more in magnesium hydroxide, preferably aluminium oxide；
Preferably, the grain size of the inorganic particle be 3 μm hereinafter, preferably 1 μm hereinafter, most preferably 200nm.
Preferably, the lithium ion battery separator is also comprising compacted zone, and the compacted zone is made of the second nanofiber, position Between the supporting layer and described filler layer.
Preferably, when the amount of third nanofiber is 0 in described filler layer, the lithium ion battery separator is also comprising cause Close layer, the compacted zone are made of the second nanofiber, between the supporting layer and described filler layer.
Preferably, the quantification of 0-12g/m of the compacted zone2, preferably 2-12g/m2, more preferably 2-8g/m2, further preferably For 2-4g/m2, most preferably 2g/m2。
Preferably, in the compacted zone, the quantification of 2-12g/m of second nanofiber2, preferably 2-10g/m2, More preferably 2-8g/m2, it is further preferably 2-4g/m2, most preferably 2g/m2；
Preferably, the sum of quantitative of first nanofiber, the second nanofiber and third nanofiber is not less than 4g/ m2；
Preferably, the sum of quantitative of second nanofiber and third nanofiber is not less than 2g/m2；
Preferably, second nanofiber is each independently selected from fibrillation poly(p-phenylene terephthalamide) (PPTA) Nanofiber, fibrillation tencel nanofiber, fibrillation polyparaphenylene Benzo-dioxazole (PBO) nanofiber and fibrillation poly- third It is one or more in alkene nitrile (PAN) nanofiber；
Preferably, second nanofiber is fibrillation poly(p-phenylene terephthalamide) (PPTA) nanofiber, original Fibrillation tencel nanofiber, fibrillation polyparaphenylene Benzo-dioxazole (PBO) nanofiber or primary fibrosis polypropylene nitrile (PAN) are received Rice fiber；
Preferably, the beating degree of second nanofiber is 60-85 ° of SR, preferably 85 ° of SR.
Secondly, the present invention also provides a kind of methods for preparing above-mentioned lithium ion battery separator, and the method includes following Step：
Step a：The raw material of supporting layer, compacted zone and packing layer or supporting layer and packing layer is mixed with water, it is respectively independent Ground discongests, is beaten, mix after, online concentration is diluted with water to using fan pump；
Step b：Supporting layer, compacted zone and packing layer after dilution or supporting layer and packing layer slurry are sent into Hydroformer multilayer pulp distributors, wherein, packing layer slurry enters upper strata runner with certain runner flow, compacted zone slurry with Certain runner flow enters intermediate flow channel, and supporting layer slurry enters the runner against forming net, each runner with certain runner flow Slurry is successively manufactured paper with pulp forming simultaneously in the same area lamination, and l Water Paper page is obtained through dehydration；Preferably, it before manufacturing paper with pulp, also wraps The rectification of slurry is included, makes slurry that the flow regime of high-strength micro-turbulence be presented；
Step c：After the step b, diaphragm l Water Paper page is dried to obtain the dry page of diaphragm by Yankee cylinder；
Step d：After the step c, the dry page of diaphragm handles to obtain by metallic roll and soft calender at a certain temperature Lithium ion battery separator.
Preferably, in step a, before being diluted with water slurry, the solid weight percentage concentration of each layer slurry is 0.2wt%；
Preferably, in step a, a concentration of 0.010-0.050wt% of online of the supporting layer slurry, preferably 0.023-0.049wt%；The online a concentration of 0.010-0.050wt%, preferably 0.02- of the compacted zone slurry 0.048wt%；The online a concentration of 0.05-0.50wt%, preferably 0.064-0.38wt% of described filler layer slurry；Alternatively, The online a concentration of 0.010-0.050wt%, preferably 0.023-0.049wt% of the supporting layer slurry；Described filler layer is starched The online a concentration of 0.03-0.08wt%, preferably 0.047-0.064wt% of material；
Preferably, in stepb, the runner flow of the supporting layer slurry is 100-1000m3/ h, preferably 400- 700m3/ h, the runner flow of the compacted zone slurry is 100-1000m3/ h, preferably 200-500m3/ h, described filler layer slurry The runner flow of material is 40-1000m3/ h, preferably 100-500m3/h；Alternatively, the runner flow of the supporting layer slurry is 100-1000m3/ h, preferably 500-700m3/ h, the runner flow of described filler layer slurry is 40-1000m3/ h, preferably 300-500m3/h：
Preferably, in stepb, it is described against the runner of forming net, middle layer runner and upper strata runner cross-sectional area ratio It is 4-7: 2-5: 1, preferably 7: 2: 1 or 4: 5: 1；Alternatively, the runner against forming net and upper strata runner cross-sectional area ratio It is 1-7: 1-3, preferably 7: 3；
Preferably, in step c, the drying temperature is 80-130 DEG C；
Preferably, in step d, the press polish treatment temperature is 110-220 DEG C；
Preferably, when the thermoplastic binder fiber in the supporting layer is non-stretched PET fiber, drying temperature is 80-130 DEG C, preferably 120 DEG C, press polish treatment temperature are 170-220 DEG C, preferably 190 DEG C；
Preferably, when the thermoplastic binder fiber in the supporting layer is two-component PET/co-PET fibers or two-component PP/PE fibers, drying temperature be 80-130 DEG C, preferably 90 DEG C, press polish treatment temperature be 110-140 DEG C, preferably 120 ℃。
In addition, the present invention also provides a kind of lithium ion battery, it includes lithium ion battery separators as described above.
Compared with prior art, the present invention at least has the advantage that：Lithium ion battery separator structure of the present invention can be realized All raw materials are once-forming, without additional painting process, without adding adhesive, have better pore structure；The present invention The special structure of lithium ion battery separator and fiber composition make its it is relatively low it is quantitative under play nanofiber to the maximum extent The characteristic of high temperature resistant and high-specific surface area makes percent thermal shrinkage of the lithium ion battery separator of the present invention after 300 DEG C of processing 1h small In 3% and still have good intensity, improve the stability and isolation of high temperature lower diaphragm plate packing layer rigid structure, solve The problem of filler particles come off.
For the present invention using Hydroformer multilayer once shaping technologies, supporting layer, packing layer and/or compacted zone difference are only Vertical slurrying is with respectively specifically online concentration, runner flow are manufactured paper with pulp forming in the same area lamination, and simultaneously in specific temperature Lower drying, metallic roll and soft calender processing, obtain the heat safe lithium ion battery separator of the present invention, wherein, in pulp distributor, The specific high velocity slurry stream of the hydraulic pressure control cooperation present invention, leads to the slurry with the specific composition of the present invention and certain concentration The changes of section or geometric dimension for crossing control retaining element change and generate high intensity microturbulent motion, eliminate Free Surface, are conducive to The dispersion of fibre stuff and filler particles；Multilayer raw material is uniformly shaped and is combined closely in waterpower former later, is improved The dimensional stability of high temperature lower diaphragm plate；By the way that flow and concentration is controlled to realize the regulation and control to multilayer raw material, diaphragm of the present invention in addition Structure and fibrous raw material and the specific collocation of inorganic filler, can play this to greatest extent in the specific structure of the present invention Invent the heat resistance and high-specific surface area characteristic of the nanofiber selected and inorganic filler particle and the specific super trunk of the present invention The humidification of fiber, thermoplastic binder fiber also more efficient can neatly adjust the heat-resisting of diaphragm, aperture and strength character, Reliable technical guarantee is improved to prepare thinner high temp resistance lithium ion cell diaphragm.
Description of the drawings
Hereinafter, embodiment of the present invention is described with reference to the accompanying drawings, wherein：
Fig. 1 and Fig. 2 is lithium ion battery separator apparent form schematic diagram prepared by the present invention.
Fig. 3 is the structure diagram of tri- layers of Hydroformer that the present invention uses, and wherein A represents pulp distributor, and B represents whole Area is flowed, C represents formation zone, and D represents the l Water Paper page after forming.
Fig. 4 is the structure diagram of Hydroformer bilayers that the present invention uses, and wherein A represents pulp distributor, and B represents whole Area is flowed, C represents formation zone, and D represents the l Water Paper page after forming.
Specific embodiment
The present invention is further elaborated with reference to specific embodiment.It should be appreciated that the embodiment that the present invention provides The present invention is merely to illustrate, the range being not intended to restrict the invention.
Test method without specific conditions in following embodiments, usually according to normal condition or according to institute of manufacturer It is recommended that condition.Unless otherwise defined, all professional and scientific terms used in text are familiar with one skilled in the art Meaning it is identical.In addition, any method similar or impartial to described content and material all can be applied in the method for the present invention. The preferred methods and materials described herein are for illustrative purposes only.
The Hydroformer multilayer titled net formation utensils that the present invention uses have the control of hydraulic pressure, cloth slurry and rectification member Part is designed using multiple flow passages；Wherein, embodiment 1-11,14-20,23-25 uses tri- layers of Hydroformer shown in Fig. 3, system The standby obtained apparent form of lithium ion battery separator is as shown in Figure 1；Preparation example 12,13,21,22 uses shown in Fig. 4 Hydroformer is double-deck, and the apparent form for the lithium ion battery separator being prepared is as shown in Figure 2.
Example 1 below -25 and comparative example 1-15 are only listed using few fibers material preparation lithium ion battery separator Example, can also be used the other fibrous materials listed in description of the invention and combinations thereof mode prepare the present invention lithium ion Battery diaphragm.
Embodiment 1
A kind of once-forming lithium ion battery separator is made of supporting layer, compacted zone and packing layer three-decker, matches Fang Zucheng is as shown in table 1, is prepared via a method which to obtain：
Step a：The raw material of supporting layer, compacted zone and packing layer is formulated according to table 1 Suo Shi, each independently in fluffer It mixes, discongest with water, being beaten to a concentration of 0.2wt% of solid weight percentage, then respectively by supporting layer, compacted zone and filler The raw material of layer is diluted using fan pump, wherein, it is a concentration of that supporting layer fibrous raw material is diluted to solid weight percentage 0.026wt% obtains slurry 1；Compacted zone fibrous raw material is diluted to a concentration of 0.040wt% of solid weight percentage, obtains Slurry 2；Packing layer raw material is diluted to a concentration of 0.140wt% of solid weight percentage, obtains slurry 3.
Step b：Piece position of floaing in former is adjusted, control is against the runner of forming net：Middle layer runner：Upper strata runner is horizontal Sectional area ratio is 7: 2: 1, and each layer slurry after dilution is respectively fed to tri- layers of hydraulic inclined net formers of Hydroformer, Middle slurry 1 enters the runner against forming net, and runner flow is 700m3/ h, slurry 2 enter middle layer runner, and runner flow is 200m3/ h, slurry 3 enter upper strata runner, and runner flow is 100m3/ h, after rectified, three layers of forming of manufacturing paper with pulp simultaneously, by dehydration Processing obtains l Water Paper page.
Step c：The l Water Paper page that step b is obtained is dry under the conditions of 120 DEG C in Yankee cylinder temperature, obtains the dry page of diaphragm.
Step d：The dry page paper that step c is obtained, through metallic roll and soft roller hot pressing light processing, obtains lithium at a temperature of 190 DEG C Ion battery diaphragm.
Embodiment 2
A kind of once-forming lithium ion battery separator is made of supporting layer, compacted zone and packing layer three-decker, matches Fang Zucheng is as shown in table 1, is prepared via a method which to obtain：
Step a：The raw material of supporting layer, compacted zone and packing layer is formulated according to table 1 Suo Shi, each independently in fluffer It mixes, discongest with water, being beaten to a concentration of 0.2wt% of solid weight percentage, then respectively by supporting layer, compacted zone and filler The raw material of layer is diluted using fan pump, wherein, it is a concentration of that supporting layer fibrous raw material is diluted to solid weight percentage 0.031wt% obtains slurry 1；Compacted zone fibrous raw material is diluted to a concentration of 0.020wt% of solid weight percentage, obtains Slurry 2；Packing layer raw material is diluted to a concentration of 0.140wt% of solid weight percentage, obtains slurry 3.
Step b, step c and step d are the same as embodiment 1.
Embodiment 3,4
A kind of once-forming lithium ion battery separator is made of supporting layer, packing layer, compacted zone three-decker, matches Fang Zucheng is as shown in table 1, and preparation method is the same as embodiment 2.
Embodiment 5
A kind of once-forming lithium ion battery separator is made of supporting layer, compacted zone and packing layer three-decker, matches Fang Zucheng is as shown in table 1, is prepared via a method which to obtain：
Step a：The raw material of supporting layer, compacted zone and packing layer is formulated according to table 1 Suo Shi, each independently in fluffer It mixes, discongest with water, being beaten to a concentration of 0.2wt% of solid weight percentage, then respectively by supporting layer, compacted zone and filler The raw material of layer is diluted using fan pump, wherein, it is a concentration of that supporting layer fibrous raw material is diluted to solid weight percentage 0.023wt% obtains slurry 1；Compacted zone fibrous raw material is diluted to a concentration of 0.020wt% of solid weight percentage, obtains Slurry 2；Packing layer raw material is diluted to a concentration of 0.100wt% of solid weight percentage, obtains slurry 3.
Step b, step c and step d are the same as embodiment 1.
Embodiment 6
A kind of once-forming lithium ion battery separator is made of supporting layer, compacted zone and packing layer three-decker, matches Fang Zucheng is as shown in table 1, is prepared via a method which to obtain：
Step a：The raw material of supporting layer, compacted zone and packing layer is formulated according to table 1 Suo Shi, each independently in fluffer It mixes, discongest with water, being beaten to a concentration of 0.2wt% of solid weight percentage, then respectively by supporting layer, compacted zone and filler The raw material of layer is diluted using fan pump, wherein, it is a concentration of that supporting layer fibrous raw material is diluted to solid weight percentage 0.049wt% obtains slurry 1；Compacted zone fibrous raw material is diluted to a concentration of 0.020wt% of solid weight percentage, obtains Slurry 2；Packing layer raw material is diluted to a concentration of 0.100wt% of solid weight percentage, obtains slurry 3.
Step b, step c and step d are the same as embodiment 1.
Embodiment 7
A kind of once-forming lithium ion battery separator is made of supporting layer, compacted zone and packing layer three-decker, matches Fang Zucheng is as shown in table 1, is prepared via a method which to obtain：
Step a：The raw material of supporting layer, compacted zone and packing layer is formulated according to table 1 Suo Shi, each independently in fluffer It mixes, discongest with water, being beaten to a concentration of 0.2wt% of solid weight percentage, then respectively by supporting layer, compacted zone and filler The raw material of layer is diluted using fan pump, wherein, it is a concentration of that supporting layer fibrous raw material is diluted to solid weight percentage 0.030wt% obtains slurry 1；Compacted zone fibrous raw material is diluted to a concentration of 0.048wt% of solid weight percentage, obtains Slurry 2；Packing layer raw material is diluted to a concentration of 0.100wt% of solid weight percentage, obtains slurry 3.
Step b：Piece position of floaing in former is adjusted, control is against the runner of forming net：Middle layer runner：Upper strata runner is horizontal Sectional area ratio is 4: 5: 1, and each layer slurry after dilution is respectively fed to tri- layers of hydraulic inclined net formers of Hydroformer, Middle slurry 1 enters the runner against forming net, and runner flow is 400m3/ h, slurry 2 enter middle layer runner, and runner flow is 500m3/ h, slurry 3 enter upper strata runner, and runner flow is 100m3/ h, after rectified, three layers of forming of manufacturing paper with pulp simultaneously, by dehydration Processing obtains l Water Paper page.
Step c and step d are the same as embodiment 1.
Embodiment 8
A kind of once-forming lithium ion battery separator is made of supporting layer, compacted zone and packing layer three-decker, matches Fang Zucheng is as shown in table 1, is prepared via a method which to obtain：
Step a：The raw material of supporting layer, compacted zone and packing layer is formulated according to table 1 Suo Shi, each independently in fluffer It mixes, discongest with water, being beaten to a concentration of 0.2wt% of solid weight percentage, then respectively by supporting layer, compacted zone and filler The raw material of layer is diluted using fan pump, wherein, it is a concentration of that supporting layer fibrous raw material is diluted to solid weight percentage 0.023wt% obtains slurry 1；Compacted zone fibrous raw material is diluted to a concentration of 0.020wt% of solid weight percentage, obtains Slurry 2；Packing layer raw material is diluted to a concentration of 0.380wt% of solid weight percentage, obtains slurry 3.
Step b, step c and step d are the same as embodiment 1.
Embodiment 9
A kind of once-forming lithium ion battery separator is made of supporting layer, compacted zone and packing layer three-decker, matches Fang Zucheng is as shown in table 1, is prepared via a method which to obtain：
Step a：The raw material of supporting layer, compacted zone and packing layer is formulated according to table 1 Suo Shi, each independently in fluffer It mixes, discongest with water, being beaten to a concentration of 0.2wt% of solid weight percentage, then respectively by supporting layer, compacted zone and filler The raw material of layer is diluted using fan pump, wherein, it is a concentration of that supporting layer fibrous raw material is diluted to solid weight percentage 0.040wt% obtains slurry 1；Compacted zone fibrous raw material is diluted to a concentration of 0.020wt% of solid weight percentage, obtains Slurry 2；Packing layer raw material is diluted to a concentration of 0.100wt% of solid weight percentage, obtains slurry 3.
Step b, step c and step d are the same as embodiment 1.
Embodiment 10,11
A kind of once-forming lithium ion battery separator is made of supporting layer, packing layer, compacted zone three-decker, matches Fang Zucheng is as shown in table 1, and preparation method is the same as embodiment 7.
Embodiment 12
A kind of once-forming lithium ion battery separator, is made, formula composition of supporting layer and packing layer double-layer structure As shown in table 1, it is prepared via a method which to obtain：
Step a：The raw material of supporting layer and packing layer according to table 1 Suo Shi is formulated, is mixed each independently in fluffer and water It closes, discongest, being beaten to a concentration of 0.2wt% of solid weight percentage, then respectively using the raw material of supporting layer and packing layer Fan pump is diluted, wherein, supporting layer fibrous raw material is diluted to a concentration of 0.032wt% of solid weight percentage, obtains Slurry 1；Packing layer raw material is diluted to a concentration of 0.064wt% of solid weight percentage, obtains slurry 2.
Step b：Piece position of floaing in former is adjusted, control is against the runner of forming net：Upper strata runner cross-sectional area ratio is 5 : 5, each layer slurry after dilution is respectively fed to Hydroformer bilayer hydraulic titled net formation devices, wherein slurry 1 enters tight By the runner of forming net, runner flow is 500m3/ h, slurry 2 enter upper strata runner, and runner flow is 500m3/ h, after rectified, Double-deck forming of manufacturing paper with pulp simultaneously, l Water Paper page is obtained by dehydration.
Step c and step d are the same as embodiment 1.
Embodiment 13
A kind of once-forming lithium ion battery separator, is made, formula composition of supporting layer and packing layer double-layer structure As shown in table 1, it is prepared via a method which to obtain：
Step a：The raw material of supporting layer and packing layer according to table 1 Suo Shi is formulated, is mixed each independently in fluffer and water It closes, discongest, being beaten to a concentration of 0.2wt% of solid weight percentage, then respectively using the raw material of supporting layer and packing layer Fan pump is diluted, wherein, supporting layer fibrous raw material is diluted to a concentration of 0.040wt% of solid weight percentage, obtains Slurry 1；Packing layer raw material is diluted to a concentration of 0.047wt% of solid weight percentage, obtains slurry 2.
Step b：Piece position of floaing in former is adjusted, control is against the runner of forming net：Upper strata runner cross-sectional area ratio is 7 : 3, each layer slurry after dilution is respectively fed to Hydroformer bilayer hydraulic titled net formation devices, wherein slurry 1 enters tight By the runner of forming net, runner flow is 700m3/ h, slurry 2 enter upper strata runner, and runner flow is 300m3/ h, after rectified, Double-deck layer is manufactured paper with pulp forming simultaneously, and l Water Paper page is obtained by dehydration.
Step c and step d are the same as embodiment 1.
Embodiment 14
A kind of once-forming lithium ion battery separator is made of supporting layer, compacted zone and packing layer three-decker, matches Fang Zucheng is as shown in table 1, is prepared via a method which to obtain：
Step a：The raw material of supporting layer, compacted zone and packing layer is formulated according to table 1 Suo Shi, each independently in fluffer It mixes, discongest with water, being beaten to a concentration of 0.2wt% of solid weight percentage, then respectively by supporting layer, compacted zone and filler The raw material of layer is diluted using fan pump, wherein, it is a concentration of that supporting layer fibrous raw material is diluted to solid weight percentage 0.031wt% obtains slurry 1；Compacted zone fibrous raw material is diluted to a concentration of 0.020wt% of solid weight percentage, obtains Slurry 2；Packing layer raw material is diluted to a concentration of 0.180wt% of solid weight percentage, obtains slurry 3.
Step b, step c and step d are the same as embodiment 1.
Embodiment 15,16
A kind of once-forming lithium ion battery separator is made of supporting layer, packing layer, compacted zone three-decker, matches Fang Zucheng is as shown in table 1, and preparation method is the same as embodiment 1.
Embodiment 17,18,19,20,23-25
A kind of once-forming lithium ion battery separator is made of supporting layer, compacted zone and packing layer three-decker, matches Fang Zucheng is as shown in table 1, is prepared via a method which to obtain：
Step a, b is the same as embodiment 2；
Step c：The l Water Paper page that step b is obtained is dry under the conditions of 90 DEG C in Yankee cylinder temperature, obtains the dry page of diaphragm.
Step d：The dry page paper that step c is obtained, through metallic roll and soft roller hot pressing light processing, obtains lithium at a temperature of 120 DEG C Ion battery diaphragm.
Embodiment 21,22
A kind of once-forming lithium ion battery separator, is made, formula composition of supporting layer and packing layer double-layer structure As shown in table 1, it is prepared via a method which to obtain：
Step a：The raw material of supporting layer and packing layer according to table 1 Suo Shi is formulated, is mixed each independently in fluffer and water It closes, discongest, being beaten to a concentration of 0.2wt% of solid weight percentage, then respectively using the raw material of supporting layer and packing layer Fan pump is diluted, wherein, supporting layer fibrous raw material is diluted to a concentration of 0.031wt% of solid weight percentage, obtains Slurry 1；Packing layer raw material is diluted to a concentration of 0.06wt% of solid weight percentage, obtains slurry 2.
Step b：Piece position of floaing in former is adjusted, control is against the runner of forming net：Upper strata runner cross-sectional area ratio is 7 : 3, each layer slurry after dilution is respectively fed to Hydroformer bilayer hydraulic titled net formation devices, wherein slurry 1 enters tight By the runner of forming net, runner flow is 700m3/ h, slurry 2 enter upper strata runner, and runner flow is 300m3/ h, after rectified, Double-deck forming of manufacturing paper with pulp simultaneously, l Water Paper page is obtained by dehydration.
Step c and step d are the same as embodiment 1.
Comparative example 1
A kind of lithium ion battery separator is made of supporting layer single layer structure, and formula composition is as shown in table 2, by as follows Method is prepared：
Step a：Supporting layer raw material according to table 2 Suo Shi is formulated, is mixed with water in fluffer, discongested to percent weight solids Specific concentration is 0.2wt%, is then diluted supporting layer raw material using fan pump, supporting layer fibrous raw material is diluted to solid Weight percent concentration is 0.018wt%, obtains slurry 1.
Step b：Slurry after dilution is sent into Hydroformer hydraulic inclined net formers, runner flow is 1000m3/ H, rectified and dehydration obtain l Water Paper page.
Step c：The l Water Paper page that step b is obtained is dry under the conditions of 120 DEG C in Yankee cylinder temperature, obtains the dry page of diaphragm.
Step d：The dry page paper that step c is obtained, through metallic roll and soft roller hot pressing light processing, obtains lithium at a temperature of 190 DEG C Ion battery diaphragm.
Comparative example 2
A kind of once-forming lithium ion battery separator, is made, formula composition of supporting layer and compacted zone double-layer structure As shown in table 2, it is prepared via a method which to obtain：
Step a：The raw material of supporting layer and compacted zone according to table 2 Suo Shi is formulated, is mixed each independently in fluffer and water It closes, discongest, being beaten to a concentration of 0.2wt% of solid weight percentage, then respectively using the raw material of supporting layer and compacted zone Fan pump is diluted, wherein, supporting layer fibrous raw material is diluted to a concentration of 0.026wt% of solid weight percentage, obtains Slurry 1；Compacted zone raw material is diluted to a concentration of 0.027wt% of solid weight percentage, obtains slurry 2.
Step b：Piece position of floaing in former is adjusted, control is against the runner of forming net：Upper strata runner cross-sectional area ratio is 7：3, each layer slurry after dilution is respectively fed to Hydroformer bilayer hydraulic titled net formation devices, wherein slurry 1 enters tight By the runner of forming net, runner flow is 700m3/ h, slurry 2 enter upper strata runner, and runner flow is 300m3/ h, after rectified, Double-deck forming of manufacturing paper with pulp simultaneously, l Water Paper page is obtained by dehydration.
Step c：The l Water Paper page that step b is obtained is dry under the conditions of 120 DEG C in Yankee cylinder temperature, obtains the dry page of diaphragm.
Step d：The dry page paper that step c is obtained, through metallic roll and soft roller hot pressing light processing, obtains lithium at a temperature of 190 DEG C Ion battery diaphragm.
Comparative example 3
A kind of once-forming lithium ion battery separator, is made, formula composition of supporting layer and packing layer double-layer structure As shown in table 2, it is prepared via a method which to obtain：
Step a：The raw material of supporting layer and packing layer according to table 2 Suo Shi is formulated, is mixed each independently in fluffer and water It closes, discongest, being beaten to a concentration of 0.2wt% of solid weight percentage, then respectively using the raw material of supporting layer and packing layer Fan pump is diluted, wherein, supporting layer fibrous raw material is diluted to a concentration of 0.026wt% of solid weight percentage, obtains Slurry l；Packing layer raw material is diluted to a concentration of 0.047wt% of solid weight percentage, obtains slurry 2.
Step b：Piece position of floaing in former is adjusted, control is against the runner of forming net：Upper strata runner cross-sectional area ratio is 7 : 3, each layer slurry after dilution is respectively fed to Hydroformer bilayer hydraulic titled net formation devices, wherein slurry 1 enters tight By the runner of forming net, runner flow is 700m3/ h, slurry 2 enter upper strata runner, and runner flow is 300m3/ h, after rectified, Double-deck forming of manufacturing paper with pulp simultaneously, l Water Paper page is obtained by dehydration.
Step c and step d are the same as comparative example 1.
Comparative example 4
A kind of once-forming lithium ion battery separator is made of supporting layer, compacted zone and packing layer three-decker, matches Fang Zucheng is as shown in table 2, is prepared via a method which to obtain：
Step a：The raw material of supporting layer, compacted zone and packing layer is formulated according to table 2 Suo Shi, each independently in fluffer It mixes, discongest with water, being beaten to a concentration of 0.2wt% of solid weight percentage, then respectively by supporting layer, compacted zone and filler The raw material of layer is diluted using fan pump, wherein, it is a concentration of that supporting layer fibrous raw material is diluted to solid weight percentage 0.026wt% obtains slurry 1；Compacted zone fibrous raw material is diluted to a concentration of 0.030wt% of solid weight percentage, obtains Slurry 2；Packing layer raw material is diluted to a concentration of 0.100wt% of solid weight percentage, obtains slurry 3.
Step b：Piece position of floaing in former is adjusted, control is against the runner of forming net：Middle layer runner：Upper strata runner is horizontal Sectional area ratio is 7: 2: 1, and each layer slurry after dilution is respectively fed to tri- layers of hydraulic inclined net formers of Hydroformer, Middle slurry 1 enters the runner against forming net, and runner flow is 700m3/ h, slurry 2 enter middle layer runner, and runner flow is 200m3/ h, slurry 3 enter upper strata runner, and runner flow is 100m3/ h, after rectified, three layers of forming of manufacturing paper with pulp simultaneously, by dehydration Processing obtains l Water Paper page.
Step c and step d are the same as comparative example 1.
Comparative example 5
A kind of once-forming lithium ion battery separator is made of supporting layer, compacted zone and packing layer three-decker, matches Fang Zucheng is as shown in table 2, is prepared via a method which to obtain：
Step a：The raw material of supporting layer, compacted zone and packing layer is formulated according to table 2 Suo Shi, each independently in fluffer It mixes, discongest with water, being beaten to a concentration of 0.2wt% of solid weight percentage, then respectively by supporting layer, compacted zone and filler The raw material of layer is diluted using fan pump, wherein, it is a concentration of that supporting layer fibrous raw material is diluted to solid weight percentage 0.029wt% obtains slurry 1；Compacted zone fibrous raw material is diluted to a concentration of 0.020wt% of solid weight percentage, obtains Slurry 2；Packing layer raw material is diluted to a concentration of 0.100wt% of solid weight percentage, obtains slurry 3.
Step b, step c and step d are the same as comparative example 4.
Comparative example 6
A kind of once-forming lithium ion battery separator is made of supporting layer, compacted zone and packing layer three-decker, matches Fang Zucheng is as shown in table 2, is prepared via a method which to obtain：
Step a：The raw material of supporting layer, compacted zone and packing layer is formulated according to table 2 Suo Shi, each independently in fluffer It mixes, discongest with water, being beaten to a concentration of 0.2wt% of solid weight percentage, then respectively by supporting layer, compacted zone and filler The raw material of layer is diluted using fan pump, wherein, it is a concentration of that supporting layer fibrous raw material is diluted to solid weight percentage 0.031wt% obtains slurry 1；Compacted zone fibrous raw material is diluted to a concentration of 0.010wt% of solid weight percentage, obtains Slurry 2；Packing layer raw material is diluted to a concentration of 0.100wt% of solid weight percentage, obtains slurry 3.
Step b, step c and step d are the same as comparative example 4.
Comparative example 7
A kind of once-forming lithium ion battery separator, is made, formula composition of supporting layer and packing layer double-layer structure As shown in table 2, it is prepared via a method which to obtain：
Step a：The raw material of supporting layer and packing layer according to table 2 Suo Shi is formulated, is mixed each independently in fluffer and water It closes, discongest, being beaten to a concentration of 0.2wt% of solid weight percentage, then respectively using the raw material of supporting layer and packing layer Fan pump is diluted, wherein, supporting layer fibrous raw material is diluted to a concentration of 0.029wt% of solid weight percentage, obtains Slurry 1；Packing layer raw material is diluted to a concentration of 0.047wt% of solid weight percentage, obtains slurry 2.
Step b, step c and step d are the same as comparative example 3.
Comparative example 8
A kind of once-forming lithium ion battery separator, is made, formula composition of supporting layer and packing layer double-layer structure As shown in table 2, it is prepared via a method which to obtain：
Step a：The raw material of supporting layer and packing layer according to table 2 Suo Shi is formulated, is mixed each independently in fluffer and water It closes, discongest, being beaten to a concentration of 0.2wt% of solid weight percentage, then respectively using the raw material of supporting layer and packing layer Fan pump is diluted, wherein, supporting layer fibrous raw material is diluted to a concentration of 0.045wt% of solid weight percentage, obtains Slurry 1；Packing layer raw material is diluted to a concentration of 0.070wt% of solid weight percentage, obtains slurry 2.
Step b：Piece position of floaing in former is adjusted, control is against the runner of forming net：Upper strata runner cross-sectional area ratio is 4 : 1, each layer slurry after dilution is respectively fed to Hydroformer bilayer hydraulic titled net formation devices, wherein slurry 1 enters tight By the runner of forming net, runner flow is 800m3/ h, slurry 2 enter upper strata runner, and runner flow is 200m3/ h, after rectified, Double-deck forming of manufacturing paper with pulp simultaneously, l Water Paper page is obtained by dehydration.
Step c and step d are the same as comparative example 1.
Comparative example 9
A kind of once-forming lithium ion battery separator is made of supporting layer, compacted zone and packing layer three-decker, matches Fang Zucheng is as shown in table 2, is prepared via a method which to obtain：
Step a：The raw material of supporting layer, compacted zone and packing layer is formulated according to table 2 Suo Shi, each independently in fluffer It mixes, discongest with water, being beaten to a concentration of 0.2wt% of solid weight percentage, then respectively by supporting layer, compacted zone and filler The raw material of layer is diluted using fan pump, wherein, it is a concentration of that supporting layer fibrous raw material is diluted to solid weight percentage 0.040wt% obtains slurry 1；Compacted zone fibrous raw material is diluted to a concentration of 0.043wt% of solid weight percentage, obtains Slurry 2；Packing layer raw material is diluted to a concentration of 0.100wt% of solid weight percentage, obtains slurry 3.
Step b：Piece position of floaing in former is adjusted, control is against the runner of forming net：Middle layer runner：Upper strata runner is horizontal Sectional area ratio is 3: 6: 1, and each layer slurry after dilution is respectively fed to tri- layers of hydraulic inclined net formers of Hydroformer, Middle slurry 1 enters the runner against forming net, and runner flow is 300m3/ h, slurry 2 enter middle layer runner, and runner flow is 600m3/ h, slurry 3 enter upper strata runner, and runner flow is 100m3/ h, after rectified, three layers of forming of manufacturing paper with pulp simultaneously, by dehydration Processing obtains l Water Paper page.
Step c and step d are the same as comparative example 1.
Comparative example 10
A kind of once-forming lithium ion battery separator is made of supporting layer, compacted zone and packing layer three-decker, matches Fang Zucheng is as shown in table 2, is prepared via a method which to obtain：
Step a：The raw material of supporting layer, compacted zone and packing layer is formulated according to table 2 Suo Shi, each independently in fluffer It mixes, discongest with water, being beaten to a concentration of 0.2wt% of solid weight percentage, then respectively by supporting layer, compacted zone and filler The raw material of layer is diluted using fan pump, wherein, it is a concentration of that supporting layer fibrous raw material is diluted to solid weight percentage 0.031wt% obtains slurry 1；Compacted zone fibrous raw material is diluted to a concentration of 0.050wt% of solid weight percentage, obtains Slurry 2；Packing layer raw material is diluted to a concentration of 0.080wt% of solid weight percentage, obtains slurry 3.
Step b, step c and step d are the same as comparative example 4.
Comparative example 11
A kind of once-forming lithium ion battery separator, is made, formula composition of supporting layer and packing layer double-layer structure As shown in table 2, it is prepared via a method which to obtain：
Step a：The raw material of supporting layer and packing layer according to table 2 Suo Shi is formulated, is mixed each independently in fluffer and water It closes, discongest, being beaten to a concentration of 0.2wt% of solid weight percentage, then respectively using the raw material of supporting layer and packing layer Fan pump is diluted, wherein, supporting layer fibrous raw material is diluted to a concentration of 0.023wt% of solid weight percentage, obtains Slurry 1；Packing layer raw material is diluted to a concentration of 0.147wt% of solid weight percentage, obtains slurry 2.
Step b, step c and step d are the same as comparative example 3.
Comparative example 12,13
A kind of once-forming lithium ion battery separator is made of supporting layer, compacted zone and packing layer three-decker, matches Fang Zucheng is as shown in table 2, is prepared via a method which to obtain：
Step a：The raw material of supporting layer, compacted zone and packing layer is formulated according to table 2 Suo Shi, each independently in fluffer It mixes, discongest with water, being beaten to a concentration of 0.2wt% of solid weight percentage, then respectively by supporting layer, compacted zone and filler The raw material of layer is diluted using fan pump, wherein, it is a concentration of that supporting layer fibrous raw material is diluted to solid weight percentage 0.046wt% obtains slurry 1；Compacted zone fibrous raw material is diluted to a concentration of 0.020wt% of solid weight percentage, obtains Slurry 2；Packing layer raw material is diluted to a concentration of 0.100wt% of solid weight percentage, obtains slurry 3.
Step b, step c and step d are the same as comparative example 4.
Comparative example 14,15
A kind of once-forming lithium ion battery separator is made of supporting layer, compacted zone and packing layer three-decker, matches Fang Zucheng is as shown in table 2, is prepared via a method which to obtain：
Step a：The raw material of supporting layer, compacted zone and packing layer is formulated according to table 2 Suo Shi, each independently in fluffer It mixes, discongest with water, being beaten to a concentration of 0.2wt% of solid weight percentage, then respectively by supporting layer, compacted zone and filler The raw material of layer is diluted using fan pump, wherein, it is a concentration of that supporting layer fibrous raw material is diluted to solid weight percentage 0.043wt% obtains slurry 1；Compacted zone fibrous raw material is diluted to a concentration of 0.020wt% of solid weight percentage, obtains Slurry 2；Packing layer raw material is diluted to a concentration of 0.100wt% of solid weight percentage, obtains slurry 3.
Step b, step c and step d are the same as comparative example 4.
Composition of raw materials (the g/m of 1 embodiment 1-25 of table2)
Note：A) a diameter of 2 μm of PET fiber, length 3mm are stretched；
B) a diameter of 2 μm of PAN fiber, length 3mm；
C) a diameter of 2 μm of PA fibers, length 3mm；
D) a diameter of 4um of non-stretched PET fiber, length 3mm；
E) a diameter of 4um of two-component PET/co-PET fibers, length 3mm；
F) a diameter of 4um of two-component PP/PE fibers, length 3mm；
G) fibrillation tencel nanofiber beating degree be 95 ° of SR, Austrian Lenzing companies；
H) fibrillation PPTA nanofibers beating degree is 85 ° of SR, Dupont Kevlar；
I) fibrillation PBO nanofibers beating degree be 85 ° of SR, Toyobo, Japan；
J) fibrillation PAN nanofibers beating degree is 85 ° of SR；
K) aluminum oxide nanoparticle average diameter 200nm；
1) nano SiO 2 particle average diameter 200nm；
M) water nurse stone nano particle average diameter 200nm；
N) magnesium hydroxide nanoparticles average diameter 200nm.
Composition of raw materials (the g/m of 2 comparative example 1-15 of table2)
Note：A) a diameter of 2 μm of PET fiber, length 3mm are stretched；
B) a diameter of 4um of non-stretched PET fiber, length 3mm；
C) fibrillation tencel nanofiber beating degree be 95 ° of SR, Austrian Lenzing companies；
D) fibrillation PPTA nanofibers beating degree is 85 ° of SR, Dupont Kevlar；
E) aluminum oxide nanoparticle average diameter 200nm.
Lithium ion battery separator performance test
The embodiment 1-25 and comparative example 1-15 lithium ion battery separators prepared are tested for the property, test event and side Method is as follows：
1st, quantitative, thickness and tensile strength
Using TAPPI standard tests.
2nd, average pore size and maximum diameter of hole
It is measured using PMI Porosimetries.
3rd, percent thermal shrinkage
The dimensional stability of diaphragm at a certain temperature can characterize the thermal stability of diaphragm, usually with percent thermal shrinkage come table Show.The percent thermal shrinkage of diaphragm is tested as follows：
Diaphragm is cut into the length of side as L firstbSquare, diaphragm is then placed on 110 DEG C, in 300 DEG C of environment respectively 1h tests the length of side L of diaphragma, shrinkage from mold dimensions as follows.
Shrinking percentage (%)=(Lb-La)/Lb×100
4th, diaphragm intensity retains
Diaphragm is placed in 300 DEG C of environment after 1h and is taken out, the reservation of diaphragm intensity is evaluated according to following standard.
○：It folds diaphragm 10 times, is not broken；
△：It folds diaphragm 2-10 times, is broken；
×：It folds diaphragm 1 time, is broken.
The lithium ion battery separator performance test parameter of 3 present invention of table
Note：Percent thermal shrinkage of the lithium ion battery separator of the present invention at 110 DEG C is 0.
4 lithium ion battery separator performance test parameter of table
As seen from Table 3, lithium ion battery separator thickness obtained by 1-25 of the embodiment of the present invention at 30 μm hereinafter, diaphragm is by multilayer Structure is made, and includes supporting layer, packing layer and/or compacted zone.Diaphragm maximum diameter of hole is less than 1 μm, and intensity is more than 600N/m, filler Particle is without obscission, and the percent thermal shrinkage at 110 DEG C is 0, and 1h is handled at 300 DEG C still has good intensity, is heat-shrinked Rate ＜ 3% has excellent thermal stability.
As seen from Table 4, comparative example 1 is only prepared by PET fiber, and diaphragm hole is larger, and 300 DEG C of lower diaphragm plates melt Change；Inorganic nano-filler is not used in comparative example 2, causes membrane pore size bigger than normal, and 300 DEG C of processing 1h percent thermal shrinkages are more than 3%；Comparison Nanofiber is not used in example 3, and PET fiber forming hole is larger, and effective retention can not be formed to inorganic nano-filler particle, makes There are pin holes for standby obtained diaphragm, and aperture is bigger than normal, and 300 DEG C of lower diaphragm plates melt；Nanofiber in comparative example 4,5,6 and 7 The sum of dosage is less than 4g/m2, inorganic nano-filler particle keeps reduction in forming section, it is impossible to fibrous layer be formed and effectively covered Lid, causes membrane pore size bigger than normal, is quantitatively lost in larger.8,9,11,14,15 interval film thickness of comparative example is more than 30 μm, is unfavorable for The control of battery volume energy density.Packing layer inorganic particle dosage is less than 5g/m in comparative example 102, it is impossible to fibrous layer is formed Effective covering, causes membrane pore size bigger than normal.PET fiber dosage is very few in comparative example 12 and comparative example 13, causes diaphragm intensity It can not meet the requirements.
It should be understood that invention described herein is not limited to specific methodology, experimental program or reagent, because these are It can change.Discussion provided in this article and example present merely to describing specific embodiment and are not intended to limitation originally The range of invention, the scope of the present invention are only limited by claim.

Claims (10)

1. a kind of once-forming lithium ion battery separator, formed it includes or by supporting layer and packing layer, wherein, the support Layer is included or is made of at least two in ultra-fine trunk fiber, thermoplastic binder fiber and the first nanofiber, the filler Layer is included or is made of at least one of inorganic filler and third nanofiber；
Preferably, the thickness of the diaphragm is 19-31 μm, preferably 19-26 μm；Preferably, the quantification of 15- of the diaphragm 30g/m2, preferably 15-25g/m2, more preferably 19-22g/m2；Preferably, the average pore size of the diaphragm is less than 1 μm, preferably It is 0.2-0.5 μm；Preferably, the maximum diameter of hole of the diaphragm is not more than 1 μm, preferably 0.7-1 μm；Preferably, the diaphragm Percent thermal shrinkage≤2.8% at 300 DEG C.
2. lithium ion battery separator according to claim 1, which is characterized in that the quantification of 6-17g/m of supporting layer2, it is excellent It is selected as 8-14g/m2, more preferably 8-11g/m2, most preferably 11g/m2；The quantification of 5-19g/m of described filler layer2, preferably 5- 16g/m2, more preferably 5-9g/m2, it is further preferably 5-7g/m2, most preferably 7g/m2。
3. lithium ion battery separator according to claim 1 or 2, which is characterized in that described ultra-fine in the supporting layer The quantification of 3-9g/m of trunk fiber2, preferably 3-6g/m2, more preferably 5g/m2；The thermoplastic binder fiber it is quantification of 3-9g/m2, preferably 3-6g/m2, more preferably 4g/m2；The quantification of 0-11g/m of first nanofiber2, preferably 2- 11g/m2, more preferably 2-8g/m2, it is further preferably 2-6g/m2, most preferably 2g/m2；
Preferably, the supporting layer includes or by quantification of 3-9g/m2Ultra-fine trunk fiber, quantification of 3-9g/m2Thermoplasticity Viscose fibre and quantification of 0-11g/m2The first nanofiber be made；
Preferably, the supporting layer includes or by quantification of 3-6g/m2Ultra-fine trunk fiber, quantification of 3-6g/m2Thermoplasticity Viscose fibre and quantification of 2-11g/m2The first nanofiber be made；
Preferably, the supporting layer includes or by quantification of 5g/m2Ultra-fine trunk fiber, quantification of 4g/m2Thermoplastic binder Fiber and quantification of 2g/m2The first nanofiber be made；
Preferably, in described filler layer, the quantification of 5-19g/m of the inorganic particle2, preferably 5-16g/m2, more preferably 5-10g/m2, it is further preferably 5-7g/m2, most preferably 7g/m2；The quantification of 0-11g/m of the third nanofiber2, preferably 2-11g/m2, more preferably 2-8g/m2, in preferably 2-4g/m2, most preferably 0 or 2g/m2；
Preferably, described filler layer includes or by quantification of 5-19g/m2Inorganic particle and quantification of 0-11g/m2Third receive Rice fiber is made；
Preferably, described filler layer includes or by quantification of 5-7g/m2Inorganic particle and quantification of 0-11g/m2Third nanometer Fiber is made；
Preferably, described filler layer includes or by quantification of 5-7g/m2Inorganic particle and quantification of 2-11g/m2Third nanometer Fiber is made；
Preferably, described filler layer is by quantification of 5-7g/m2Inorganic particle be made；
Preferably, described filler layer is by quantification of 7g/m2Inorganic particle be made；
Preferably, described filler layer is by quantification of 7g/m2Inorganic particle and quantification of 2g/m2Third nanofiber be made；
Preferably, the sum of quantitative of first nanofiber and third nanofiber is not less than 4g/m2；
Preferably, the quantification of 6-17g/m of the supporting layer2, the quantification of 5-19g/m of described filler layer2；
Preferably, the quantification of 8-14g/m of the supporting layer2, the quantification of 5-16g/m of described filler layer2；
Preferably, the quantification of 8-14g/m of the supporting layer2, the quantification of 5-9g/m of described filler layer2；
Preferably, the quantification of 8-11g/m of the supporting layer2, the quantification of 5-7g/m of described filler layer2；
Preferably, the quantification of 8-11g/m of the supporting layer2, the quantification of 5-7g/m of described filler layer2；
Preferably, the quantification of 11g/m of the supporting layer2, the quantification of 7g/m of described filler layer2。
4. lithium ion battery separator according to any one of claim 1 to 3, which is characterized in that the ultra-fine trunk is fine Dimension selected from stretch dacron fibre (stretch PET), polyacrylonitrile fibre (PAN), Fypro (PA) and It is one or more in polypropylene fibre (PP), preferably stretch dacron fibre (stretching PET)；
Preferably, a diameter of 0.1-6 μm of the ultra-fine trunk fiber, preferably 0.5-4 μm, more preferably 0.5-3 μm are optimal It is selected as 1-3 μm；Preferably, the fibre length of the ultra-fine trunk fiber is 1-6mm, most preferably preferably 2-4mm, 3mm；
Preferably, the thermoplastic binder fiber is selected from polyethylene fibre (PE), polypropylene fibre (PP), non-stretched poly- to benzene two Two ester fiber of formic acid second (non-stretched PET), two-component PP/PE fibers, two-component PET/PE fibers, two-component PET/PP fibers and One or more in two-component PET/co-PET fibers, preferably non-stretched dacron fibre is (non-stretched PET)；
Preferably, a diameter of 0.1-8 μm of the thermoplastic binder fiber, preferably 0.5-6 μm, more preferably 1-5 μm are optimal It is selected as 3-5 μm；Preferably, the fibre length that the thermoplasticity coheres fiber is 1-6mm, preferably 2-4mm.
5. lithium ion battery separator according to any one of claim 1 to 4, which is characterized in that first Nanowire Dimension is gathered pair selected from fibrillation poly(p-phenylene terephthalamide) (PPTA) nanofiber, fibrillation tencel nanofiber, fibrillation Penylene Benzo-dioxazole (PBO) nanofiber, primary fibrosis polypropylene nitrile (PAN) nanofiber, polyimides (PI) nanofiber With one or more in nano-cellulose fiber, preferably fibrillation poly(p-phenylene terephthalamide) (PPTA) nanofiber Or fibrillation tencel nanofiber；
Preferably, the beating degree of first nanofiber is 70-95 ° of SR, preferably 95 ° of SR；
Preferably, the third nanofiber is each independently selected from fibrillation poly(p-phenylene terephthalamide) (PPTA) nanometer Fiber, fibrillation tencel nanofiber, fibrillation polyparaphenylene Benzo-dioxazole (PBO) nanofiber and primary fibrosis polypropylene nitrile (PAN) it is one or more in nanofiber；
Preferably, the third nanofiber is fibrillation poly(p-phenylene terephthalamide) (PPTA) nanofiber, fibrillation Polyparaphenylene's Benzo-dioxazole (PBO) nanofiber or primary fibrosis polypropylene nitrile (PAN) nanofiber；
Preferably, the beating degree of the third nanofiber is 60-85 ° of SR, preferably 85 ° of SR.
6. lithium ion battery separator according to any one of claim 1 to 5, which is characterized in that the inorganic filler is Inorganic particle, the inorganic particle is one or more in aluminium oxide, silica, Shui Mushi, magnesium hydroxide, preferably Aluminium oxide；
Preferably, the grain size of the inorganic particle be 3 μm hereinafter, preferably 1 μm hereinafter, most preferably 200nm.
7. lithium ion battery separator according to any one of claim 1 to 6, which is characterized in that the lithium ion battery Diaphragm is also comprising compacted zone, and the compacted zone is made of the second nanofiber, between the supporting layer and described filler layer；
Preferably, when the amount of third nanofiber is 0 in described filler layer, the lithium ion battery separator is also comprising densification Layer, the compacted zone is made of the second nanofiber, between the supporting layer and described filler layer；
Preferably, the quantification of 0-12g/m of the compacted zone2, preferably 2-12g/m2, more preferably 2-8g/m2, it is further preferably 2- 4g/m2, most preferably 2g/m2；
Preferably, in the compacted zone, the quantification of 2-12g/m of second nanofiber2, preferably 2-10g/m2, it is more excellent It is selected as 2-8g/m2, it is further preferably 2-4g/m2, most preferably 2g/m2；
Preferably, the sum of quantitative of first nanofiber, the second nanofiber and third nanofiber is not less than 4g/m2；
Preferably, the sum of quantitative of second nanofiber and third nanofiber is not less than 2g/m2；
Preferably, second nanofiber is each independently selected from fibrillation poly(p-phenylene terephthalamide) (PPTA) nanometer Fiber, fibrillation tencel nanofiber, fibrillation polyparaphenylene Benzo-dioxazole (PBO) nanofiber and primary fibrosis polypropylene nitrile (PAN) it is one or more in nanofiber；
Preferably, second nanofiber is fibrillation poly(p-phenylene terephthalamide) (PPTA) nanofiber, fibrillation Tencel nanofiber, fibrillation polyparaphenylene Benzo-dioxazole (PBO) nanofiber or primary fibrosis polypropylene nitrile (PAN) Nanowire Dimension；
Preferably, the beating degree of second nanofiber is 60-85 ° of SR, preferably 85 ° of SR.
8. a kind of method for preparing the lithium ion battery separator described in any one of claim 1 to 7, the method includes following Step：
Step a：The raw material of supporting layer, compacted zone and packing layer or supporting layer and packing layer with water is mixed, is dredged each independently After solution, mashing, mixing, online concentration is diluted with water to using fan pump；
Step b：Supporting layer, compacted zone and packing layer after dilution or supporting layer and packing layer slurry are sent into Hydroformer Multilayer pulp distributor, wherein, packing layer slurry enters upper strata runner with certain runner flow, and compacted zone slurry is with certain runner flow Into intermediate flow channel, supporting layer slurry enters the runner against forming net with certain runner flow, and each runner slurry is successively same One region lamination is manufactured paper with pulp forming simultaneously, and l Water Paper page is obtained through dehydration；Preferably, before manufacturing paper with pulp, the rectification of slurry is further included, Make slurry that the flow regime of high-strength micro-turbulence be presented；
Step c：After the step b, diaphragm l Water Paper page is dried to obtain the dry page of diaphragm by Yankee cylinder；
Step d：After the step c, the dry page of diaphragm at a certain temperature by metallic roll and soft calender handle to obtain lithium from Sub- battery diaphragm.
9. according to the method described in claim 8, it is characterized in that, before being diluted with water slurry in step a, each layer slurry is consolidated Body weight percentage concentration is 0.2wt%；
Preferably, in step a, the online a concentration of 0.010-0.050wt%, preferably 0.023- of the supporting layer slurry 0.049wt%；The online a concentration of 0.010-0.050wt%, preferably 0.02-0.048wt% of the compacted zone slurry；It is described The online a concentration of 0.05-0.50wt%, preferably 0.064-0.38wt% of packing layer slurry；Alternatively, the supporting layer slurry Online a concentration of 0.010-0.050wt%, preferably 0.023-0.049wt%；The online of described filler layer slurry is a concentration of 0.03-0.08wt%, preferably 0.047-0.064wt%；
Preferably, in stepb, the runner flow of the supporting layer slurry is 100-1000m3/ h, preferably 400-700m3/ h, The runner flow of the compacted zone slurry is 100-1000m3/ h, preferably 200-500m3/ h, the runner of described filler layer slurry Flow is 40-1000m3/ h, preferably 100-500m3/h；Alternatively, the runner flow of the supporting layer slurry is 100-1000m3/ H, preferably 500-700m3/ h, the runner flow of described filler layer slurry is 40-1000m3/ h, preferably 300-500m3/h；
Preferably, in stepb, it is described against the runner of forming net, middle layer runner and upper strata runner cross-sectional area ratio be 4-7 : 2-5: 1, preferably 7: 2: 1 or 4: 5: 1；Alternatively, the runner against forming net is 1-7 with upper strata runner cross-sectional area ratio: 1-3, preferably 7: 3；
Preferably, in step c, the drying temperature is 80-130 DEG C；
Preferably, in step d, the press polish treatment temperature is 110-220 DEG C；
Preferably, when the thermoplastic binder fiber in the supporting layer is non-stretched PET fiber, drying temperature 80-130 DEG C, preferably 120 DEG C, press polish treatment temperature is 170-220 DEG C, preferably 190 DEG C；
Preferably, when the thermoplastic binder fiber in the supporting layer is two-component PET/co-PET fibers or two-component PP/PE Fiber, drying temperature are 80-130 DEG C, and preferably 90 DEG C, press polish treatment temperature is 110-140 DEG C, preferably 120 DEG C.
10. a kind of lithium ion battery, it includes the lithium ion battery separators described in any one of claim 1 to 7.
CN201711442896.9A 2017-12-26 2017-12-26 One-step formed lithium ion battery diaphragm and preparation method and application thereof Active CN108232086B (en)

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